CN118268003A

CN118268003A - Preparation method of hydrofining catalyst

Info

Publication number: CN118268003A
Application number: CN202211726238.3A
Authority: CN
Inventors: 姚文君; 向永生; 刘昕; 李景锋; 张小奇; 张永泽; 王高峰; 谢元; 高海波; 王书峰
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2022-12-29
Filing date: 2022-12-29
Publication date: 2024-07-02

Abstract

The invention provides a preparation method of a hydrofining catalyst, which comprises the following steps: forming a carrier, wherein cobalt-manganese solid solution and/or nickel-manganese solid solution are/is added in the forming process of the carrier; and carrying the active metal precursor on the carrier, and then drying the carrier at the temperature of not higher than 200 ℃ to obtain the hydrofining catalyst. The catalyst prepared by the method has the advantages of good dispersibility of the metal active components, high effective utilization rate of metal and high activity of the hydrogenation catalyst.

Description

Preparation method of hydrofining catalyst

Technical Field

The invention relates to the field of catalysts, in particular to a preparation method of a hydrofining catalyst.

Background

Hydrotreatment is one of the important technological processes for processing inferior crude oil, and along with the aggravation of crude oil heaviness and inferior trend in the world and the continuous increase of the demand of clean oil in the market, the hydrotreatment process is more and more focused by researchers at home and abroad. It is counted that more than one third of the petroleum products are hydrotreated, and even more than 80% of the petroleum products in some developed countries are hydrotreated. The hydrogenation catalyst is used as the core of the hydrotreating technology, and directly determines the depth and effect of the hydrogenation reaction.

At present, the most effective method for improving the performance of the hydrogenation catalyst is mainly development of new catalytic materials and new methods for preparing the catalyst. The hydrogenation catalyst is usually prepared by taking inorganic oxide as a carrier and loading hydrogenation active metals (generally elements of VIB group and VIII group, such as Mo, W, co, ni and the like). The preparation method adopted at home and abroad generally comprises the steps of co-impregnating a salt solution containing metal components with a carrier, then aging, drying and roasting to convert metal salts into corresponding metal oxides, and then converting the metal oxides into corresponding metal sulfides or metal simple substances through pretreatment processes such as vulcanization, reduction and the like, thereby better exerting hydrogenation activity.

The change of the preparation method of the hydrogenation catalyst can cause the change of microscopic properties such as the grain size of the catalyst active substance, the dispersion uniformity of the active components on the surface of the catalyst and the like, and even under the condition that the chemical compositions of the catalysts are the same, the catalyst performance can have larger difference due to the different preparation methods. In the preparation process of the catalyst, the roasting of the catalyst is a key link, and has a crucial effect and influence on the performance of the catalyst. The main functions of the compound include: ① The interaction between the carrier and the active component is influenced, so that the electronic performance of the active component can be improved, and the acidity of the surface of the carrier can be improved; ② The metal salt or metal complex carried on the surface of the carrier is decomposed at high temperature, so that the active component can be fixed on the surface of the carrier in an oxidized state, and the catalyst activity is stabilized.

CN 111375419B discloses a hydrogenation catalyst and a preparation method thereof, the catalyst comprises a hydrogenation active metal component, an auxiliary agent and a carrier. Wherein the active metal component is one or more of the group VIB metal and/or the group VIII metal. The preparation method comprises the steps of dissolving precursor salt of active metal components in ammonia water with a certain concentration to form an ammonia water solution containing metal ions; then a catalyst precursor is obtained by adopting an impregnation method; finally, drying and roasting at high temperature to obtain the hydrogenation catalyst with high activity.

CN 109433218B provides a catalyst for selective hydrogenation of unsaturated hydrocarbon and its preparation method, the catalyst includes silica-alumina carrier and metal active components nickel, molybdenum and magnesium loaded on the carrier, the catalyst comprises the following components based on total weight of the catalyst: the content of nickel oxide is 7-18 wt%, the content of molybdenum oxide is 3.5-12 wt%, the content of magnesium oxide is 0.05-2.0 wt%, and the content of silica-alumina carrier is 75-91 wt%. The catalyst is prepared by adopting an impregnation method, is baked for 3-9 h at 110-160 ℃, and is baked for 4-9 h at 400-650 ℃, and the catalyst has good colloid resistance and strong arsenic, sulfur and water resistance.

Although the conventional high-temperature roasting treatment is beneficial to improving the activity of the catalyst in the preparation process of the hydrogenation catalyst, the conventional high-temperature roasting treatment also brings problems, such as the action force between the active metal and the carrier is enhanced after the catalyst is roasted, particularly the high-temperature treatment is carried out, a new phase is generated, for example, a hydrogenation catalyst taking aluminum oxide as the carrier is extremely easy to generate a meta-aluminate phase if the catalyst is subjected to high-temperature treatment; in addition, the active metal is easy to migrate at high temperature so as to agglomerate, thereby reducing the effective catalytic surface area of the metal component on the catalyst, further reducing the effective utilization rate of the active metal component and inhibiting the hydrogenation activity and stability of the catalyst.

Therefore, researchers at home and abroad also propose methods for improving the activity of hydrogenation catalysts to solve the problems, for example, improving the dispersibility of active metals on the surface of a carrier by adding surface regulators such as organic complexing agents, chelating agents, dispersing agents and the like and auxiliaries; the introduction of a metal or non-metal component into the support improves the preparation process and thereby reduces the interaction between the active metal component and the support.

CN 114749193a discloses a hydrogenation catalyst for producing low sulfur boat combustion and a preparation method thereof, the catalyst comprises a silicon-aluminum material and a first metal and a second metal loaded on the silicon-aluminum material; wherein the first metal is at least one of IVB metal, VIB metal and VIII metal; the second metal is at least one selected from the group consisting of group VIB metals and group VIII metals. Preparing a first solution, preparing slurry, processing to obtain a carrier precursor, and further forming, drying and roasting to obtain a carrier; and then introducing a second metal onto the carrier to obtain the catalyst. The carrier and the catalyst provided by the invention both need high-temperature treatment, wherein the carrier is immersed in metal and then needs a water vapor high-temperature roasting mode, and the technological process is complex.

US 2004055936 proposes a preparation method of a hydrotreating catalyst, which is characterized in that a nitrogenous organic compound dispersing agent is added into an impregnation solution containing a metal active component, so that the formation of a vulcanization active phase of the metal component can be promoted, and the hydrodesulfurization and denitrification performances of the catalyst are improved to a certain extent. However, the method has the advantages that the effect of the dispersing agent is low, so that the adding amount of the dispersing agent is large, and the hydrodesulfurization and denitrification effects of the catalyst on heavy distillate oil are influenced.

CN 1552794a discloses an active metal impregnation solution and a catalyst preparation method. The method comprises the steps of firstly dissolving precursor salt of a metal component in water, then adding organic carboxylic acid substances to enable the metal component to form a stable complex, and enabling a metal impregnating solution to have the characteristic of high stability, so that the metal dispersibility and catalytic activity of the prepared catalyst are improved to a certain extent. However, the method uses organic carboxylic acid, which is easy to coke on the surface of the catalyst in the roasting process of the catalyst, thereby reducing the number of active metal centers.

CN 101157058a discloses a preparation method of roasting-free hydrotreating catalyst, the catalyst uses Al ₂O₃、SiO₂、TiO₂ and composite oxide between them as carrier, uses VIB group and VIII group metals as active metal components, adds proper quantity of organic chelating agent into metal impregnating liquor, and the chelating agent includes one or several of ethylenediamine, nitrilotriacetic acid, ethylenediamine tetraacetic acid and cyclohexanediamine tetraacetic acid, and adopts co-impregnation or distributed impregnation method to make active metal components be loaded on carrier, and makes the carrier carrying metal components undergo the processes of drying at 120 deg.C for 4-10h, and does not need roasting so as to obtain the invented high-activity hydrofining catalyst.

In summary, although the active components can be fixed on the surface of the carrier in the roasting process of the catalyst, and the surface acidity of the carrier is changed, the acting force between the active metal and the carrier is increased, and the agglomeration probability of the active metal is improved at the same time; meanwhile, the roasting treatment can increase energy consumption, so that environmental pollution to a certain extent is caused, such as emission of pollutants such as NO _X、SO_X; in addition, the introduction of organic surface modifiers, auxiliaries and the like complicates the catalyst preparation process, and increases the production cost, causes pollution and other problems. Therefore, intensive researches on oil hydrotreating catalysts are required, and development of new preparation methods is eagerly demanded, and high hydrogenation activity of the catalysts is realized by matching and adjusting catalyst compositions.

Disclosure of Invention

The invention mainly aims to provide a preparation method of a hydrofining catalyst, which aims to solve the problems of complex preparation process, high preparation cost, high energy consumption and the like of the catalyst in the prior art.

In order to achieve the above object, the present invention provides a method for preparing a hydrofining catalyst, comprising:

Forming a carrier, wherein cobalt-manganese solid solution and/or nickel-manganese solid solution are/is added in the forming process of the carrier;

And carrying the active metal precursor on the carrier, and then drying the carrier at the temperature of not higher than 200 ℃ to obtain the hydrofining catalyst.

The preparation method of the hydrofining catalyst provided by the invention comprises the steps of (Co _xMn_yO₄)_n, wherein n is an integer of 1-10, x is more than 0 and less than 5, y is more than 0 and less than 5, and Ni _aMn_bO_z, wherein a is more than or equal to 1 and less than or equal to 10, b is more than or equal to 1 and less than or equal to 5, and z is more than or equal to 1 and less than or equal to 10.

The preparation method of the hydrofining catalyst comprises the step of adding a cobalt-manganese solid solution and a nickel-manganese solid solution in the forming process of the carrier, wherein the weight ratio of the cobalt-manganese solid solution to the nickel-manganese solid solution is 0.1-10:1.

The preparation method of the hydrofining catalyst comprises the steps that the cobalt-manganese solid solution comprises at least one of CoMn ₂O₄、Co₂MnO₄、CoMnO₃ and Co ₂Mn₃O₈ crystal phases; the nickel-manganese solid solution includes at least one of NiMnO ₃、NiMn₂O₄ and Ni ₆MnO₈ crystalline phases.

The preparation method of the hydrofining catalyst provided by the invention comprises the following steps of: grinding and dry-mixing aluminum oxide, cobalt-manganese solid solution and/or nickel-manganese solid solution, adding peptizing agent and water for kneading, extruding, shaping, drying and roasting to obtain the carrier.

The preparation method of the hydrofining catalyst provided by the invention comprises the step of taking the total weight of the carrier as a reference, wherein the content of the cobalt-manganese solid solution and/or the nickel-manganese solid solution is 0.1-20%.

The preparation method of the hydrofining catalyst comprises the steps that an auxiliary agent is added in the carrier forming process, wherein the auxiliary agent is oxides, halides or salts of group IA metals, group IIA metals, group IIIA elements and group VA elements; the addition amount of the auxiliary agent is 0.1-10% of the weight of the carrier calculated by oxide.

The invention relates to a preparation method of a hydrofining catalyst, wherein an extrusion aid is added in the carrier forming process, the extrusion aid is at least one of sesbania powder, starch and methyl cellulose, and the use amount of the extrusion aid is 3-12% of the weight of the carrier.

The invention relates to a preparation method of a hydrofining catalyst, wherein the active metal precursors are a VIB metal precursor and a VIII metal precursor.

The preparation method of the hydrofining catalyst comprises the steps of taking 100 parts by weight of the hydrofining catalyst as a basis, 65-92 parts by weight of a carrier, 5-25 parts by weight of a VIB metal precursor as a metal oxide and 0.5-15 parts by weight of a VIII metal precursor as a metal oxide.

The invention has the beneficial effects that:

the hydrofining catalyst prepared by the method of the invention has the advantages that solid solution with catalytic activity is added in the preparation process of the carrier, the carrier is anchored on the carrier by the carrier roasting process, and the roasting process of the catalyst can be omitted in the catalyst preparation process in the later stage, so that the preparation process can solve the problems that the preparation process is complicated, uneconomical, the catalyst hydrogenation effect is not ideal and the like because active components such as cobalt, nickel and the like are possibly required to be impregnated and roasted step by step when being introduced in the catalyst preparation process; on the other hand, even if the catalyst can be realized by a preparation process of 'one leaching one burning', the migration and agglomeration of the active components are caused to grow along with the process of high-temperature roasting, even the effect between the active components and a carrier is enhanced, so that the dispersibility of the active components is weakened, the synergistic effect between the active components and other components such as molybdenum and tungsten is reduced, the utilization efficiency of metal is reduced, and the hydrogenation activity of the catalyst is influenced.

In addition, the high-temperature roasting treatment process of the catalyst can correspondingly increase the production cost and the processing energy consumption. According to the preparation method provided by the invention, part of the catalytic active substances are introduced into the carrier in advance in the form of solid solution, and the other part of the active components are introduced at one time in the preparation process of the catalyst at the later stage, so that the high-temperature roasting process in the preparation of the catalyst is avoided, the preparation process of the catalyst is simplified, and the production cost of the catalyst is obviously reduced; and the interaction between the active components and the carrier on the catalyst can be weakened through the action of the solid solution and the auxiliary agent, so that the dispersibility of the active metal is better improved, and the effective utilization rate of the metal is exerted.

Drawings

FIG. 1 is an XRD spectrum of a solid solution-containing carrier sample prepared in example 1 of the present invention.

FIG. 2 is a TEM photograph of the hydrofining catalyst prepared in example 1 of the present invention.

FIG. 3 is a TEM photograph of the hydrofining catalyst prepared in comparative example 2 of the present invention.

Detailed Description

The following embodiments are provided by carrying out the embodiments of the present invention on the premise of the embodiments of the present invention, and the detailed implementation process is given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not specify specific conditions, structures or experimental methods, and generally follow conventional conditions.

The invention provides a preparation method of a hydrofining catalyst, which is not particularly limited in the application field of the hydrofining catalyst, is particularly suitable for petroleum product hydrotreating processes such as gasoline hydrogenation, diesel hydrogenation, wax oil hydrogenation and the like, is particularly suitable for catalyzing hydrofining desulfurization and denitrification reactions of gasoline, and has the characteristic of high reaction activity.

The preparation method of the hydrofining catalyst provided by the invention comprises the following steps:

The hydrofining catalyst prepared by the method of the invention has the advantages that solid solution with catalytic activity is added in the preparation process of the carrier, the carrier is anchored on the carrier by the carrier roasting process, and then the residual active metal with catalytic activity is loaded on the carrier, so that the final roasting step of the catalyst can be omitted, the aggregation problem of the active metal during roasting is avoided, and the dispersibility of the catalytic active material is improved. In addition, the complex process of step-by-step loading of the active metal can be avoided, and the steps are simplified.

In the present invention, the cobalt-manganese solid solution is (Co _xMn_yO₄)_n, where n is an integer of 1 to 10, 0 < X < 5,0 < y < 5. Preferably, n is an integer of 1 to 5, 0.5 < X < 2,0.5 < y < 3. Wherein the cobalt-manganese solid solution has a crystalline phase characteristic, which means that the cobalt-manganese solid solution is subjected to an X-ray diffraction test, and a typical crystalline phase characteristic peak of the cobalt-manganese solid solution including CoMn ₂O₄、Co₂MnO₄、CoMnO₃、Co₂Mn₃O₈ is detected in comparison with an X-ray standard card library.

In the invention, the nickel-manganese solid solution is Ni _aMn_bO_z, wherein a is more than or equal to 1 and less than or equal to 10, b is more than or equal to 1 and less than or equal to 5, and z is more than or equal to 1 and less than or equal to 10. Further preferably, 1.ltoreq.a.ltoreq.7, 0.5.ltoreq.b.ltoreq.3, 2.ltoreq.z.ltoreq.9. The nickel-manganese solid solution has a crystalline phase characteristic. The crystal phase characteristics refer to the characteristic crystal phase peak of the nickel-manganese solid solution including NiMnO ₃、NiMn₂O₄、Ni₆MnO₈, which is detected by performing an X-ray diffraction test and comparing with an X-ray standard card library.

In one embodiment, the support of the present invention comprises a combination of cobalt-manganese solid solutions and nickel-manganese solid solutions in a weight ratio of 0.1 to 10:1, preferably 0.5 to 2:1.

The support of the invention also comprises alumina, the content of cobalt-manganese solid solutions and/or nickel-manganese solid solutions being between 0.1 and 20%, preferably between 2 and 15%, based on the total weight of the support. The content of solid solution in the hydrofining catalyst is preferably controlled within the protection range of the invention, and is not too low, otherwise, the due effect is not exerted; too high is not suitable, the overall pore distribution of the carrier is affected, and the total metal consumption of the catalyst is increased, so that the production cost of the catalyst is increased, and the economic value of the catalyst is affected.

In one embodiment, the preparation method of the cobalt-manganese solid solution and/or the nickel-manganese solid solution of the present invention may be any one of the following:

Firstly, mixing cobalt and/or nickel precursors with manganese precursors to form a solution, adding citric acid, evaporating water to form gel, and drying to obtain cobalt-manganese solid solution and/or nickel-manganese solid solution.

Before forming the gel, the sol can be formed first, then the gel is formed, the gel is dried in air, and then the solid solution is obtained by roasting at different temperatures.

Secondly, mixing cobalt and/or nickel precursors with manganese precursors to form a solution, adding a mixture of citric acid and acetylacetone, adjusting the pH to 0-1.5, forming gel at 50-70 ℃, drying, and roasting to obtain cobalt-manganese solid solution and/or nickel-manganese solid solution, wherein the solid solution is nano-scale.

Thirdly, mixing the cobalt and/or nickel precursor with the manganese precursor to form a solution, dropwise adding ammonia water, regulating the pH value of the solution to 8-11 to obtain a precipitate, drying and roasting to obtain cobalt-manganese solid solution and/or nickel-manganese solid solution. Wherein the temperature for drying the precipitate can be 80-150 ℃, the drying time is 2-10 hours, the roasting temperature is 500-1300 ℃, and the roasting time is 2-6 hours.

The crystal phase composition of the solid solution is mainly regulated and controlled by a synthesis process, and the conditions such as composition proportion, high-temperature heat treatment and the like are included. In the solid solution preparation process of the present invention, the precursor of cobalt or nickel may be at least one of nitrate, halide, etc. thereof, but the present invention is not particularly limited thereto.

In one embodiment, the method of molding the carrier is: grinding and dry-mixing aluminum oxide, cobalt-manganese solid solution and/or nickel-manganese solid solution, adding peptizing agent and water for kneading, extruding, shaping, drying and roasting to obtain the carrier.

In another embodiment, an auxiliary agent is further added in the grinding and dry mixing process of the aluminum oxide, the cobalt-manganese solid solution and/or the nickel-manganese solid solution, wherein the auxiliary agent is at least one of oxides, halides or salts of group IA metals, group IIA metals, group IIIA metals and group VA metals. In a further embodiment, the auxiliary agent can also be dissolved in water, added in the process of kneading and peptizing powder, kneaded into a mass, extruded into strips, dried and baked to obtain the carrier. Wherein, the group IA metal is preferably lithium and potassium; the group IIA metal is preferably magnesium and calcium; the group IIIA metal is preferably boron; the group VA metal is preferably phosphorus. The auxiliary agent can exist in the forms of oxide, halide or salt. For example, salts of potassium may include potassium carbonate, potassium dihydrogen phosphate, potassium nitrate, or the like; the magnesium salts may include magnesium carbonate, magnesium nitrate, magnesium oxalate, or the like; the boron salts may include potassium metaborate, boric acid, potassium tetraborate, and the like; the phosphorus salts may include one or a combination of more than one of phosphoric acid, ammonium dihydrogen phosphate, or potassium dihydrogen phosphate. In a further embodiment, the auxiliaries according to the invention are added in an amount of from 0.1 to 10%, preferably from 3 to 8%, by weight of the support, based on the oxide. The invention can change the surface acidity of the catalyst, reduce the polymerization of olefin and inhibit the carbon deposit of the catalyst by adding a plurality of auxiliary agents.

In one embodiment, the extrusion aid is preferably at least one of sesbania powder, starch and methyl cellulose, more preferably sesbania powder, and the extrusion aid is used in an amount of 3-12% by weight, preferably 5-10% by weight of the carrier.

In one embodiment, the alumina is added in the form of one or more of sodium metaaluminate, pseudo-boehmite, and alumina sol, preferably pseudo-boehmite. The source of alumina is not particularly limited in the present invention, and it may be obtained by a conventional preparation method or purchased.

In an embodiment, the peptizing agent is an acid, which may be an organic acid or an inorganic acid or a combination of two acids, preferably at least one of oxalic acid, citric acid, nitric acid, and hydrochloric acid. The amount of the peptizing agent is 1 to 10% by weight, preferably 2 to 6% by weight, of the carrier.

In the preparation process of the carrier, the drying and roasting process conditions are as follows: drying at 80-120 deg.c for 4-8 hr and roasting at 450-650 deg.c for 2-8 hr.

The active metal precursors of the invention are a VIB metal precursor and a VIII metal precursor, wherein the VIB metal is preferably molybdenum and/or tungsten, and the VIII metal is preferably cobalt and/or nickel. The group VIB metal precursor and the group VIII metal precursor may be present in the form of oxides, halides, salts, or the like of the group VIB and group VIII metals.

The method for supporting the metal precursor on the carrier is not particularly limited in the present invention, and is, for example, an immersion method or a spray method. The impregnation means is, for example, but not limited to, at least one of an isovolumetric impregnation method, an overdose impregnation method and a spray method. The method specifically comprises the following steps: the carrier is immersed in a solution containing a VIB group metal precursor and a VIII group metal precursor, and then the hydrotreating catalyst is obtained through aging and heat treatment.

In the catalyst prepared by the method, substances with catalytic activity comprise solid solutions in carriers and metal precursors loaded on the carriers. In one embodiment, the weight of the support is 65 to 92 parts, preferably 76 to 86 parts, the weight of the group VIB metal precursor is 5 to 25 parts, preferably 7 to 16 parts, calculated as metal oxide, and the weight of the group VIII metal precursor is 0.5 to 15 parts, preferably 1.5 to 10 parts, calculated as metal oxide, based on 100 parts of the total mass of the hydrofinished catalyst.

Wherein the drying temperature after the metal precursor is supported on the carrier is not higher than 200 ℃, for example, 100-200 ℃, and the subsequent calcination above 200 ℃ is not carried out. In the drying process, the atmosphere is not limited, and may be an air atmosphere, a mixed atmosphere of air and nitrogen, or an inert atmosphere such as nitrogen. According to the invention, as part of active substances are added into the carrier in the form of solid solution, the pressure caused by the subsequent impregnation amount is reduced, and the roasting step can be omitted, so that the aggregation of the loaded active components is avoided, and the dispersibility of the active components is improved.

In one embodiment, the isovolumetric infusion method, for example but not limited to, specifically includes the steps of: according to the saturated water absorption of the carrier, sequentially dissolving the VIB group metal precursor and the VIII group metal precursor in ammonia water to prepare a mixed impregnating solution with stable system, impregnating the mixed impregnating solution on the carrier in an equal volume, aging and heat treating to prepare the hydrofining catalyst.

In another embodiment, the spraying method of the present invention, for example, but not limited to, specifically comprises the steps of: firstly, weighing a proper amount of a VIB metal precursor and a proper amount of a VIII metal precursor according to a catalyst formula, and testing the saturated water absorption of a carrier used by the catalyst to determine the dissolved water amount of the metal precursor; sequentially adding metal precursors into deionized water, and adjusting the pH value by adding concentrated ammonia water, for example, the mass fraction of the ammonia water is 25%, so that all the active metal precursors are dissolved into a mixed solution with stable system; spraying the precursor impregnating solution on the carrier in a mist form in a rotating environment of the rotary drum in a spraying mode, so as to obtain a catalyst precursor; finally, ageing and heat treatment are carried out on the catalyst precursor, the heat treatment condition is that the drying is carried out at 100-200 ℃, and the subsequent roasting at more than 200 ℃ is not carried out. In the drying process, the atmosphere is not limited, and can be air atmosphere, mixed atmosphere of air and nitrogen, or inert atmosphere such as nitrogen, and the catalyst product can be obtained.

Therefore, the invention provides a preparation method of the hydrofining catalyst, the catalyst obtained by the method has better dispersibility of the metal active component, can better exert the effective utilization rate of the metal and improves the activity of the hydrogenation catalyst.

The technical scheme of the invention is further described by the following specific examples.

To further illustrate the effects exhibited by the methods and catalysts employed in the present invention, examples are described in terms of solid solution-containing hydrotreating catalysts prepared in accordance with the present invention and the corresponding catalytic gasoline and coker gas oil hydrofinishing reactions, but the present invention is not limited to the following examples.

The sources of raw materials used for preparing the carrier and the catalyst are as follows:

the raw material reagents used in the invention are all commercial products.

Raw material sources used for hydrofining reaction:

The invention adopts laboratory oil products as raw materials, wherein the sulfur content of the catalytic gasoline is 392mg/kg, and the nitrogen content is 34mg/kg; the sulfur content of the coked wax oil is 2820mg/kg, and the nitrogen content is 4656mg/kg.

The desulfurization rate and the denitrification rate of the product are calculated according to the following formula:

Catalyst, reactant and product analysis method:

The sulfur content of the oil product is analyzed by adopting a TSN-2000 type sulfur nitrogen analyzer.

Example 1

Solid solution Co ₂MnO₄/Ni₆MnO₈ preparation: dissolving cobalt nitrate, nickel acetate and manganese nitrate in deionized water to prepare a mixed solution containing cobalt, nickel and manganese, dropwise adding ammonia water into the solution, stirring and dropwise adding, adjusting the pH value of the solution to 8.2, filtering and washing the precipitate, drying the precipitate at 135 ℃ for 2 hours, roasting at 840 ℃ for 4 hours and 1150 ℃ for 3 hours, and obtaining cobalt-manganese solid solution Co ₂MnO₄/Ni₆MnO₈, wherein the weight ratio of Co ₂MnO₄ to Ni ₆MnO₈ is 6.7:1.

Preparation of the carrier: and grinding and dry-mixing the solid solution Co ₂MnO₄/Ni₆MnO₈, pseudo-boehmite and boric acid to obtain the powder containing Co ₂MnO₄/Ni₆MnO₈. Adding the powder containing Co ₂MnO₄/Ni₆MnO₈ and methyl cellulose into a mixer for mixing, introducing an aqueous solution of oxalic acid and nitric acid into the mixer for kneading after the powder and the methyl cellulose are uniformly mixed, obtaining a agglomerated material, extruding and molding the agglomerated material, drying the agglomerated material at 100 ℃ for 6 hours, and roasting the agglomerated material at 580 ℃ for 4 hours to finally obtain the carrier A-1 containing Co ₂MnO₄/Ni₆MnO₈. The components and contents of the carrier A-1 are shown in Table 1.

Dissolving ammonium heptamolybdate, cobalt nitrate and nickel carbonate in an aqueous solution to prepare an active component impregnating solution, impregnating the active component impregnating solution in an equal volume on a carrier A-1 at room temperature to obtain a catalyst precursor, aging for 5 hours at room temperature, and drying for 8 hours in a nitrogen atmosphere at 140 ℃ to prepare the hydrofining catalyst C-1. The components and contents of the hydrofining catalyst C-1 are shown in Table 2.

FIG. 1 is an XRD spectrum of a solid solution-containing carrier sample prepared in example 1 of the present invention. As shown in FIG. 1, the XRD spectrum of the carrier of example 1 contains characteristic peaks of cobalt-manganese solid solution, nickel-manganese solid solution and gamma-Al ₂O₃, thereby indicating that the sample is an alumina carrier containing a composite solid solution.

Example 2

Co ₂Mn₃O₈ preparation: dissolving cobalt nitrate and manganese acetate in deionized water to prepare a mixed solution containing cobalt and manganese, adding a mixture of citric acid and acetylacetone into the solution, stirring while introducing, adjusting the pH value of the solution to 0.7, forming gel at 65 ℃, drying at 95 ℃ for 8 hours, roasting at 980 ℃ for 5 hours, and performing ball milling treatment to obtain cobalt-manganese solid solution Co ₂Mn₃O₈.

Preparation of the carrier: and grinding and dry-mixing Co ₂Mn₃O₈ and sodium metaaluminate to obtain powder containing Co ₂Mn₃O₈. Adding the powder containing Co ₂Mn₃O₈ and sesbania powder into a mixer for mixing, introducing the aqueous solution of citric acid into the mixer for kneading after the mixture is uniformly mixed, obtaining an agglomerated material, extruding and molding the agglomerated material, drying the agglomerated material at 120 ℃ for 5h, and roasting the agglomerated material at 640 ℃ for 3h to finally obtain the carrier A-2 containing Co ₂Mn₃O₈. The components and contents of the carrier A-2 are shown in Table 1.

Dissolving ammonium heptamolybdate and cobalt acetate in an aqueous solution to prepare an active component impregnating solution, spraying the active component impregnating solution on a carrier A-2 in a mist form under the rotating environment of a rotary drum at room temperature to obtain a catalyst precursor, aging for 3 hours at room temperature, and drying for 10 hours in a mixed gas atmosphere of air and nitrogen at 115 ℃, wherein the volume ratio of the air to the nitrogen is 3:1, so as to prepare the hydrofining catalyst C-2. The respective components and contents of the hydrofining catalyst C-2 are shown in Table 2.

Example 3

Preparation of NiMnO ₃: dissolving nickel chloride and manganese acetate in deionized water to prepare a mixed solution containing nickel and manganese, adding citric acid, stirring, evaporating water to form gel by adopting a rotary evaporation method, drying at 120 ℃ for 6 hours, and roasting at 670 ℃ for 6 hours to obtain the nickel-manganese solid solution NiMnO ₃.

Preparation of the carrier: and grinding and dry-mixing NiMnO ₃, pseudo-boehmite and magnesium nitrate to obtain powder containing NiMnO ₃. Adding the powder containing NiMnO ₃ and methyl cellulose into a mixer for mixing, introducing oxalic acid aqueous solution into the mixer for kneading after the mixture is uniformly mixed to obtain an agglomerated material, extruding and molding the agglomerated material, drying the agglomerated material at 110 ℃ for 3h, and roasting the agglomerated material at 520 ℃ for 7h to finally obtain the carrier A-3 containing NiMnO ₃. The components and contents of the carrier A-3 are shown in Table 1.

Dissolving ammonium tungstate and nickel chloride in an aqueous solution to prepare an active component impregnating solution, excessively impregnating the active component impregnating solution in a carrier A-3 at room temperature to obtain a catalyst precursor, aging for 7 hours at room temperature, and drying for 5 hours in an air atmosphere at 150 ℃ to obtain the hydrofining catalyst C-3. The components and contents of the hydrofining catalyst C-3 are shown in Table 2.

Example 4

Co ₂Mn₃O₈ preparation: dissolving cobalt chloride and manganese acetate in deionized water to prepare a mixed solution containing cobalt and manganese, adding a mixture of citric acid and acetylacetone into the solution, stirring while introducing, adjusting the pH value of the solution to 1.3, forming gel at 60 ℃, drying at 80 ℃ for 9h, roasting at 900 ℃ for 3h, and grinding to obtain cobalt-manganese solid solution Co ₂Mn₃O₈.

Preparation of the carrier: and grinding and dry-mixing Co ₂Mn₃O₈, sodium metaaluminate and potassium dihydrogen phosphate to obtain powder containing Co ₂Mn₃O₈. Adding the powder containing Co ₂Mn₃O₈ and sesbania powder into a mixer for mixing, introducing the aqueous solution of citric acid into the mixer for kneading after the mixture is uniformly mixed, obtaining an agglomerated material, extruding and molding, drying at 105 ℃ for 6h, and roasting at 640 ℃ for 3h, thus finally obtaining the carrier A-4 containing Co ₂Mn₃O₈. The components and contents of the carrier A-4 are shown in Table 1.

Dissolving ammonium heptamolybdate and cobalt nitrate in an aqueous solution to prepare an active component impregnating solution, impregnating the active component impregnating solution in an equal volume in a carrier A-4 at room temperature to obtain a catalyst precursor, aging for 2 hours at room temperature, and drying for 6 hours in a mixed gas atmosphere of air and nitrogen at 135 ℃ with the volume ratio of air to nitrogen being 1:4 to prepare the hydrofining catalyst C-4. The components and contents of the hydrofining catalyst C-4 are shown in Table 2.

Example 5

Solid solution CoMn ₂O₄/NiMn₂O₄ preparation: dissolving cobalt acetate, nickel chloride and manganese nitrate in deionized water to prepare a mixed solution containing cobalt, nickel and manganese, dropwise adding ammonia water into the solution, stirring and dropwise adding, adjusting the pH value of the solution to 10.1, filtering and washing the precipitate, drying the precipitate at 110 ℃ for 5h, roasting at 920 ℃ for 2h and roasting at 1080 ℃ for 2h to obtain cobalt-manganese solid solution CoMn ₂O₄/NiMn₂O₄, wherein the weight ratio of CoMn ₂O₄ to NiMn ₂O₄ is 0.4:1.

Preparation of the carrier: and grinding and dry-mixing the solid solution CoMn ₂O₄/NiMn₂O₄, pseudo-boehmite and potassium carbonate to obtain powder containing CoMn ₂O₄/NiMn₂O₄. Adding powder containing CoMn ₂O₄/NiMn₂O₄ and starch into a mixer for mixing, introducing a nitric acid aqueous solution into the mixer for kneading after the powder and the starch are uniformly mixed, obtaining an agglomerated material, extruding and forming the agglomerated material, drying the agglomerated material at 85 ℃ for 7h, and roasting the agglomerated material at 610 ℃ for 5h to finally obtain the carrier A-5 containing CoMn ₂O₄/NiMn₂O₄. The components and contents of the carrier A-5 are shown in Table 1.

Dissolving ammonium heptamolybdate, ammonium tungstate and cobalt chloride in an aqueous solution to prepare an active component impregnating solution, excessively impregnating the active component impregnating solution into a carrier A-5 at room temperature to obtain a catalyst precursor, aging for 4 hours at room temperature, and drying for 3 hours in an air atmosphere at 180 ℃ to prepare the hydrofining catalyst C-5. The components and contents of the hydrofining catalyst C-5 are shown in Table 2.

Comparative example 1

The catalyst was prepared similarly to example 5, except that: no solid solution CoMn ₂O₄/NiMn₂O₄ was prepared and no CoMn ₂O₄/NiMn₂O₄ was added in the preparation of the support. The components and contents of the obtained carrier B-1 are shown in Table 1, and the components and contents of the obtained hydrofining catalyst C-D1 are shown in Table 2.

Comparative example 2

The catalyst was prepared similarly to example 1, except that: the catalyst is prepared by adopting a process of twice dipping and twice roasting. Wherein, nickel carbonate is adopted for the first impregnation; the second impregnation was with ammonium heptamolybdate and cobalt nitrate. After the two times of impregnation are completed, aging is carried out for 5 hours at room temperature, drying is carried out for 8 hours in nitrogen atmosphere at 140 ℃ and roasting is carried out for 4 hours at 520 ℃, thus obtaining the hydrofining catalyst C-D2. The components and contents of the obtained carrier B-2 are shown in Table 1, and the components and contents of the hydrofining catalyst C-D2 are shown in Table 2.

Fig. 2 is a TEM photograph of the hydrofining catalyst prepared in example 1 of the present invention, and fig. 3 is a TEM photograph of the hydrofining catalyst prepared in comparative example 2 of the present invention. As shown in FIGS. 2 and 3, the metal dispersibility of the hydrofinished catalyst prepared by baking-free in example 1 was better than that of the catalyst obtained by baking in comparative example 2.

TABLE 1 composition and content of the vectors

TABLE 2 composition and content of hydrofining catalyst

Hydrofining performance reaction evaluation

The catalysts obtained in examples and comparative examples were used for the performance evaluation of hydrofining reaction under the following conditions:

The hydrorefining catalysts obtained in the examples and comparative examples were packed in a 50mL fixed bed isothermal reactor to evaluate the desulfurization and denitrification refining reaction performance. Before evaluation, the hydrofining catalyst was sulfided using a sulfided oil. Wherein, the catalytic gasoline adopts a hydrogen atmosphere, straight-run gasoline is used as vulcanized oil, CS ₂ is used as vulcanizing agent, and the vulcanization is carried out under the conditions of the pressure of 2.2MPa, the volume space velocity of 3.0h ^-1 and the hydrogen-oil volume ratio of 350:1. During the sulfiding, the catalyst bed temperature was raised at a rate of 20 ℃/h and was thermostated for 5h at both 230 ℃ and 280 ℃. The coking wax oil takes 2wt percent of CS ₂/cyclohexane as a vulcanizing agent, and the catalyst is vulcanized in a sectional way under the conditions of 4.0MPa of pressure, 6h ^-1 of airspeed and 400:1 of hydrogen-oil volume ratio: vulcanizing for 1.5h at 200 ℃, heating to 400 ℃, and continuously vulcanizing for 2.5h. After the vulcanization treatment process is finished, the reaction operation process conditions are adjusted to start-up operation conditions, and the vulcanized oil is switched into a reaction oil product to enter the reaction. Catalytic gasoline activity evaluation conditions: the reaction temperature is 240 ℃, the pressure is 1.6MPa, the volume space velocity is 2.5h ^-1, and the hydrogen-oil volume ratio is 320:1. Coker gas oil activity evaluation conditions: the reaction temperature is 430 ℃, the pressure is 6.0MPa, the volume space velocity is 0.8h ^-1, and the hydrogen-oil volume ratio is 850:1.

The results of evaluating the hydrofining reaction performance of the catalysts obtained in examples and comparative examples using catalytic gasoline as a raw material are shown in Table 3.

TABLE 3 evaluation results of hydrogenation reaction Performance of catalysts of examples and comparative examples

Catalyst name	Desulfurization rate, percent	Denitrification rate of%
			C-1	94.67	34.28
C-2	88.20	28.59
			C-3	89.56	32.81
C-4	91.09	29.77
			C-5	92.11	32.65
C-D1	84.74	22.63
			C-D2	89.25	30.06

Further, the catalysts obtained in example 1 and comparative examples 1 and 2 were evaluated for the performance of hydrofining reaction using coker wax oil as a raw material. The evaluation results showed that the desulfurization rate and denitrification rate were 83.49% and 55.14% in this order at the initial stage of the reaction (example 1); 75.11%, 42.37% (comparative example 1); 78.59%, 49.55% (comparative example 2). After 1000h stability evaluation, the desulfurization rate and the denitrification rate are 83.02 percent and 53.90 percent in sequence (example 1); 72.25%, 38.16% (comparative example 1); 71.97%, 40.09% (comparative example 2). From this, example 1 shows a better hydrogenation stability.

The results of the examples and the comparative examples show that the preparation process of the hydrofining catalyst provided by the invention omits a high-temperature treatment process, and is simple to operate and low in cost. Meanwhile, the catalyst shows better hydrogenation activity in the hydrofining reaction process, and particularly can improve the desulfurization and denitrification activity and stability aiming at inferior oil products.

Of course, the present invention is capable of other various embodiments and modifications thereof, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention, which is limited only by the appended claims.

Claims

1. A method for preparing a hydrofining catalyst, which is characterized by comprising the following steps:

2. The method for producing a hydrofining catalyst according to claim 1, wherein the cobalt-manganese solid solution is (Co _xMn_yO₄)_n, wherein n is an integer of 1 to 10, 0 < x <5, 0 < y < 5), and the nickel-manganese solid solution is Ni _aMn_bO_z, wherein 1.ltoreq.a.ltoreq.10, 1.ltoreq.b.ltoreq.5, 1.ltoreq.z.ltoreq.10.

3. The method for producing a hydrorefining catalyst according to claim 2, wherein a cobalt-manganese solid solution and a nickel-manganese solid solution are added in the course of the formation of the carrier, and the weight ratio of the cobalt-manganese solid solution to the nickel-manganese solid solution is 0.1 to 10:1.

4. The method for producing a hydrofinishing catalyst according to claim 3, wherein the cobalt-manganese solid solution comprises at least one of CoMn ₂O₄、Co₂MnO₄、CoMnO₃ and Co ₂Mn₃O₈ crystal phases; the nickel-manganese solid solution includes at least one of NiMnO ₃、NiMn₂O₄ and Ni ₆MnO₈ crystalline phases.

5. The method for producing a hydrorefining catalyst according to claim 1, wherein the carrier is molded as: grinding and dry-mixing aluminum oxide, cobalt-manganese solid solution and/or nickel-manganese solid solution, adding peptizing agent and water for kneading, extruding, shaping, drying and roasting to obtain the carrier.

6. The method for producing a hydrofinishing catalyst according to claim 5, wherein the cobalt-manganese solid solution and/or nickel-manganese solid solution is contained in an amount of 0.1 to 20%, preferably 2 to 15%, based on the total weight of the support.

7. The method for preparing hydrofining catalyst according to claim 1, wherein an auxiliary agent is added in the carrier forming process, and the auxiliary agent is oxide, halide or salt of group IA metal, group IIA metal, group IIIA element or group VA element; the addition amount of the auxiliary agent calculated by oxide is 0.1-10% of the weight of the carrier.

8. The method for preparing hydrofining catalyst according to claim 1, wherein an extrusion aid is added in the carrier forming process, wherein the extrusion aid is at least one of sesbania powder, starch and methyl cellulose, and the extrusion aid is 3-12% of the weight of the carrier.

9. The method for preparing a hydrofinishing catalyst according to claim 1, wherein the active metal precursors are a group VIB metal precursor and a group VIII metal precursor.

10. The method for producing a hydrofining catalyst according to claim 9, wherein the weight of the carrier is 65 to 92 parts by weight based on 100 parts by weight of the hydrofining catalyst, the weight of the group VIB metal precursor is 5 to 25 parts by weight based on metal oxide, and the weight of the group VIII metal precursor is 0.5 to 15 parts by weight based on metal oxide.