CN113559875B

CN113559875B - Hydrogenation catalyst, preparation method and application thereof

Info

Publication number: CN113559875B
Application number: CN202010351478.4A
Authority: CN
Inventors: 贾燕子; 杨清河; 曾双亲; 赵新强; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2023-09-05
Anticipated expiration: 2040-04-28
Also published as: CN113559875A

Abstract

The invention relates to the technical field of hydrogenation catalysts, and discloses a hydrogenation catalyst and a preparation method and application thereof, wherein the hydrogenation catalyst comprises a carrier and a hydrogenation active metal component loaded on the carrier, the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, the content of the carrier is 30-99 wt% based on the total amount of the hydrogenation catalyst, the content of the VIB group metal component is 0.5-50 wt% based on oxides, and the content of the VIII group metal component is 0.5-20 wt%; the carrier is alumina containing phosphorus and magnesium, the alumina containing phosphorus and magnesium has a bimodal pore structure, the bimodal pore structure is measured by mercury intrusion method, and the pore distribution is positioned at the mesoporous pore volume V of 3-100nm _{Middle hole} 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.7-4.7mL/g, total pore volume V _{Total (S)} 2.4-6.4mL/g. Compared with the prior art, the hydrogenation catalyst provided by the invention has more excellent hydrogenation activity and reaction stability.

Description

Hydrogenation catalyst, preparation method and application thereof

Technical Field

The invention relates to the technical field of hydrogenation catalysts, in particular to a hydrogenation catalyst, a preparation method and application thereof.

Background

The hydrogenation catalyst is the core of the perhydro refinery, and the hydrogenation catalyst mainly comprises a carrier and an active metal component. Since the catalyst support serves to provide a diffusion path for reactants and products and an attachment site for the formation of a reactive phase during the catalytic reaction, the adsorption of the reactants and products and the interaction with the active components on the surface of the support can have an important impact on the performance of the catalyst. Alumina, particularly gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. The precursor of alumina is hydrated alumina, such as pseudo-boehmite, and the particle size, morphology, crystallinity, impurity crystal content and the like of the alumina carrier have influence on the properties of pore volume, pore distribution, specific surface area and the like. In the prior art, by modulating the properties of particle size, morphology, crystallinity and the like of hydrated alumina, one can obtain an alumina carrier which can meet specific requirements.

CN100371077a discloses a macroporous alumina carrier and a preparation method thereof, which contains boron oxide and can also contain auxiliary agents such as phosphorus, silicon, zirconium, iron and the like. In the preparation process of the alumina carrier, boric acid is dissolved in water or peptized acid which is higher than room temperature, and then the boric acid is added into a mixture of an alumina precursor and a physical pore-expanding agent, and the final carrier is prepared by kneading, forming, drying and roasting. The carrier contains proper auxiliary agent and has the characteristics of large pore diameter, concentrated pore distribution, certain acid quantity and the like.

However, in the prior art solutions, it is difficult to obtain alumina supports having both large mesopore volumes (3-100 nm), large macropore volumes (100-5000 nm) and total pore volumes.

Disclosure of Invention

The invention aims to overcome the defect that the hydrogenation activity of a hydrogenation catalyst needs to be further improved in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof.

The inventors of the present invention found during the course of the study that during the preparation of the carrier precursor of the hydrogenation catalyst, a catalyst was prepared by adding phosphorus to the feedstockA compound and a magnesium-containing compound, and controlling the pH of the precipitation reaction or the hydrolysis reaction to 4-7, and then adjusting the pH to 7-10.5, thereby preparing a specific phosphorus-and magnesium-containing alumina having a bimodal pore structure as measured by mercury intrusion, wherein the pore distribution is located at a mesopore volume V of 3-100nm _{Middle hole} 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.7-4.7mL/g, total pore volume V _{Total (S)} 2.4-6.4mL/g; preferably, the pore distribution is located at a pore volume V of 3-100nm _{Middle hole} 0.9-1.5mL/g, pore distribution at a pore volume V of 100-5000nm _{Macropores are formed} 1.8-3.2mL/g, and the total pore volume V is 2.7-4.7mL/g; further preferably, the pore distribution is located at a pore volume V of 3-100nm _{Middle hole} 0.9-1.4mL/g, pore distribution at a pore volume V of 100-5000nm _{Macropores are formed} 1.8-2.5mL/g and a total pore volume V of 2.7-3.9mL/g. The hydrogenation catalyst prepared by taking the specific alumina containing phosphorus and magnesium as a carrier and loading the hydrogenation active metal component on the carrier has good hydrogenation activity and reaction stability.

In order to achieve the above object, a first aspect of the present invention provides a hydrogenation catalyst comprising a carrier and a hydrogenation active metal component supported on the carrier, the hydrogenation active metal component containing at least one group VIB metal component and at least one group VIII metal component, the carrier being present in an amount of 30 to 99 wt.% based on the total amount of the hydrogenation catalyst, the group VIB metal component being present in an amount of 0.5 to 50 wt.% based on oxides, the group VIII metal component being present in an amount of 0.5 to 20 wt.%;

The carrier is alumina containing phosphorus and magnesium, the alumina containing phosphorus and magnesium has a bimodal pore structure, the bimodal pore structure is measured by mercury intrusion method, and the pore distribution is positioned at the mesoporous pore volume V of 3-100nm _{Middle hole} 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.7-4.7mL/g, total pore volume V _{Total (S)} 2.4-6.4mL/g.

Preferably, the phosphorus and magnesium containing alumina has a bimodal pore structure, the bimodal poresThe structure is measured by mercury intrusion method, and the pore distribution is in the mesoporous pore volume V of 3-100nm _{Middle hole} 0.9-1.5mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.8-3.2mL/g, total pore volume V _{Total (S)} 2.7-4.7mL/g.

The second aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising the steps of:

(1) The inorganic aluminum-containing compound solution is contacted with acid or alkali to carry out precipitation reaction, or the organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus and magnesium;

(2) Aging the hydrated alumina containing phosphorus and magnesium obtained in the above way at a pH of 7-10.5;

(3) Roasting the solid product obtained by ageing in the step (2) to obtain aluminum oxide containing phosphorus and magnesium;

(4) Loading a hydrogenation active metal component onto an alumina comprising phosphorus and magnesium;

the precipitation reaction or the hydrolysis reaction in the step (1) is carried out in the presence of a phosphorus-containing compound and a magnesium-containing compound at a pH of 4 to 7;

the hydrogenation active metal component comprises at least one VIB metal component and at least one VIII metal component;

the hydrogenation active metal component and the alumina containing phosphorus and magnesium are used in an amount such that the content of the alumina containing phosphorus and magnesium is 30-99 wt% based on the total amount of the hydrogenation catalyst, the content of the group VIB metal component is 0.5-50 wt% based on oxide, and the content of the group VIII metal component is 0.5-20 wt% in the prepared hydrogenation catalyst.

A third aspect of the present invention provides the use of a hydrogenation catalyst as described in the first aspect or as produced by the production process as described in the second aspect in the hydrogenation of a hydrocarbon oil.

Compared with the prior art, the hydrogenation catalyst provided by the invention has more excellent hydrogenation activity and reaction stability. The reason is presumed to be that the hydrogenation active metal component is supported on a specific phosphorus and magnesium-containing alumina carrier having a specific bimodal pore structure, the composition and pore structure of which cooperate to give the catalyst more excellent hydrogenation activity and reaction stability.

According to the preparation method of the hydrogenation catalyst, the phosphorus-containing compound and the magnesium-containing compound are added in the preparation process of the carrier precursor, and the pH value in the preparation process is controlled in a segmented manner, so that the generation and growth of seed crystals in pseudo-boehmite can be slowed down, the obtained phosphorus-containing and magnesium-containing alumina has a specific bimodal pore structure, and the pore distribution in the phosphorus-containing and magnesium-containing alumina is positioned at a mesopore volume V of 3-100nm _{Middle hole} 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.7-4.7mL/g, total pore volume V _{Total (S)} The catalyst is 2.4-6.4mL/g, is more suitable for being used as a catalyst carrier, and the obtained hydrogenation catalyst has more excellent hydrogenation activity and stability. For example, the hydrogenation catalyst prepared in example 1 was used at a reaction temperature of 380℃and a hydrogen partial pressure of 15 MPa and a liquid hourly space velocity of 0.6 hr ^-1 The hydrogenation and de-hydrogenation (Ni+V) performance, the desulfurization performance, the carbon residue removal and the denitrification performance are tested under the condition that the volume ratio of the hydrogen oil is 600, the de-hydrogenation (Ni+V) rate of the product obtained after the reaction is 200 hours is 81%, the desulfurization rate is 89%, and the carbon residue removal rate is 62%; under the condition that other conditions are identical, the hydrogenation catalyst prepared in the comparative example 1 is reacted for 200 hours, the product has a de (Ni+V) ratio of 60%, a desulfurization ratio of 61% and a carbon residue removal ratio of 39%; the removal rate of the former is at least 21% higher than that of the latter, and the reaction stability of the former is better.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

In the present invention, the pore distribution refers to a distribution of pore diameters unless otherwise specified. The pore diameter refers to the pore diameter.

The first aspect of the invention provides a hydrogenation catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, the content of the carrier is 30-99 wt% based on the total amount of the hydrogenation catalyst, the content of the VIB group metal component is 0.5-50 wt% based on oxide, and the content of the VIII group metal component is 0.5-20 wt%;

The inventor of the present invention found that having a specific pore structure in the carrier can make the obtained hydrogenation catalyst have excellent hydrogenation activity and reaction stability, and pores too large or too small are unfavorable for the hydrogenation activity of the hydrogenation catalyst; it has further been found that when the support is an alumina containing phosphorus and magnesium and the alumina containing phosphorus and magnesium has a bimodal pore structure, as measured by mercury intrusion, the pore distribution is at a mesopore volume V of 3-100nm _{Middle hole} 0.7-1.7mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.7-4.7mL/g, total pore volume V _{Total (S)} In the case of 2.4-6.4mL/g, the obtained hydrogenation catalyst has excellent hydrogenation activity and reaction stability.

Preferably, the phosphorus and magnesium containing alumina has a bimodal pore structure, as measured by mercury intrusion, with a pore distribution of mesopore volume V in the range of 3 to 100nm _{Middle hole} 0.9-1.5mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.8-3.2mL/g, total pore volume V _{Total (S)} 2.7-4.7mL/g. Further preferably, the pore distribution is located at a pore volume V of 3-100nm _{Middle hole} 0.9-1.4mL/g, pore distribution at pore volume V of 100-5000nm _{Macropores are formed} 1.8-2.5mL/g and a total pore volume V of 2.7-3.9mL/g.

According to the invention, the phosphorus and magnesium containing alumina contains P element, mg element and optional auxiliary elements, wherein the auxiliary elements comprise metal auxiliary elements and/or nonmetal auxiliary elements; preferably, al is based on the total amount of the phosphorus and magnesium containing alumina ₂ O ₃ The content of P is 84-99.8 wt% ₂ O ₅ The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0-5 wt%.

In the invention, the auxiliary elements do not comprise P and Mg.

In a preferred embodiment of the present invention, the phosphorus and magnesium-containing alumina contains P element, mg element and auxiliary element, preferably Al based on the total amount of the phosphorus and magnesium-containing alumina ₂ O ₃ The content of P is 84-99.7 wt% ₂ O ₅ The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0.1-5 wt%. Further preferably, al is based on the total amount of the phosphorus and magnesium containing alumina ₂ O ₃ The content of P is 85-98.8 wt% ₂ O ₅ The content of MgO is 1-6 wt%, the content of MgO is 1-4 wt%, and the content of auxiliary element is 0.2-5 wt%.

The metal auxiliary agent element is not limited, and the performance of the catalyst is improved; preferably, the metal promoter element is selected from at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium, and titanium, more preferably from at least one of lithium, sodium, potassium, beryllium, calcium, zirconium, and titanium.

The non-metal auxiliary agent element is not limited, and the performance of the catalyst is improved; preferably, the nonmetallic aid element is selected from at least one of boron element, fluorine element, and silicon element.

In the invention, when the auxiliary element is F element, the content of the auxiliary element is calculated by element; when the auxiliary element is other element than the F element, the content of the auxiliary element is calculated as oxide.

In the present invention, preferably, the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

Preferably, the carrier is present in an amount of 40 to 94 wt.%, calculated as oxides, of the group VIB metal component and the group VIII metal component is present in an amount of 1 to 15 wt.%, calculated as oxides, based on the total amount of the hydrogenation catalyst. More preferably, the carrier is present in an amount of 64 to 86 wt.%, calculated as oxides, of 12 to 30 wt.% and the group VIII metal component is present in an amount of 2 to 6 wt.%, calculated as oxides, based on the total amount of the hydrogenation catalyst.

Compared with the hydrogenation catalyst provided by the prior art, the hydrogenation catalyst provided by the invention has better hydrogenation activity and reaction stability due to the fact that the hydrogenation active metal component is loaded on the specific alumina containing phosphorus and magnesium. The hydrogenation catalyst provided by the invention can be used singly or in combination with other catalysts when being used for hydrocarbon oil hydrogenation reaction.

According to the invention, the precipitation reaction or the hydrolysis reaction is carried out in the presence of the phosphorus-containing compound and the magnesium-containing compound under the condition that the pH is 4-7, so that the precipitation of phosphorus-containing hydrated alumina can be satisfied, the condition of lower pH is maintained, the growth of pseudo-boehmite crystal grains is prevented from being too fast under high pH, and the common regulation effect of phosphorus and magnesium on the growth of pseudo-boehmite is enhanced. The grain growth of pseudo-boehmite in the whole process of hydrated alumina generation and aging is carried out in the presence of phosphorus-containing compound and magnesium-containing compound, so that the prepared pseudo-boehmite has a special bimodal pore structure, and is particularly suitable for serving as a carrier precursor of heavy oil hydrogenation catalyst.

According to one embodiment of the invention, step (1) comprises: the inorganic aluminum-containing compound solution, the phosphorus-containing compound, the magnesium-containing compound and the acid or alkali are contacted to carry out precipitation reaction, or the organic aluminum-containing compound, the phosphorus-containing compound and the magnesium-containing compound are subjected to hydrolysis reaction with water; controlling the pH of the precipitation reaction or the hydrolysis reaction to be 4-7.

According to a preferred embodiment of the present invention, the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a magnesium-containing compound and a phosphorus-containing compound at a pH of 4 to 6.5. The precipitation reaction or the hydrolysis reaction is carried out at the preferable pH value, which is more beneficial to improving the hydrogenation activity of the prepared hydrogenation catalyst in heavy oil hydrogenation.

The present invention is not particularly limited in terms of the conditions other than pH of the precipitation reaction and the hydrolysis reaction. In the present invention, preferably, the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30 to 90 ℃.

In the present invention, the conditions for the precipitation reaction are selected in a wide range, and preferably, the conditions for the precipitation reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 10-60 minutes. Further preferably, the conditions of the precipitation reaction include: the reaction temperature is 45-80 ℃, and the reaction time is 10-30 minutes.

The conditions for the hydrolysis reaction are not particularly limited in the present invention, as long as water is brought into contact with the organic aluminum-containing compound to cause hydrolysis reaction to produce hydrated alumina. The water consumption in the hydrolysis reaction process is selected in a wider range, so long as the molar ratio of water to the organic aluminum-containing compound is greater than the stoichiometric ratio. Conditions under which hydrolysis specifically occurs are well known to those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours.

In the present invention, the manner of adding the phosphorus-containing compound and the magnesium-containing compound is not particularly limited, and the phosphorus-containing compound (or the aqueous solution of the phosphorus-containing compound) and the magnesium-containing compound (or the aqueous solution of the magnesium-containing compound) may be added separately, or the phosphorus-containing compound (or the aqueous solution thereof) and the magnesium-containing compound (or the aqueous solution thereof) may be mixed with one or more of the raw materials in advance, and then the raw materials containing the phosphorus-containing compound and the magnesium-containing compound are reacted, as long as the precipitation reaction or the hydrolysis reaction is ensured to be carried out in the presence of the phosphorus-containing compound and the magnesium-containing compound. The preparation method provided by the invention can ensure the regulation effect of the phosphorus-containing compound and the magnesium-containing compound on the growth of crystal grains.

According to the invention, the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a phosphorus-containing compound, a magnesium-containing compound and optionally an auxiliary element comprising a metallic auxiliary element and/or a non-metallic auxiliary element.

In the present invention, preferably, the phosphorus-containing compound, the magnesium-containing compound and the auxiliary element-containing compound are used in such an amount that, in the produced phosphorus-and magnesium-containing alumina, al is contained based on the total amount of the phosphorus-and magnesium-containing alumina ₂ O ₃ The content of P is 85-99.8 wt% ₂ O ₅ The content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0-5 wt%.

More preferably, the phosphorus-containing compound, the magnesium-containing compound and the auxiliary element-containing compound are used in such amounts that, based on the total amount of the phosphorus-and magnesium-containing alumina, al ₂ O ₃ The content of P is 84-99.7 wt% ₂ O ₅ The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0.1-5 wt%. Further preferably, al is based on the total amount of the phosphorus and magnesium containing alumina ₂ O ₃ The content of P is 85-98.8 wt% ₂ O ₅ The content of MgO is 1-6 wt%, the content of MgO is 1-4 wt%, and the content of auxiliary element is 0.2-5 wt%.

The phosphorus-containing compound of the present invention may be a water-soluble inorganic phosphorus-containing compound, and preferably, the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate.

The magnesium-containing compound of the present invention may be a water-soluble inorganic magnesium-containing compound having a wide selection range, and preferably, the magnesium-containing compound is at least one selected from the group consisting of magnesium chloride, magnesium nitrate and magnesium sulfate.

In the preparation method provided by the second aspect of the present invention, the metal auxiliary element and the nonmetal auxiliary element are the same as the metal auxiliary element and the nonmetal auxiliary element provided by the first aspect.

The invention has wider optional range for the compound containing the auxiliary agent element; preferably, the auxiliary element-containing compound is selected from at least one of oxides, alkalis and salts containing lithium, sodium, potassium, rubidium, francium, beryllium or calcium elements.

In one embodiment of the present invention, the auxiliary element-containing compound is a nonmetallic auxiliary element-containing compound; preferably, the auxiliary element-containing compound is selected from at least one of a fluorine-containing compound, a silicon-containing compound, and a boron-containing compound.

Preferably, the fluorine-containing compound is hydrofluoric acid and/or ammonium fluoride.

Preferably, the silicon-containing compound is selected from at least one of silicon oxide, silica sol, sodium silicate and potassium silicate.

Preferably, the boron-containing compound is selected from at least one of boric acid, sodium borate, ammonium borate and potassium borate.

It should be noted that, in the research process, the phosphorus-containing compound and the magnesium-containing compound are added in the precipitation reaction or the hydrolysis reaction process, which is more favorable for adjusting the generation and growth rate of crystal grains, so that the prepared pseudo-boehmite forms the specific bimodal pore structure. The phosphorus-containing compound and the magnesium-containing compound are added during the precipitation reaction or the hydrolysis reaction, so that the aging reaction to be carried out later is also carried out in the presence of the phosphorus-containing compound and the magnesium-containing compound. Preferably, no additional phosphorus-containing compound or magnesium-containing compound is added during the aging process.

According to the invention, in step (1), the inorganic aluminium-containing compound is preferably an aluminium salt and/or an aluminate. Accordingly, the inorganic aluminum-containing compound may be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution may be various aluminum salt solutions, for example, may be one or more aqueous solutions of aluminum sulfate, aluminum chloride and aluminum nitrate. Because of its low cost, aluminum sulfate solution and/or aluminum chloride solution are preferred. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solution is preferred because of its ease of availability and low cost. The aluminate solutions may also be used alone or in mixtures. The concentration of the inorganic aluminum-containing compound solution is not particularly limited, and preferably the concentration of the inorganic aluminum-containing compound solution is 20 to 200 g/l in terms of aluminum oxide.

According to the preparation method provided by the invention, the organic aluminum-containing compound in the step (1) can be at least one of various aluminum alkoxides which can be subjected to hydrolysis reaction with water to generate hydrated alumina precipitate, and can be at least one of aluminum isopropoxide, aluminum isobutanol, aluminum triisopropoxide, aluminum trite-butoxide and aluminum isooctanoxide.

According to the production method provided by the present invention, the acid in step (1) may be various protonic acids or oxides acidic in an aqueous medium, for example, may be at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid, and preferably the protonic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid. The carbonic acid may be generated in situ by passing carbon dioxide into the aluminum salt solution and/or the aluminate solution. The acid may be introduced in the form of a solution, and the concentration of the acid solution is not particularly limited, preferably H ⁺ The concentration of (2) is 0.2-2 mol/L.

According to the preparation method provided by the invention, the alkali in the step (1) can be hydroxide or salt which is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, preferably, the hydroxide is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from at least one of sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate. When sodium metaaluminate and/or potassium metaaluminate are used as the base, the amounts of the phosphorus-containing compound and the magnesium-containing compound are calculated, and the corresponding amounts of aluminum oxide in sodium metaaluminate and/or potassium metaaluminate are also considered.

Specifically, in order to regulate the pH of the hydrolysis reaction, an acid or a base may be introduced into the hydrolysis reaction, and the manner and kind of introduction of the acid or the base may be as described above, which will not be described herein.

Among them, the method of precipitating aluminum by controlling the pH with respect to the amount of alkali or acid in the reactant is well known to those skilled in the art, and will not be described herein.

The aging condition in the step (2) is selected in a wide range, so long as the aging condition is ensured to be performed under the condition that the pH is 7-10.5. Since the precipitation reaction or the hydrolysis reaction in step (1) is carried out at a pH of 4 to 7, it is preferable to introduce a base to adjust the pH of the aging reaction before aging is carried out. The base isCan be introduced in the form of a solution, the concentration of the alkali solution is not particularly limited, and OH is preferred ^- The concentration of (2) is 0.2-4 mol/L.

More preferably, the ageing of step (2) is carried out at a pH of 8-10.

The conditions of the aging other than pH in step (2) are selected in the present invention in a wide range, preferably the aging temperature is 50 to 95℃and preferably 55 to 90 ℃. The aging time is appropriately selected depending on the aging temperature, and preferably, the aging time is 0.5 to 8 hours, preferably 2 to 6 hours.

The invention also includes separating, washing and drying the aged product after the aging reaction. The separation according to the method provided by the present invention may be a method known in the art, such as filtration or centrifugation. The washing and drying method may be a method commonly used in the preparation of pseudo-boehmite, for example, the washing agent may be water and the drying may be at least one of drying, forced air drying, spray drying and flash drying. The drying temperature may be 100-350 ℃, preferably 120-300 ℃.

In the preparation method provided by the invention, the roasting process in the step (3) is not particularly limited. Preferably, the method provided by the invention further comprises shaping the solid product or the phosphorus and magnesium containing alumina before or after the firing. Preferably, the solid product obtained by aging in step (2) is dried after molding, preferably extrusion molding, and then the baking is performed. In order to ensure that the molding is carried out smoothly, water, an extrusion aid and/or an adhesive and optionally a pore-expanding agent can be added into the solid product obtained by aging in the step (2), wherein the types and the amounts of the extrusion aid, the peptizing agent and the pore-expanding agent are known to those skilled in the art; for example, the usual extrusion aid may be at least one selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene alcohol, the peptizing agent may be an inorganic acid and/or an organic acid, and the pore expanding agent may be at least one selected from starch, synthetic cellulose, a polymeric alcohol and a surfactant. Wherein the synthetic cellulose is preferably at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymeric alcohol is preferably at least one of polyethylene glycol, polypropylene glycol and polyvinyl alcohol; the surfactant is preferably at least one of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and acrylic alcohol copolymer and maleic acid copolymer with molecular weight of 200-10000. The drying conditions of step (3) preferably include: the drying temperature may be 40-350 ℃, more preferably 100-200 ℃; the drying time may be 1 to 24 hours, more preferably 2 to 12 hours.

In the preparation method provided by the present invention, the condition of the firing in the step (3) is not particularly limited, and preferably, the condition of the firing in the step (3) includes: the temperature is 350-1000deg.C, preferably 400-800deg.C, and the time is 1-10 hr, preferably 2-6 hr.

According to the preparation method provided by the invention, preferably, the VIB group metal component is Mo and/or W, and the VIII group metal component is Co and/or Ni.

According to the preparation method provided by the invention, preferably, the hydrogenation active metal component and the alumina containing phosphorus and magnesium are used in amounts such that the content of the alumina containing phosphorus and magnesium in the prepared hydrogenation catalyst is 40-94 wt% based on the total amount of the hydrogenation catalyst, the content of the group VIB metal component is 5-45 wt% based on oxide, and the content of the group VIII metal component is 1-15 wt%. More preferably, the content of the aluminium oxide containing phosphorus and magnesium is 40-94 wt.%, calculated as oxides, the content of the group VIB metal component is 5-45 wt.%, and the content of the group VIII metal component is 1-15 wt.%, based on the total amount of the hydrogenation catalyst.

According to the present invention, the method for supporting the hydrogenation active metal component on the alumina containing phosphorus and magnesium is not particularly limited, and may be any conventional method in the art, for example, a kneading method, a dry mixing method, an impregnation method; preferably, the method of supporting the hydrogenation-active metal component on a phosphorus and magnesium containing alumina comprises impregnating the phosphorus and magnesium containing alumina with an impregnation solution comprising at least one group VIB metal compound and at least one group VIII metal compound, followed by drying and calcination.

According to the preparation method provided by the invention, further, the group VIB metal compound and the group VIII metal compound are each independently selected from at least one of their soluble compounds (including the corresponding metal compounds that are soluble in water in the presence of a cosolvent). Specifically, the group VIB metal compound, for example, molybdenum, may be selected from salts and/or oxides of molybdenum-containing metals, for example, may be selected from at least one of molybdenum oxide, molybdate, para-molybdate, phosphomolybdate, preferably at least one of molybdenum oxide, ammonium molybdate, ammonium paramolybdate, phosphomolybdic acid; the group VIII metal compound, for example cobalt, may be selected from at least one of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride, preferably cobalt nitrate and/or basic cobalt carbonate, for example nickel, may be selected from at least one of nickel-containing salts, oxides and hydroxides, for example may be selected from at least one of nickel nitrate, chloride, formate, acetate, phosphate, citrate, oxalate, carbonate, basic carbonate, hydroxide, phosphide, sulfide and oxide, preferably at least one of nickel oxalate, carbonate, basic carbonate, hydroxide, phosphate and oxide, more preferably at least one of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel carbonate.

According to the preparation method provided by the invention, the invention can also contain organic additives in the preparation process of the catalyst, such as in the preparation process of the soluble compounds of the VIB group metal compound and the VIII group metal compound. The manner of introducing the organic additive is not particularly limited in the present invention, and the organic additive may be introduced in any manner, for example, may be introduced together with the group VIII metal, may be introduced together with the group VIB metal element, may be introduced after the group VIII and/or group VIB metal element is introduced, and may be introduced before the group VIII and/or group VIB element is introduced. The kind of the organic additive is not particularly limited in the present invention, and the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic matters selected from organic alcohols and/or organic acids, and the nitrogen-containing organic matters are at least one selected from organic amines and organic amine salts; specifically, the oxygen-containing organic matter is selected from at least one of ethylene glycol, glycerol, polyethylene glycol (with a molecular weight of 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and preferably at least one of ethylene glycol, glycerol, polyethylene glycol and citric acid; the nitrogen-containing organic matter is selected from at least one of ethylenediamine, diethylenetriamine, cyclohexanediamine tetraacetic acid, glycine, nitrilotriacetic acid, EDTA and amine salts thereof, preferably EDTA and/or nitrilotriacetic acid.

Further, the method and time of the impregnation are not particularly limited, and the impregnation method may be excessive liquid impregnation, pore saturation impregnation, multiple impregnation and the like according to the amount of the impregnation liquid, and may be soaking, spray impregnation and the like according to the manner of the impregnation; the impregnation time is preferably 0.5 to 3 hours. Further, by adjusting and controlling the concentration, amount or amount of support of the impregnation liquid, a specific amount of hydrogenation catalyst can be prepared, as is well known to those skilled in the art.

According to the production method provided by the present invention, the drying conditions in the method for supporting the hydrogenation-active metal component on the alumina containing phosphorus and magnesium are not particularly limited, and preferably the drying conditions include: the drying temperature is 80-200deg.C, preferably 100-150deg.C; the drying time is 1 to 8 hours, preferably 2 to 6 hours. The drying mode is not particularly limited in the present invention, and the drying may be at least one of drying, forced air drying, spray drying and flash drying.

According to the production method provided by the present invention, the range of the calcination conditions in the method in which the hydrogenation active metal component is supported on the alumina containing phosphorus and magnesium is broad, and preferably, the calcination conditions include: the roasting temperature is 200-700 ℃, preferably 350-600 ℃; the calcination time is 1 to 10 hours, preferably 2 to 8 hours.

According to the production method provided by the present invention, the atmosphere of the firing and the drying is not particularly limited, and may be at least one of air, oxygen and nitrogen, preferably air.

According to a preferred embodiment of the present invention, the preparation method comprises the steps of:

(1) Adding an inorganic aluminum-containing compound solution containing phosphorus compounds and magnesium compounds and an alkali solution or an acid solution in parallel flow or intermittently into a reaction vessel for precipitation reaction to obtain hydrated alumina slurry containing phosphorus and magnesium; or adding a phosphorus-containing compound and a magnesium-containing compound into deionized water to carry out hydrolysis reaction with aluminum alkoxide to obtain hydrated alumina slurry containing phosphorus and magnesium, and carrying out precipitation reaction or hydrolysis reaction under the condition that the pH is 4-7, preferably 4-6.5 by using an acid solution or an alkali solution;

(2) Adding alkaline solution into the hydrated alumina slurry containing phosphorus and magnesium obtained in the step (1) to adjust the pH to 7-10.5, aging for 0.5-8 hours at 50-95 ℃, and then filtering, washing and drying to obtain a solid product;

(3) Roasting the solid product obtained by ageing in the step (2) at 350-1000 ℃ for 1-10 hours to obtain alumina containing phosphorus and magnesium;

(4) Impregnating the alumina containing phosphorus and magnesium with impregnating solution containing at least one VIB group metal compound and at least one VIII group metal compound, drying at 80-200 ℃ for 1-8 hours, and roasting at 360-700 ℃ for 1-10 hours to obtain the hydrogenation catalyst provided by the invention.

According to the preparation method provided by the invention, the alumina containing phosphorus and magnesium obtained in the step (3) can be used as various adsorbents, catalyst carriers and matrixes of catalysts.

According to the present invention, the hydrogenation catalyst may be presulfided prior to use in accordance with conventional methods in the art to convert the active metal component supported thereon to a metal sulfide component; the pre-vulcanization method can be as follows: presulfiding the hydrogenation catalyst with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140-400 ℃. This pre-vulcanization may be performed ex-situ or in-situ.

The hydrogenation conditions in the application of the hydrogenation catalyst are not particularly limited, and reaction conditions common in the art can be adopted; preferably, the reaction temperature is 200-420 ℃, more preferably 220-400 ℃, the pressure is 2-18MPa, more preferably 2-16MPa, and the liquid hourly space velocity is 0.1-10 hours ^-1 And more preferably 0.15 to 6 hours ^-1 The hydrogen oil volume ratio is 50 to 5000, more preferably 50 to 4000.

The hydrotreating reaction apparatus in the application of the hydrotreating catalyst in the present invention is not particularly limited, and may be any reactor sufficient to allow the feedstock oil to contact the hydrotreating catalyst under hydrotreating reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor or an ebullated bed reactor.

The application object of the hydrogenation catalyst is not particularly limited, and the hydrogenation catalyst can be directly used for processing various hydrocarbon oil raw materials so as to carry out hydro-upgrading or hydro-cracking on the hydrocarbon oil raw materials. The hydrocarbon oil raw material may be various heavy mineral oils or synthetic oils or their mixed distillate oils, for example, may be at least one selected from crude oil, distillate oil, solvent refined oil, cerate, underfills oil, fischer-tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil; is particularly suitable for the hydrotreatment of at least one of gasoline, diesel oil, wax oil, lubricating oil, kerosene, naphtha, atmospheric residuum, vacuum residuum, petroleum wax and Fischer-Tropsch synthetic oil.

The present invention will be described in detail by examples. In the following examples, the materials involved are commercially available unless otherwise indicated.

Pore volumes in the different pore size ranges of the phosphorus and magnesium containing alumina were measured using mercury porosimetry.

Example 1

This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.

(1) Preparation of hydrated alumina PA1:

in a 2L reaction tank, 5000 mL of aluminum sulfate solution with the concentration of 60 g/L and containing 40 g of magnesium nitrate, 8.0mL of 85 wt% concentrated phosphoric acid and ammonia water solution with the concentration of 6 wt% are added in parallel to carry out precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into slurry to enable the pH value of the slurry to be 8.7, the slurry is aged for 120 minutes at 70 ℃ and then filtered, a filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried for 24 hours at 120 ℃ to obtain hydrated aluminum oxide PA1, and the PA1 has a pseudo-boehmite structure by adopting XRD. The contents of phosphorus element, magnesium element and auxiliary element in PA1 are shown in table 1.

(2) Preparation of vector Z1:

1000 g of hydrated alumina PA1 and 30 g of sesbania powder (produced by Henan orchid sesbania gum factory) were weighed and mixed uniformly, then 1100 ml of an aqueous solution containing 8g of nitric acid was added, and a butterfly-shaped wet strip with an outer diameter of 1.6mm was extruded on a plunger type strip extruder. Then the butterfly wet strip is dried for 4 hours at 120 ℃, and then baked for 3 hours at 600 ℃ to obtain Z1. The pore structure in the carrier was measured and the results are shown in Table 1.

(3) Preparation of hydrogenation catalyst C1:

100 g of Z1 are taken and 108 ml of the mixture containing MoO ₃ 247 g/l, niO 55 g/l, and the mixture of ammonium molybdate and nickel nitrate was immersed in the water for 1 hour, dried at 110℃for 4 hours, and calcined at 400℃for 3 hours to obtain a hydrogenation catalyst C1.

Comparative example 1

Pseudo-boehmite, a support and a catalyst were prepared as in example 1, except that only 8.0mL of phosphoric acid having a concentration of 85% by weight was added to the aluminum sulfate solution without magnesium nitrate, to obtain alumina hydrate CPA1. The composition of CPA1, as calculated by XRD characterization, is shown in Table 1, and the pore structure in the support is determined as indicated in Table 1, as characterized by XRD for CPA1 having pseudo-boehmite structure.

Comparative example 2

Pseudo-boehmite, a carrier and a catalyst were prepared in the same manner as in example 1 except that magnesium nitrate was not contained in the aluminum sulfate solution, the flow rate of the aqueous ammonia solution was directly controlled to bring the pH of the reaction system to 8.7, and after the completion of the precipitation reaction, it was not necessary to add aqueous ammonia to the slurry to adjust the pH to obtain alumina hydrate CPA2. The composition of CPA2, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA2 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Comparative example 3

Pseudo-boehmite, a support and a catalyst were prepared as in example 1, except that concentrated phosphoric acid and magnesium nitrate were not contained in the aluminum sulfate solution, to obtain alumina hydrate CPA3. The composition of CPA3, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA3 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 2

(1) Preparation of hydrated alumina PA2:

in a 2L reaction tank, 4000 mL of an alumina solution containing 85 wt% concentrated phosphoric acid and having a concentration of 45 g/L, 22.1mL of magnesium nitrate and 20 g of a sodium metaaluminate solution containing 210 g/L of alumina and having a caustic coefficient of 1.58 are added in parallel to carry out precipitation reaction, the reaction temperature is 80 ℃, the flow rate of reactants is adjusted to enable the neutralization pH value to be 4.0, and the reaction residence time is 15 minutes; dilute ammonia water with the concentration of 5 weight percent is added into the obtained slurry to adjust the pH of the slurry to 9.0, the temperature is raised to 85 ℃, the aging is carried out for 3 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20 liters of deionized water (the temperature is 85 ℃) is added on a filter cake to wash the filter cake for about 30 minutes. And adding the qualified filter cake into 3 liters of deionized water, stirring to form slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer to be in the range of 100-110 ℃, and drying the material for about 2 minutes to obtain the hydrated alumina PA2. The composition of PA2, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA2 having a pseudo-boehmite structure.

(2) PA 2A support Z2 was prepared as in example 1; the pore structure in the carrier was measured and the results are shown in table 1.

(3) Preparation of hydrogenation catalyst C2:

100 g of Z2 are taken and 110 ml of the mixture containing MoO ₃ 227 g/L and CoO 55 g/L of ammonium molybdate and cobalt nitrate mixed water solution are soaked for 1 hour, and are dried at 120 ℃ for 3 hours and baked at 420 ℃ for 3 hours, so that the hydrogenation catalyst C2 is obtained.

Example 3

(1) Preparation of hydrated alumina PA3:

in a2 liter reaction tank, adding 3000 mL of 60 g alumina/liter, 16 g magnesium nitrate, 3.5mL aluminum sulfate solution containing 85 wt% concentrated phosphoric acid and 1000 mL sodium metaaluminate solution containing 200 g alumina/liter and having a caustic coefficient of 1.58 in parallel flow to carry out precipitation reaction, adjusting the reaction temperature to 55 ℃ and the reactant flow rate to neutralize the pH value to 6.5, keeping the reaction for 15 minutes, adding 100 g/liter sodium carbonate solution into the obtained slurry, adjusting the pH of the slurry to 9.5, heating to 75 ℃ and aging for 5 hours, filtering by a vacuum filter, and after the filtering is completed, adding 20L deionized water (temperature 85 ℃) to the filter cake to wash the filter cake for about 30 minutes. The filter cake was dried at 120℃for 24 hours to give hydrated alumina PA3. The composition of PA3, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA3 having a pseudo-boehmite structure.

(2) PA3 was used to prepare support Z3 as in example 1; the pore structure in the carrier was measured and the results are shown in table 1.

(3) Preparation of hydrogenation catalyst C3:

100 g of Z3 are taken and 100 ml of the solution containing WO ₃ 387 g/L, and NiO 44 g/L, and nickel nitrate, is baked at 110deg.C for 4 hr and at 400deg.C for 3 hr to obtain hydrogenation catalyst C3.

Example 4

The procedure of example 3 was followed except that during the precipitation reaction, the reactant flow was adjusted so that the neutralization pH was 7. Hydrated alumina PA4 is obtained. The composition of PA4, as calculated by XRD characterization, is listed in table 1, as characterized by XRD for PA4 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 5

(1) Preparation of hydrated alumina PA5:

into a 2 liter three-neck flask with a stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content 15 wt%) was added, 4.6mL of 85% concentrated phosphoric acid and 8 g of magnesium nitrate were added, the pH was adjusted to 5.1 by adding ammonia water, then heated to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, after reacting for 2 hours, the pH was adjusted to 8.5 by adding ammonia water, after reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aging was conducted for 6 hours at 80 ℃, aqueous isopropyl alcohol was distilled off while aging was conducted, and after aging hydrated alumina was filtered, it was dried at 120 ℃ for 24 hours to obtain hydrated alumina PA5. The composition of PA5, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA5 having a pseudo-boehmite structure.

(2) PA 5A support Z5 was prepared as in example 1; the pore structure in the carrier was measured and the results are shown in table 1.

(3) The PA5 was used to prepare support Z5 and hydrogenation catalyst C5 as in example 1.

Comparative example 4

Pseudo-boehmite, a support, and a catalyst were prepared in the same manner as in example 5 except that magnesium nitrate was not added to a three-necked flask to obtain alumina hydrate CPA4. The composition of CPA4, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA4 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Comparative example 5

Pseudo-boehmite, a support and a catalyst were prepared as in example 5 except that magnesium nitrate was not added to a three-necked flask, and ammonia water was added to adjust the pH to 8.5, followed by heating to 60 ℃, and then 500 g of molten aluminum isopropoxide was slowly dropped into the flask through a separating funnel to obtain alumina hydrate CPA5. The composition of CPA5, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA5 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Comparative example 6

Pseudo-boehmite, a support, and a catalyst were prepared in the same manner as in example 5 except that concentrated phosphoric acid and magnesium nitrate were not added to a three-necked flask to obtain alumina hydrate CPA6. The composition of CPA6, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA6 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 6

(1) Preparation of hydrated alumina PA6:

into a 2 liter three-neck flask with a stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content: 15 wt%) was added, 7.0mL of 85% concentrated phosphoric acid, 4 g of magnesium chloride, and aqueous ammonia were added to adjust the pH to 6.2, heated to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, reacted for 5 hours, and then, aqueous ammonia was added to adjust the pH to 8.5, after the reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aged for 6 hours at 80 ℃, aqueous isopropyl alcohol was distilled off while aging, and after the aged hydrated alumina was filtered, dried for 24 hours at 120 ℃ to obtain hydrated alumina PA6. The composition of PA6, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA6 having a pseudo-boehmite structure.

The PA6 was used to prepare support Z6 and hydrogenation catalyst C6 as in example 1. The pore structure in the carrier was measured and the results are shown in table 1.

Comparative example 7

The phosphorus-containing pseudo-boehmite is prepared according to the typical method in heavy oil hydrogenation catalyst carrier material research, and the concentration of 8.8mL of 85% concentrated phosphoric acid is 57 g.L ^-1 3000mL of aluminum sulfate solution with a concentration of 64 g.L ^-1 2500mL of sodium metaaluminate solution is subjected to precipitation reaction, the neutralization pH value is 8.0, the reaction time is 70min, then the aging is carried out, the aging temperature is 90 ℃, the aging pH value is 8.5, the filtering is carried out after the aging, the filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried at 120 ℃ for 24 hours to prepare the phosphorus-containing pseudo-boehmite CPA7. The composition of CPA7, as calculated by XRD characterization, is shown in Table 1, as characterized by XRD for CPA7 having a pseudo-boehmite structure.

The CPA7 was prepared as described in example 1 to obtain DZ7 and DC7. The pore structure in the carrier was measured and the results are shown in table 1.

Example 7

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 1, except that 2 g of sodium acetate was further added to the aluminum sulfate solution to obtain alumina hydrate PA7. The composition of PA7, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA7 having pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 8

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared in the same manner as in example 5 except that 2g of lithium nitrate and 9 g of titanium chloride were further added to a three-necked flask to obtain pseudo-boehmite PA8.

The composition of PA8, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA8 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 9

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 1, except that 4g of ammonium fluoride was further added to the aluminum sulfate solution to obtain pseudo-boehmite PA9.

The composition of PA9, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA9 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

Example 10

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 2, except that 29 g of silica sol was further added to the aluminum sulfate solution to obtain pseudo-boehmite PA10.

The composition of PA10, as calculated by XRD characterization, is set forth in table 1, as characterized by XRD for PA10 having a pseudo-boehmite structure. The pore structure in the carrier was measured and the results are shown in table 1.

TABLE 1

Note that: v (V) _{Middle hole} Refers to the mesoporous pore volume with the pore distribution of 3-100nm, and the unit is mL/g; v (V) _{Macropores are formed} Refers to the macropore pore volume with the pore distribution of 100-5000nm, and the unit is mL/g; v (V) _{Total (S)} Refers to the total pore volume in mL/g.

As can be seen from the results of Table 1, the pseudo-boehmite containing phosphorus and magnesium prepared by the method provided by the invention has a bimodal pore structure, the bimodal pore structure is measured by mercury intrusion method, and the pore distribution is positioned at a mesopore volume V of 3-100nm _{Middle hole} 0.9-1.4mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.8-2.5mL/g, total pore volume V _{Total (S)} 2.7-3.9mL/g, and various pseudo-boehmite V prepared by the prior art method and the method in the comparative example _{Middle hole} Are all below 0.7, V _{Macropores are formed} Are all below 1, total pore volume V _{Total (S)} Are all below 2.

Test example 1

The 100mL of the hydrogenation catalysts prepared in examples 1-10 and comparative examples 1-7, respectively, were crushed into particles having a diameter of 2-3 mm and then subjected to presulfiding under the conditions including: vulcanized oilThe Shanghai normal two-line diesel oil containing 5w percent of dimethyl disulfide is adopted, and the liquid hourly space velocity of the vulcanized oil is 1.2h ^-1 The hydrogen partial pressure is 14.0MPa, the hydrogen oil volume ratio is 600, and the constant temperature is carried out for 3 hours at 360 ℃.

Then, the hydrogenation activity and stability of the catalyst were evaluated in a 100 ml small fixed bed reactor using a poor heavy oil (Ni element content of 21ppm, V element content of 55ppm, density of 0.987, carbon residue value of 10.9%, S content of 4.8%, N content of 0.29%) as a raw material, a hydrogen partial pressure of 15 MPa at a reaction temperature of 380℃and a liquid hourly space velocity of 0.6 hours ^-1 Sample analysis was performed after 200 hours of reaction at a hydrogen/oil volume ratio of 600, and the results are shown in table 2.

Wherein, the calculation methods of the de (Ni+V) rate, the desulfurization rate and the carbon residue removal rate are the same; the present invention exemplifies a calculation method by taking the removal (ni+v) rate as an example, and the removal (ni+v) rate= (the (ni+v) content in the raw material-the (ni+v) content in the hydrogenated product)/the (ni+v) content in the raw material.

Wherein, the content of nickel and vanadium in the oil sample is measured by an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is PE-5300 type plasma light meter of PE company in the United states, and the specific method is RIPP124-90 of petrochemical analysis method);

the sulfur content in the oil sample is measured by an electric quantity method (the specific method is shown in the petrochemical analysis method RIPP 62-90);

the carbon residue content in the oil sample is determined by a micro method (the specific method is shown in the petrochemical analysis method RIPP 149-90).

TABLE 2

As can be seen from Table 2, when the phosphorus and magnesium containing alumina prepared by roasting the phosphorus and magnesium containing pseudo-boehmite provided by the invention is used as a catalyst carrier, the catalyst has better demetallization, desulfurization and carbon residue removal activities under the same other conditions, and the catalyst has excellent activity and stability.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims

1. A hydrogenation catalyst comprising a carrier and a hydrogenation active metal component supported on the carrier, wherein the hydrogenation active metal component contains at least one group VIB metal component and at least one group VIII metal component, the content of the carrier is 30-99 wt%, the content of the group VIB metal component is 0.5-50 wt% and the content of the group VIII metal component is 0.5-20 wt% based on the total amount of the hydrogenation catalyst;

The carrier is alumina containing phosphorus and magnesium, the alumina containing phosphorus and magnesium has a bimodal pore structure, the bimodal pore structure is measured by mercury intrusion method, and the pore distribution is positioned at the mesoporous pore volume V of 3-100nm _{Middle hole} 0.9-1.5mL/g, a macropore pore volume V with a pore distribution of 100-5000nm _{Macropores are formed} 1.8-3.2 mL/g, total pore volume V _{Total (S)} 2.7-4.7mL/g.

2. The hydrogenation catalyst of claim 1, wherein,

the phosphorus and magnesium containing alumina contains P element, mg element and optional auxiliary elements, wherein the auxiliary elements comprise metal auxiliary elements and/or non-metal auxiliary elements.

3. The hydrogenation catalyst according to claim 1 or 2, wherein Al is based on the total amount of phosphorus and magnesium containing alumina ₂ O ₃ The content of P is 84-99.8 wt% ₂ O ₅ The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0-5 wt%.

4. According to claim 3The hydrogenation catalyst, wherein, based on the total amount of the alumina containing phosphorus and magnesium, al ₂ O ₃ The content of P is 84-99.7 wt% ₂ O ₅ The content of MgO is 0.1-6 wt%, the content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0.1-5 wt%.

5. The hydrogenation catalyst of claim 2, wherein the metal promoter element is selected from at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium, and titanium elements.

6. The hydrogenation catalyst according to claim 5, wherein the metal auxiliary element is at least one element selected from the group consisting of lithium, sodium, potassium, beryllium, calcium, zirconium, and titanium.

7. The hydrogenation catalyst according to claim 2, wherein the nonmetallic aid element is selected from at least one of boron element, fluorine element, and silicon element.

8. The hydrogenation catalyst according to claim 1 or 2, wherein the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

9. The hydrogenation catalyst according to claim 8, wherein the carrier is present in an amount of 40-94 wt.% based on the total amount of the hydrogenation catalyst, the group VIB metal component is present in an amount of 5-45 wt.% and the group VIII metal component is present in an amount of 1-15 wt.% on an oxide basis.

10. The method for preparing the hydrogenation catalyst as claimed in claim 1, which comprises the steps of:

11. The production process according to claim 10, wherein the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a phosphorus-containing compound and a magnesium-containing compound at a pH of 4 to 6.5.

12. The production method according to claim 10 or 11, wherein the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30 to 90 ℃.

13. The method of claim 12, wherein the precipitation reaction conditions include: the reaction temperature is 40-90 ℃ and the reaction time is 10-60 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 2-30 hours.

14. The method of claim 13, wherein the precipitation reaction conditions include: the reaction temperature is 45-80 ℃ and the reaction time is 10-30 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 45-80 ℃ and the reaction time is 2-20 hours.

15. The production method according to claim 10 or 11, wherein the precipitation reaction or the hydrolysis reaction of step (1) is performed in the presence of a phosphorus-containing compound, a magnesium-containing compound, and optionally an auxiliary element-containing compound, the auxiliary element including a metal auxiliary element and/or a non-metal auxiliary element.

16. The process according to claim 15, wherein the phosphorus-containing compound, the magnesium-containing compound and the auxiliary element-containing compound are used in such an amount that, based on the total amount of phosphorus-and magnesium-containing alumina, al ₂ O ₃ The content of P is 85-99.8 wt% ₂ O ₅ The content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0-5 wt%.

17. The process according to claim 16, wherein the phosphorus-containing compound, the magnesium-containing compound and the auxiliary element-containing compound are used in such an amount that, based on the total amount of phosphorus-and magnesium-containing alumina, al ₂ O ₃ The content of P is 85-99.7 wt% ₂ O ₅ The content of MgO is 0.1-5 wt%, and the content of auxiliary elements is 0.1-5 wt%.

18. The production method according to claim 10 or 11, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate.

19. The production method according to claim 10 or 11, wherein the magnesium-containing compound is selected from at least one of magnesium chloride, magnesium nitrate, and magnesium sulfate.

20. The method of claim 15, wherein the metal promoter element is selected from at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, calcium, zirconium, and titanium.

21. The production method according to claim 20, wherein the metal auxiliary element is at least one element selected from the group consisting of lithium, sodium, potassium, beryllium, calcium, zirconium, and titanium.

22. The production method according to claim 21, wherein the nonmetallic aid element is at least one selected from the group consisting of boron element, fluorine element, and silicon element.

23. The method of claim 15, wherein the auxiliary element-containing compound is selected from at least one of oxides, bases, and salts containing lithium, sodium, potassium, rubidium, francium, beryllium, or calcium elements.

24. The production method according to claim 15, wherein the compound containing an auxiliary element is selected from at least one of a fluorine-containing compound, a silicon-containing compound, and a boron-containing compound.

25. The method according to claim 24, wherein the fluorine-containing compound is hydrofluoric acid and/or ammonium fluoride.

26. The production method according to claim 24, wherein the silicon-containing compound is at least one selected from the group consisting of silicon oxide, silica sol, sodium silicate and potassium silicate.

27. The production method according to claim 24, wherein the boron-containing compound is at least one selected from the group consisting of boric acid, sodium borate, ammonium borate and potassium borate.

28. The method according to claim 10 or 11, wherein the aging in step (2) is performed at a pH of 8 to 10.

29. The preparation method according to claim 10 or 11, wherein the temperature of the aging is 50-95 ℃; the aging time is 0.5-8 hours.

30. The method of claim 29, wherein the aging temperature is 55-90 ℃; the aging time is 2-6 hours.

31. The production method according to claim 10 or 11, wherein the conditions of the firing in step (3) include: the temperature is 350-1000 ℃ and the time is 1-10 hours.

32. The method of claim 31, wherein the firing conditions of step (3) include: the temperature is 500-750 ℃ and the time is 2-6 hours.

33. The method of preparation according to claim 10 or 11, wherein the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

34. The process according to claim 33, wherein the hydrogenation active metal component is used in an amount such that the hydrogenation catalyst is produced having an alumina content of from 40 to 94% by weight, calculated as oxide, of phosphorus and magnesium, the group VIB metal component being from 5 to 45% by weight and the group VIII metal component being from 1 to 15% by weight, based on the total amount of the hydrogenation catalyst.

35. The process according to claim 10 or 11, wherein the step (4) of supporting the hydrogenation-active metal component on the phosphorus and magnesium containing alumina comprises impregnating the phosphorus and magnesium containing alumina with an impregnation solution comprising at least one group VIB metal compound and at least one group VIII metal compound, followed by drying and calcination.

36. The method of claim 35, wherein the drying conditions of step (4) comprise: the drying temperature is 80-200 ℃; the drying time is 1-8 hours.

37. The method of claim 36, wherein the drying conditions of step (4) comprise: the drying temperature is 100-150 ℃; the drying time is 2-6 hours.

38. The method of claim 35, wherein the firing conditions of step (4) include: the roasting temperature is 200-700 ℃; the roasting time is 1-10 hours.

39. The method of claim 38, wherein the firing conditions of step (4) include: the roasting temperature is 350-600 ℃; the roasting time is 2-8 hours.

40. The production method according to claim 10 or 11, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate;

the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitation through hydrolysis reaction with water;

the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid;

the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.

41. Use of a hydrogenation catalyst according to any one of claims 1 to 9 in a hydrocarbon oil hydrogenation reaction.