CN113559891B

CN113559891B - Hydrogenation catalyst, preparation method and application thereof

Info

Publication number: CN113559891B
Application number: CN202010352304.XA
Authority: CN
Inventors: 贾燕子; 聂红; 曾双亲; 杨清河; 刘学芬; 任亮
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: 2023-03-10
Anticipated expiration: 2040-04-28
Also published as: CN113559891A

Abstract

The invention relates to the technical field of hydrogenation catalysts, and discloses a hydrogenation catalyst, a preparation method and application thereof, wherein the catalyst comprises a carrier and hydrogenation active metal components loaded on the carrier, the hydrogenation active metal components comprise at least one VIB group metal component and at least one VIII group metal component, and the carrier is phosphorus-containing alumina; when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1-3. Compared with the prior art, the hydrogenation catalyst provided by the invention has excellent heteroatom removal effect and excellent stability when being applied to hydrogenation treatment.

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 and a preparation method and application thereof.

Background

With the deterioration of crude oil and the stricter requirements of environmental regulations on the quality of clean oil products, the all-hydrogen refinery has become the development direction of the refinery in the future. Wherein, the hydrogenation catalyst is the core of the hydrogenation technology.

Metal deposition, carbon deposition and accumulation of the active phase are three major factors that lead to deactivation of the hydrogenation catalyst. Wherein, the metal deposition can cover and destroy the original active phase structure of the hydrogenation catalyst, the carbon deposit can cover the active phase and the active center on the surface of the catalyst, and the reduction of the reaction performance of the catalyst can be aggravated along with the layer-falling aggregation of the active phase per se in the running process.

The catalyst carrier plays a role in providing a diffusion path for reactants and products and providing attachment sites for the formation of a reaction active phase in the process of catalytic reaction, so that the adsorption effect of the surface of the carrier with the reactants and products and the interaction force with an active component have important influence on the performance of the catalyst. These interaction forces are closely related to the specific surface area of the alumina carrier and the number and type of hydroxyl groups on the surface.

Therefore, how to optimize and match the acting force between the metal and the carrier by upgrading the carrier property and the catalyst preparation process is the key for improving the activity stability of the catalyst, and reducing the damage, aggregation and poisoning of the catalyst active phase structure in the reaction process while improving the diffusion performance and the scale capacity of the catalyst.

In the prior art, an alumina carrier which can meet specific requirements can be obtained by modulating the properties of the hydrated alumina, such as particle size, morphology, crystallinity and the like.

The introduction of phosphorus into alumina can change the pore structure, surface acidity and thermal stability of the carrier, thereby improving the activity of the hydrogenation catalyst. According to the forming process of the aluminum oxide, the introduction mode of the phosphorus is divided, and the method comprises the following steps: 1. phosphorus is introduced in the preparation process of the pseudo-boehmite, such as gelling, aging and washing processes, 2 phosphorus is introduced in the forming process or the dipping process, and the like. CN102247882A discloses a method for preparing phosphorus modified alumina by adding a phosphorus-containing compound in the process of forming pseudo-boehmite and then roasting the formed compound. In another general method, an alumina carrier is prepared from pseudo-boehmite powder by molding and roasting, and phosphorus is introduced into the alumina carrier by an impregnation method to prepare phosphorus-modified alumina.

Although the above documents disclose various processes for preparing pseudo-boehmite containing phosphorus and the obtained pseudo-boehmite is excellent in some aspects, when alumina prepared therefrom is used as a catalyst support, the heavy oil hydrodesulfurization performance of the catalyst is to be further improved and the catalyst is highly acidic and rapidly deactivated in the heavy oil hydrogenation reaction, and thus it is not suitable for the heavy oil hydrogenation reaction.

CN108421561A discloses a heavy oil hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Loading water-soluble salt of the hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst; (2) And (2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting. The preparation method of the catalyst provided by the invention is complex, is not suitable for large-scale production of the catalyst, and has low pore volume, so that the catalyst is easy to inactivate in the industrial process of heavy oil hydrogenation and the pressure drop of a catalyst bed is increased.

CN106925285A discloses a heavy oil hydrogenation catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: taking layered clay and silicon-containing alumina as carriers and one or more of molybdenum, tungsten, nickel and cobalt as active components; mixing molybdenum and/or tungsten compound and/or nickel and/or cobalt compound with deionized water or ammonia water to prepare active metal solution, adopting saturation spray-dipping method, spraying the solution on the above-mentioned carrier in atomized state, drying for 1-8 hr at 80-150 deg.C, then roasting for 2-6 hr in air at 300-650 deg.C to obtain the invented catalyst. The catalyst provided by the invention has high silicon content in the carrier, so that the surface acidity of the catalyst is extremely high, and adsorption coking of macromolecules such as asphaltene, colloid and the like in heavy oil is caused, so that the activity and the stability are low.

Disclosure of Invention

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

The inventors of the present invention found in the course of research that, in the preparation of a hydrogenation catalyst, by supporting a hydrogenation active metal component on a phosphorus-containing alumina and performing activation, and the conditions defining the activation included: the temperature is 600-800 ℃, the time is 1-10 hours, thereby preparing the specific hydrogenation catalyst, and the absorbances at 630nm and 500nm of the hydrogenation catalyst are respectively F when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS) ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1-3. The hydrogenation catalyst of the invention has good hydrogenation activity and high stability.

In order to achieve the above object, the first aspect of the present 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 comprises at least one group VIB metal component and at least one group VIII metal component, and the carrier is phosphorus-containing alumina;

when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1-3.

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

(1) Loading a hydrogenation active metal component on phosphorus-containing alumina, and then optionally drying;

(2) Activating the solid product obtained in the step (1), wherein the activating conditions comprise: the temperature is 600-800 ℃, and the time is 1-10 hours;

the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.

In a third aspect, the present invention provides the use of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the preparation method described in the second aspect in hydrogenation reaction of hydrocarbon oil.

Compared with the prior art, the hydrogenation catalyst provided by the invention has the advantages that the specific hydrogenation active metal component is loaded on the phosphorus-containing alumina, so that the prepared hydrogenation catalyst contains a large amount of Ni (Co) Al with a spinel structure formed by the specific metal component and aluminum ₂ O ₄ When the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1 to 3; furthermore, the hydrogenation catalyst provided by the invention has excellent heteroatom removal effect and excellent stability when being applied to hydrogenation treatment.

The preparation method of the hydrogenation catalyst provided by the invention has the advantages that the specific hydrogenation active metal component is loaded on the phosphorus-containing alumina, and the specific activation treatment is carried out, so that the prepared hydrogenation catalyst has the specific spinel structure Ni (Co) Al ₂ O ₄ And when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1 to 3; further, the hydrogenation catalyst has more excellent hydrogenation activity and high stability.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a hydrogenation catalyst, which comprises a carrier and hydrogenation active metal components loaded on the carrier, wherein the hydrogenation active metal components comprise at least one VIB group metal component and at least one VIII group metal component, and the carrier is phosphorus-containing alumina;

The inventor of the invention finds that although the initial activity of the catalyst is influenced by the formation of the spinel structure, the formation of a proper amount of the spinel structure does not bring too much influence on the total activity of the catalyst, and the formed spinel structure gradually releases the reaction activity along with the extension of the catalyst participating in the reaction process, so that the activity stability of the catalyst is better, the service life of the catalyst is greatly prolonged on the premise of meeting the basic activity requirement, and the production efficiency is improved.

The inventors of the present invention have further found that when the above-mentioned ratio Q representing the content of the spinel structure in the catalyst is 1 to 3, by supporting a specific hydrogenation-active metal component on a phosphorus-containing alumina containing a phosphorus element, the catalyst can obtain a better initial activity and a better activity stability, preferably the ratio Q is 1.1 to 2.5. When the Q value is less than 1, the improvement of the activity stability is not obvious; when the Q value is more than 3, the initial activity is too low, which affects the normal use of the catalyst.

The VIB group metal component and the VIII group metal component are not particularly limited, so long as the hydrogenation activity and the stability of the hydrogenation catalyst are improved; preferably, the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

The dosage ranges of the VIB group metal component and the VIII group metal component are wide, and preferably, based on the total amount of the hydrogenation catalyst, the content of the carrier is 30-99 wt%, and calculated by oxides, the content of the VIB group metal component is 0.5-50 wt%, and the content of the VIII group metal component is 0.5-20 wt%.

Further preferably, based on the total amount of the hydrogenation catalyst, the content of the carrier is 40 to 94 wt%, the content of the group VIB metal component is 5 to 45 wt% and the content of the group VIII metal component is 1 to 15 wt% calculated by oxides. More preferably, the carrier is present in an amount of 64 to 86 wt%, calculated as oxides, the group VIB metal component is present in an amount of 12 to 30 wt%, and the group VIII metal component is present in an amount of 2 to 6 wt%, based on the total amount of the hydrogenation catalyst.

The hydrogenation catalyst contains phosphorus element, and preferably, based on the total amount of the phosphorus-containing alumina, al ₂ O ₃ In an amount of 94 to 99 wt.%, preferably 95 to 98 wt.%; p ₂ O ₅ The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

According to the invention, the optional range of the phosphorus-containing alumina is wider as long as the hydrogenation activity and the stability of the hydrogenation catalyst are improved; preferably, the phosphorus-containing alumina has a specific surface hydroxyl group distribution, and the phosphorus-containing alumina has an IR spectrum of (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) 1.9-2.8; wherein, I ₃₆₇₀ Is 3670cm ^-1 Peak height, I ₃₅₈₀ Is 3580cm ^-1 Peak height, I ₃₇₇₀ Is 3770cm ^-1 Peak height, I ₃₇₂₀ Is 3720cm ^-1 Peak height.

In the present invention, the IR spectrum is obtained by measurement with a Nicolet 870 type Fourier Infrared spectrometer, nicolet corporation, USA. The method specifically comprises the following steps: pressing the sample into a self-supporting sheet, placing the self-supporting sheet in an infrared cell, treating the sample for 3 hours at 450 ℃ under a vacuum condition, and measuring the infrared spectrum of the sample. According to the spectrum 3670cm ^-1 Peak height, 3580cm ^-1 Peak height, 3770cm ^-1 Peak height, 3720cm ^-1 Calculation of the value of the peak height (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The value of (c).

(I ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The value of (A) satisfies the above-specified requirement that the phosphorus-containing alumina has a specific hydroxyl group distribution, and is more favorable for improving the hydrogenation activity of a hydrogenation catalyst prepared by using the phosphorus-containing alumina as a carrier. Prior art alumina Supports (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Generally lower than 1.8.

Preferably, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Is 2-2.7.

According to the invention, the nitrogen adsorption method pore volume of the phosphorus-containing alumina is 0.7-1.6 ml/g, the BET nitrogen adsorption method specific surface area is 250-380 square meters/g, and the diameter of several possible pores is 8-16 nanometers. The diameters of the small holes refer to the diameter corresponding to the highest point of a curve in a hole distribution curve.

According to the invention, the phosphorus-containing alumina can be obtained by roasting phosphorus-containing pseudo-boehmite. In the present invention, the conditions of the calcination are not particularly limited, and preferably, the calcination conditions include: the temperature is 350-1000 deg.C, preferably 500-750 deg.C, and the time is 1-10 hr, preferably 2-6 hr.

The present invention is not particularly limited as long as the above-mentioned phosphorus-containing alumina having a specific structure can be obtained by firing, and preferably, h of the phosphorus-containing pseudo-boehmite satisfies 1.7. Ltoreq. H.ltoreq.3, wherein h = D (031)/D (020), wherein D (031) represents a crystal grain size of a crystal face represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents a crystal grain size of a crystal face represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, wherein the 031 peak represents a peak having a2 θ of 34 to 43 ° in the XRD spectrum, wherein the 020 peak represents a peak having a2 θ of 10 to 15 ° in the XRD spectrum, D = K λ/(Bcos θ), K is a Scherrer constant, λ is a diffraction wavelength of the target material, B is a half width of the diffraction peak, and 2 θ is a position of the diffraction peak. The adoption of the preferred embodiment is more beneficial to improving the activity and stability of the catalyst.

In the present invention, for different diffraction peaks, B and 2 θ both take the corresponding peak value, for example, when D (031) is calculated, D (031) = K λ/(Bcos θ), where B is the half-peak width of the 031 diffraction peak and 2 θ is the position of the 031 diffraction peak; when calculating D (020), D (020) = K λ/(Bcos θ), where B is the half-peak width of the 020 diffraction peak and 2 θ is the position of the 020 diffraction peak.

More preferably, h of the pseudoboehmite satisfies 1.9. Ltoreq. H.ltoreq.3, further preferably satisfies 2.2. Ltoreq. H.ltoreq.2.8. Within this preferred range, the hydrogenation activity of the resulting catalyst is better.

The phosphorus-containing alumina prepared by roasting the phosphorus-containing pseudo-boehmite which meets the specification has specific hydroxyl distribution, and is more favorable for improving the hydrogenation activity of the hydrogenation catalyst prepared by taking the phosphorus-containing alumina as a carrier. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.

According to the present invention, the relative crystallinity of the pseudo-boehmite containing phosphorus (based on commercial SB powder from Condea) is generally in the range of 45 to 77%, preferably 65 to 77%.

In the present invention, the crystal structure of the pseudoboehmite was measured by X-ray diffractometer model D5005 from Siemens Germany with CuKa radiation of 44 kV and 40 mA at a scanning speed of 2 ^° In terms of a/minute.

In the invention, the pseudo-boehmite containing phosphorus contains phosphorus and has a specific crystal structure, so that the hydrogenation catalyst prepared by the alumina carrier containing phosphorus and the hydrogenation active metal component loaded on the carrier shows excellent hydrogenation activity and reaction stability.

The hydrogenation catalyst provided by the invention can also contain any auxiliary agent which does not affect the performance of the hydrogenation catalyst or can improve the performance of the hydrogenation catalyst, such as at least one of elements in groups IA, IIA, IIIA, IVA, VA, VIIA, IIB, IIIB and IVB and rare earth metal elements, preferably at least one of boron, fluorine, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated by simple substance elements is not more than 10 wt%, preferably 0.05-8 wt% based on the 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. The hydrogenation catalyst provided by the invention can be used alone or combined with other catalysts when used for hydrogenation reaction of hydrocarbon oil.

The inventors of the present invention have found that a hydrogenation catalyst having a specific spinel structure according to the first aspect described above can be formed only by activation at a temperature of 600 to 800 ℃ for 1 to 10 hours after loading a hydrogenation-active metal component on a phosphorus-containing alumina. The activation temperature is too low or the activation time is too short, the content of spinel in the obtained catalyst is too low, and the activity stability improvement effect is not obvious; if the activation temperature is too high or the activation time is too long, the spinel content in the obtained catalyst is too high, and the initial activity of the catalyst is influenced.

Preferably, the temperature of the activation is 610-780 ℃, more preferably 630-750 ℃, most preferably 650-730 ℃.

In the present invention, the above activation refers to activation that is conventional in the art, and the activation may be raised from an ambient temperature to an activation temperature, or may be raised from a drying temperature after impregnation of the metal component directly to the activation temperature, and is not particularly limited. The rate of temperature rise during activation may be 50 to 600 deg.C/hr, preferably 100 to 550 deg.C/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, the selectable range of the usage amounts of the VIB group metal component and the VIII group metal component is wide, and preferably, the usage amounts of the VIB group metal component and the VIII group metal component are such that the carrier content in the prepared hydrogenation catalyst is 30-99 wt%, the VIB group metal component content is 0.5-50 wt% and the VIII group metal component content is 0.5-20 wt% in terms of oxides, based on the total amount of the hydrogenation catalyst.

Further preferably, the content of the carrier is 40-94 wt%, 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% calculated by oxide, 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, the group VIB metal component is present in an amount of 12 to 30 wt%, and the group VIII metal component is present in an amount of 2 to 6 wt%, based on the total amount of the hydrogenation catalyst.

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

According to the preparation method provided by the invention, further, the group VIB metal compound and the group VIII metal compound are respectively and independently selected from at least one of soluble compounds (including corresponding metal compounds 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, at least one selected from molybdenum oxide, molybdate, paramolybdate and phosphomolybdate, and preferably at least one selected from molybdenum oxide, ammonium molybdate, ammonium paramolybdate and phosphomolybdic acid; the group VIII metal compound may be selected from at least one of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride, and cobalt oxide, preferably cobalt nitrate and/or basic cobalt carbonate, and nickel, for example, may be selected from at least one of salts, oxides, and hydroxides of nickel, for example, at least one of nitrates, chlorides, formates, acetates, phosphates, citrates, oxalates, carbonates, basic carbonates, hydroxides, phosphides, sulfides, and oxides of nickel, preferably at least one of oxalates, carbonates, basic carbonates, hydroxides, phosphates, and oxides of nickel, and more preferably at least one of nickel oxide, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, and nickel carbonate.

According to the preparation method provided by the invention, the catalyst can also contain organic additives in the preparation process of the catalyst, such as the preparation process of soluble compounds of the VIB group metal compound and the VIII group metal compound. The method for introducing the organic additive is not particularly limited, 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 introducing the group VIII and/or group VIB metal element, or may be introduced before introducing the group VIII and/or group VIB element. The invention is not particularly limited to the type of the organic additive, the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic substances, the oxygen-containing organic substances are selected from organic alcohol and/or organic acid, and the nitrogen-containing organic substances are selected from at least one selected from organic amine and organic amine salt; specifically, the oxygen-containing organic matter is selected from at least one of ethylene glycol, glycerol, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic 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 substance is at least one selected from ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, glycine, nitrilotriacetic acid, EDTA and amine salts thereof, preferably EDTA and/or nitrilotriacetic acid.

Further, the present invention does not limit the method and time of the impregnation, and the impregnation method may be excess liquid impregnation, pore saturation impregnation, multiple impregnation, etc. according to the amount of the impregnation liquid, and may be immersion method, spray impregnation, etc. 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 carrier amount of the impregnation solution, a specific content of the hydrogenation catalyst can be prepared, which 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 phosphorus-containing alumina are not particularly limited, and preferably, the drying conditions include: the drying temperature is 50-350 deg.C, and the drying time is 1-12 hr, preferably 80-250 deg.C, and the drying time is 2-8 hr. The present invention does not particularly limit the drying method, and the drying may be at least one of drying, air-blast drying, spray drying, and flash drying. The drying atmosphere in the present invention is not particularly limited, and may be at least one of air, oxygen and nitrogen, and is preferably air.

The hydrogenation catalyst carrier contains phosphorus element, and preferably, based on the total amount of the phosphorus-containing alumina, al ₂ O ₃ In an amount of 94 to 99 wt.%, preferably 95 to 98 wt.%; p ₂ O ₅ The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

The present invention is not particularly limited in its method of production as long as it can produce a phosphorus-containing alumina, and preferably, the method of production can produce a phosphorus-containing alumina having the specific structure of the aforementioned first aspect; preferably, the preparation method of the phosphorus-containing alumina comprises the following steps:

(1-1) contacting an inorganic aluminum-containing compound solution with acid or alkali to perform a precipitation reaction, or contacting an organic aluminum-containing compound with water to perform a hydrolysis reaction to obtain hydrated alumina containing phosphorus;

(1-2) aging the obtained hydrated alumina containing phosphorus at a pH of 7 to 10.5;

(1-3) roasting the solid product obtained by aging in the step (1-2) to obtain phosphorus-containing alumina;

the precipitation reaction or the hydrolysis reaction in the step (1-1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound under the condition that the pH value is 4-7; the grain growth regulator is a substance capable of regulating the growth speed of grains on different crystal faces.

The inventors of the present invention found in the research process that, in the preparation process of the carrier precursor of the hydrogenation catalyst, the adjustment of the grain growth mode is enhanced by adding a phosphorus-containing compound to the raw material, adding a grain growth regulator during the precipitation reaction or the hydrolysis reaction, controlling the pH of the precipitation reaction or the hydrolysis reaction to 4 to 7, and then adjusting the pH to 7 to 10.5 for aging, thereby preparing the phosphorus-containing alumina having the specific hydroxyl distribution structure according to the first aspect.

According to the present invention, the solid product obtained by aging in said step (1-2) is pseudoboehmite according to the aforementioned first aspect of the present invention.

According to the invention, the precipitation reaction or the hydrolysis reaction is carried out in the presence of a grain growth regulator and a phosphorus-containing compound under the condition that the pH is 4-7, so that the precipitation of phosphorus-containing hydrated alumina can be met, the pH condition is kept low, the condition that the pseudo-boehmite grains grow too fast under high pH is avoided, and the joint regulation effect of phosphorus and the growth regulator on the growth of the pseudo-boehmite is enhanced. The generation and aging of hydrated alumina are carried out in the presence of phosphorus compound and crystal grain regulator, so that the prepared pseudoboehmite has special crystal structure and is especially suitable for use as carrier precursor of heavy oil hydrogenating catalyst.

According to an embodiment of the present invention, the step (1-1) includes: contacting an inorganic aluminum-containing compound solution, a phosphorus-containing compound, a grain growth regulator and acid or alkali to perform a precipitation reaction, or performing a hydrolysis reaction on an organic aluminum-containing compound, a phosphorus-containing compound, a grain growth regulator and 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 (1-1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5. The precipitation reaction or 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 conditions other than pH for the precipitation reaction and hydrolysis reaction are not particularly limited in the present invention. In the present invention, it is preferable that the temperature of the precipitation reaction and the hydrolysis reaction is each independently 30 to 90 ℃.

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

In the present invention, the conditions of the hydrolysis reaction are not particularly limited as long as water is brought into contact with the organic aluminum-containing compound to cause the hydrolysis reaction to produce hydrated alumina. The invention has wide selection range of the water dosage in the hydrolysis reaction process, as long as the molar ratio of the water to the organic aluminum-containing compound is larger than the stoichiometric ratio. The conditions under which hydrolysis occurs in particular are well known to those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 deg.C, preferably 45-80 deg.C, and the reaction time is 2-30 hr, preferably 2-20 hr.

In the present invention, the grain growth regulator is a substance capable of regulating the growth rate of crystal grains on different crystal planes, and preferably a substance capable of regulating the growth rate of crystal grains on a 020 crystal plane and a 031 crystal plane. For example, the adsorbent may be any substance that strongly adsorbs hydrated alumina; preferably, the grain growth regulator is at least one of a polyhydric sugar alcohol and carboxylate and sulfate thereof; further preferably, the grain growth regulator is selected from at least one of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, gluconate, and sulfate. The gluconate, the gluconate and the sulfate can be soluble salts thereof, for example, one or more of potassium salt, sodium salt and lithium salt.

In the present invention, the addition method of the grain growth regulator is not particularly limited, and the grain growth regulator may be added alone, or the grain growth regulator may be mixed with one or more of the raw materials in advance, and then the raw materials containing the grain growth regulator may be reacted.

The amount of the grain growth regulator used in the present invention is not particularly limited, and preferably, the grain growth regulator is used in an amount of 1 to 10 wt%, preferably 1.5 to 8.5 wt%, and more preferably 2 to 6 wt%, based on the weight of the inorganic aluminum-containing compound, in the precipitation reaction, based on the weight of alumina.

Preferably, the grain growth regulator is used in the hydrolysis reaction in an amount of 1 to 10 wt%, preferably 1.5 to 8.5 wt%, and more preferably 2 to 6 wt%, based on the weight of the aluminum oxide.

In the present invention, unless otherwise specified, the grain growth regulator is used in amounts calculated based on the weight of the corresponding alumina in the organic aluminum-containing compound and the inorganic aluminum-containing compound, respectively.

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

The phosphorus-containing compound of the present invention can be selected from a wide range of types, and can 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.

In order to better exert the regulating effect of the phosphorus-containing compound on the grain growth, the phosphorus-containing compound is preferably used in such an amount that P in the prepared phosphorus-containing alumina is present based on the total amount of the phosphorus-containing alumina ₂ O ₅ The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

It should be noted that, in the research process of the present invention, it is found that the addition of the grain growth regulator and the phosphorus-containing compound in the precipitation reaction or the hydrolysis reaction is more beneficial to regulate the growth speed of the grains in the 020 crystal plane and the 031 crystal plane, so that h satisfies 1.7. Ltoreq. H.ltoreq.3, preferably satisfies 1.9. Ltoreq. H.ltoreq.3, and more preferably satisfies 2.2. Ltoreq. H.ltoreq.2.8. The grain growth regulator and the phosphorus-containing compound are added during the precipitation reaction or the hydrolysis reaction, so that the aging reaction which is carried out later is also carried out in the presence of the grain growth regulator and the phosphorus-containing compound. Preferably, no additional grain growth regulator and no additional phosphorus-containing compound are added during the aging process.

According to the preparation method provided by the invention, in the step (1-1), the inorganic aluminum-containing compound is preferably an aluminum salt and/or an aluminate. Correspondingly, the inorganic aluminum-containing compound can also be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution can be various aluminum salt solutions, such as an aqueous solution of one or more of aluminum sulfate, aluminum chloride and aluminum nitrate. Aluminum sulfate solution and/or aluminum chloride solution is preferred because of low cost. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as a sodium aluminate solution and/or a potassium aluminate solution. Sodium aluminate solution is preferred because of its availability and low cost. The aluminate solutions may also be used alone or in admixture. 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 alumina.

According to the preparation method provided by the present invention, the organic aluminum-containing compound in step (1-1) may be at least one of various aluminum alkoxides which can undergo a hydrolysis reaction with water to produce a precipitate of hydrated alumina, and may be at least one of aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate, for example.

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

According to the preparation method provided by the invention, the alkali in the step (1-1) 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 and/or potassium metaaluminate is used as the alkali, the amounts of the grain growth regulator and the phosphorus-containing compound are calculated taking into account the corresponding amounts of alumina in the sodium and/or potassium metaaluminate.

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

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

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

More preferably, the aging of step (1-2) is carried out at a pH of 8 to 10.

The conditions for the aging in step (1-2) of the present invention are selected from a wide range except for pH, and preferably, the temperature for the aging is 50 to 95 ℃, 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.

In a preferred embodiment of the invention, the invention further comprises, after the aging reaction, isolating, washing and optionally drying the aged product. According to the methods provided herein, the separation may be by techniques 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, air-blast drying, spray drying, and flash drying. The drying temperature may be 100 to 350 ℃ and preferably 120 to 300 ℃.

In the method for producing the phosphorus-containing alumina of the present invention, the calcination step in the step (1-3) is not particularly limited. Preferably, the method provided by the invention further comprises shaping the solid product or the phosphorus-containing alumina before or after the roasting. Preferably, the solid product obtained by aging in the step (1-2) is shaped, dried and then roasted, and the shaping is preferably extrusion molding. In order to ensure that the molding is carried out smoothly, water, extrusion assistant and/or adhesive and optionally pore-expanding agent can be added into the solid product obtained by aging in the step (1-2), wherein the types and the use amounts of the extrusion assistant, the peptizing agent and the pore-expanding agent are known to those skilled in the art; for example, a common extrusion aid may be selected from at least one of sesbania powder, methyl cellulose, starch, polyvinyl alcohol and polyvinyl alcohol, the peptizing agent may be an inorganic acid and/or an organic acid, and the pore-expanding agent may be at least one of starch, synthetic cellulose, 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 allyl alcohol copolymer and maleic acid copolymer with molecular weight of 200-10000. The drying conditions in step (1-3) preferably include: the drying temperature may be 40-350 deg.C, more preferably 100-200 deg.C; the drying time may be from 1 to 24 hours, more preferably from 2 to 12 hours; the conditions for the calcination in the step (1-3) preferably include: the temperature is 350-1000 deg.C, preferably 400-800 deg.C, and the time is 1-10 hr, preferably 2-6 hr.

According to a preferred embodiment of the present invention, the method for preparing the phosphorus-containing alumina comprises the steps of:

(1-1) adding an inorganic aluminum-containing compound solution containing a phosphorus compound and a grain growth regulator and an alkali solution or an acid solution into a reaction container in a concurrent flow or intermittent manner for precipitation reaction to obtain phosphorus-containing hydrated alumina slurry; or, adding a phosphorus-containing compound and a grain growth regulator into deionized water to perform hydrolysis reaction with aluminum alkoxide to obtain phosphorus-containing hydrated alumina slurry, and performing precipitation reaction or hydrolysis reaction under the condition that the pH value is 4-7, preferably 4-6.5, by using the amount of an acid solution or an alkali solution;

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

and (1-3) roasting the solid product obtained by aging in the step (1-2) at 350-1000 ℃ for 1-10 hours to obtain the phosphorus-containing alumina.

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

(1) Adding an inorganic aluminum-containing compound solution containing a phosphorus-containing compound and a grain growth regulator and an alkali solution or an acid solution into a reaction container in a concurrent flow or intermittent manner for precipitation reaction to obtain phosphorus-containing hydrated alumina slurry; or, adding a phosphorus-containing compound and a grain growth regulator into deionized water to perform hydrolysis reaction with aluminum alkoxide to obtain phosphorus-containing hydrated alumina slurry, and performing precipitation reaction or hydrolysis reaction under the condition that the pH value is 4-7, preferably 4-6.5, by using the amount of an acid solution or an alkali solution;

adding an alkaline solution into the obtained phosphorus-containing hydrated alumina slurry, adjusting the pH to 7-10.5, aging at 50-95 ℃ for 0.5-8 hours, and then filtering, washing and drying to obtain a solid product;

roasting the solid product at 350-1000 ℃ for 1-10 hours to obtain phosphorus-containing alumina;

impregnating the phosphorus-containing alumina with an impregnating solution containing at least one VIB group metal compound and at least one VIII group metal compound, and then drying at 80-200 ℃ for 1-8 hours;

(2) And (2) activating the solid product obtained in the step (1) at the temperature of 600-800 ℃ for 1-10 hours to obtain the hydrogenation catalyst provided by the invention.

In a third aspect, the present invention provides the use of the hydrogenation catalyst described in the first aspect or the hydrogenation catalyst prepared by the preparation method described in the second aspect in a hydrogenation reaction of hydrocarbon oil.

According to the present invention, the hydrogenation catalyst may be presulfided according to a conventional method in the art before use to convert the active metal component supported thereon into a metal sulfide component; the prevulcanization method can be as follows: the hydrogenation catalyst is presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at 140-400 ℃ in the presence of hydrogen. The prevulcanisation can be carried out either ex situ or in situ.

In the present invention, the hydrogenation conditions for the application of the hydrogenation catalyst are not particularly limited, and the reaction conditions generally used in the art may be employed; 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 More preferably 0.15 to 6 hours ^-1 The hydrogen-oil volume ratio is 50 to 5000, and more preferably 50 to 4000.

The hydrotreating reaction apparatus in the application of the hydrogenation catalyst in the present invention is not particularly limited, and may be any reactor sufficient for the contact reaction of the feedstock oil with the hydrogenation catalyst under the hydrotreating reaction conditions, such as a fixed bed reactor, a slurry bed reactor, a moving bed reactor, or a fluidized 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 hydrogenation modification or hydrocracking on the hydrocarbon oil raw materials. The hydrocarbon oil raw material can be various heavy mineral oils or synthetic oils or their mixed distillate oil, and can be at least one selected from crude oil, distillate oil, solvent refined oil, cerate, under-wax oil, fischer-Tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil; the catalyst is particularly suitable for hydrotreating at least one of gasoline, diesel oil, wax oil, lubricating oil, kerosene, naphtha, atmospheric residue, vacuum residue, petroleum wax and Fischer-Tropsch synthetic oil.

The present invention will be described in detail below by way of examples. In the following examples, XRD was measured on a SIMENS D5005X-ray diffractometer with CuKa radiation, 44 kV, 40 mA, and a scanning speed of 2 DEG/min. According to the Scherrer formula: d = K λ/(Bcos θ) (D is the crystal grain size, λ is the diffraction wavelength of the target material, B is the half-width of the corrected diffraction peak, and 2 θ is the position of the diffraction peak), the crystal grain size of (020) is calculated as D (020) using the parameter that 2 θ is the 10-15 ° peak, and the crystal grain size of (031) is calculated as D (031) using the parameter that 2 θ is the 34-43 ° peak, respectively, and h = D (031)/D (020) is calculated.

The IR spectrum is obtained by measuring with a Nicolet 870 type Fourier infrared spectrometer of Nicolet company in the United states. The method specifically comprises the following steps: pressing the sample into a self-supporting sheet, placing the self-supporting sheet in an infrared cell, treating the sample for 3 hours at 450 ℃ under a vacuum condition, and measuring the infrared spectrum of the sample. According to the spectrum 3670cm ^-1 Peak height, 3580cm ^-1 Peak height, 3770cm ^-1 Peak height, 3720cm ^-1 Calculation of the value of the peak height (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The value of (c).

The formation of spinel structure of the metal component with aluminum in the catalyst was determined by ultraviolet visible spectroscopy (DRUVS). The instrument adopts a Cary300 ultraviolet visible light analyzer of Agilent company, and the wavelength ranges are as follows: 190nm-1100nm, wavelength precision: ± 0.1nm, wavelength reproducibility: ± 0.1nm, baseline stability: 0.0003/h, stray light: 0.02% or less, photometric accuracy: + -0.003.

In the following examples, the starting materials are all commercially available unless otherwise indicated.

Example 1

This example illustrates the hydrogenation catalyst and the method of preparation of the hydrogenation catalyst provided by the present invention.

5000 mL of aluminum sulfate solution with the concentration of 60 g of alumina/l and the ribitol content of 6.0 g and 8.0mL of 85 wt% concentrated phosphoric acid and 6 wt% ammonia water solution are added into a 2-liter reaction tank in parallel flow for precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow of the ammonia water solution is controlled to ensure that the pH value of a reaction system is 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into the slurry to ensure that the pH value of the slurry is 8.7, the slurry is aged at 70 ℃ for 120 minutes and then filtered, a filter cake is pulped and washed for 2 times by deionized water, and the filter cake is dried at 120 ℃ for 24 hours to obtain hydrated alumina PA1 which is characterized by XRD, wherein the PA1 has a pseudo-boehmite structure.

The h values for PA1 calculated by XRD characterization are shown in Table 1. Relative crystallinity of PA1 and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

1000 g of the PA1 and 30g of sesbania powder (produced by Shunhun corporation, fengshu county), then 920 ml of aqueous solution containing 28g of nitric acid is added for mixing, and then a butterfly-shaped wet strip with the outer diameter of 1.7mm is extruded on a plunger type extruding machine, the butterfly-shaped wet strip is dried for 4 hours at 120 ℃, and then is roasted for 3 hours at 600 ℃, so that the carrier Z1 is obtained. P in vector Z1 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z1 are taken and 110 ml of a mixed aqueous solution consisting of ammonium molybdate, nickel nitrate and citric acid (the mixed aqueous solution contains MoO) ₃ 434 g/l, niO 78 g/l and citric acid 160 g/l) was impregnated in the carrier Z for 1 hour, dried at 110 ℃ for 4 hours and activated at 650 ℃ for 3 hours to obtain a hydrogenation catalyst C1. Spinel structure measurement Q of the hydrogenation catalyst and its metal oxide (MoO) ₃ And NiO) are shown in table 3.

Comparative example 1

The support DZ1 and the hydrogenation catalyst DC1 were prepared and tested accordingly as in example 1, except that the activation conditions were: activating at 420 ℃ for 3 hours.

Comparative example 2

The support DZ2 and the hydrogenation catalyst DC2 were prepared and tested accordingly as in example 1, except that the activation conditions were: activation at 820 ℃ for 3 hours.

Example 2

The carrier Z2 and the hydrogenation catalyst C2 were prepared by following the procedure of example 1, except that 8.0mL of phosphoric acid having a concentration of 85% by weight was added to the aluminum sulfate solution without ribitol to obtain hydrated alumina PA2. The PA2 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of PA2 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. The pore volume, the specific surface area and possibly the pore diameter of the support Z2 are given in Table 2.

Example 3

The carrier Z3 and the hydrogenation catalyst C3 were prepared by the method of example 1, except that the flow rate of the aqueous ammonia solution was directly controlled so that the pH of the reaction system was 8.7, and after the completion of the precipitation reaction, the pH was adjusted without adding aqueous ammonia to the slurry to obtain hydrated alumina PA3. The PA3 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of PA3 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z3 ₂ O ₅ The contents of (b) and their pore volumes, specific surface areas and possibly several pore diameters are listed in Table 2.

Comparative example 3

A carrier DZ3 and a hydrogenation catalyst DC3 were prepared by following the procedure of example 1 except that 6.0 g of ribitol alone, not containing concentrated phosphoric acid, was added to the aluminum sulfate solution to obtain hydrated alumina CPA3. According to the method of example 1, CPA3 has a pseudo-boehmite structure and the h value of CPA3 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector DZ3 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2. And, the activation conditions are controlled as follows: activating at 420 ℃ for 3 hours.

Example 4

This example serves to illustrate the hydrogenation catalyst and the process for its preparation according to the invention.

4000 mL of a 45 g/l aluminum trichloride solution containing 85 wt% concentrated phosphoric acid 22.1mL and sorbitol 4.52 g/l and 1000 mL of a sodium metaaluminate solution containing 210 g/l alumina and having a caustic factor of 1.58 were added in parallel to a 2-l reaction tank to perform a precipitation reaction at a reaction temperature of 80 ℃, the flow rate of the reactants was adjusted so that the neutralization pH value was 4.0, and the reaction residence time was 15 minutes; and adding dilute ammonia water with the concentration of 5 weight percent into the obtained slurry to adjust the pH value of the slurry to 9.0, heating to 85 ℃, aging for 3 hours, then filtering by using a vacuum filter, and after filtering, additionally adding 20 liters of deionized water (the temperature is 85 ℃) into a filter cake to flush the filter cake for about 30 minutes. And adding the qualified washed filter cake into 3.0L of deionized water, stirring to obtain slurry, pumping the slurry into a spray dryer for drying, controlling the temperature of an outlet of the spray dryer to be within the range of 100-110 ℃, and drying the material for about 2 minutes to obtain the hydrated alumina PA4. PA4 has a pseudo-boehmite structure according to the method of example 1 and is characterized by XRD, and h values of PA4 calculated by XRD characterization are shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. Roasting at 600 deg.C for 4 hr, and infrared spectrum measuring for PHydroxyl on the surface of alumina was measured (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

Support Z4 was prepared according to the method of example 1, except that PA4 was used instead of PA1 and the calcination temperature was 650 ℃. P in vector Z4 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the carrier Z4 was taken, and 110 ml of a mixed aqueous solution (containing MoO) composed of ammonium molybdate, cobalt nitrate and ammonia water was added ₃ 201 g/l, coO 40 g/l, ammonia 50 g/l) was impregnated with the support Z for 4 hours, then dried at 120 ℃ for 3 hours, and then activated at 650 ℃ for 5 hours to obtain a hydrogenation catalyst C4. The spinel structure measurement Q of the hydrogenation catalyst and the content of its metal oxide are shown in table 3.

Example 5

The carrier Z5 and the hydrogenation catalyst C5 were prepared by following the procedure of example 4 except that sorbitol was not contained in the aluminum trichloride solution to obtain hydrated alumina PA5. PA5 has a pseudo-boehmite structure according to the method of example 1 and is characterized by XRD, and h values of PA5 calculated by XRD characterization are shown in Table 1, relative crystallinity and P ₂ O ₅ The contents of (A) are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z5 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 6

The carrier Z6 and the hydrogenation catalyst C6 were prepared according to the method of example 4, except that the flow rate of the sodium metaaluminate solution was directly controlled so that the pH of the reaction system was 9.0, and after the completion of the precipitation reaction, the pH was adjusted without adding ammonia water to the slurry to obtain hydrated alumina PA6. PA6 has a pseudo-boehmite structure according to the method of example 1 and is characterized by XRD, and h values of PA6 calculated by XRD characterization are shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z6 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 4

The supported DZ4 and the hydrogenation catalyst DC4 were prepared by following the procedure of example 4 except that concentrated phosphoric acid was not contained in the aluminum trichloride solution to obtain hydrated alumina CPA4. According to the method of example 1, CPA4 has a pseudo-boehmite structure and the h value of CPA4 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector DZ4 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2. And, the activation conditions are controlled as follows: activating at 400 deg.C for 3 hr.

Example 7

3000mL of an aluminum sulfate solution having a concentration of 60 g of alumina/l and a gluconic acid content of 4.5 g/l and containing 85% by weight of concentrated phosphoric acid (3.5 mL) and 1000 mL of a sodium metaaluminate solution having a concentration of 200 g of alumina/l and a caustic factor of 1.58 were concurrently charged into a 2-liter reaction tank to carry out a precipitation reaction at a reaction temperature of 55 ℃ with the adjustment of the reactant flow rate so as to neutralize the pH to 6.5, the reaction was left for 15 minutes, then a sodium carbonate solution having a concentration of 100g/l was added to the resulting slurry to adjust the pH of the slurry to 9.5 and raise the temperature to 75 ℃, followed by aging for 5 hours, and then filtration was carried out with a vacuum filter, and after completion of the filtration, 20 l of deionized water (temperature 85 ℃) was additionally added 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 PA7. According to the method of the embodiment 1, the PA7 has a pseudo-boehmite structure by adopting XRD characterization, and the h value column of the PA7 is obtained by calculation of the XRD characterizationIn Table 1, relative crystallinity and P ₂ O ₅ The contents of (A) are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

Weighing 1 kg of carrier PA7, 30g of sesbania powder (produced by Shunhun commerce, inc. in Feng county, jiangsu province) and 30g of hydroxypropyl methyl cellulose, uniformly mixing, adding 1.2 l of 1% nitric acid aqueous solution, uniformly mixing, continuously kneading on a double-screw extruder to obtain a plastic body, extruding into wet butterfly-shaped strips with the diameter of 1.1 mm, drying the wet butterfly-shaped strips at 110 ℃ for 2 hours, and roasting at 620 ℃ for 3 hours to obtain the carrier Z7. P in vector Z7 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z7 are taken and 220 ml of a mixed aqueous solution consisting of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contains MoO) ₃ 230 g/l, 54 g/l of NiO and 50g/l of phosphoric acid) is soaked in the carrier Z for 7 hours, dried for 3 hours at 120 ℃ and activated for 3 hours at 700 ℃ to obtain the hydrogenation catalyst C7. The spinel structure measurement Q of the hydrogenation catalyst and the content of its metal oxide are shown in table 3.

Example 8

Support Z8 and hydrogenation catalyst C8 were prepared according to the method of example 7, except that during the precipitation reaction, the flow of reactants was adjusted so that the neutralization pH was 7. Thus obtaining hydrated alumina PA8. PA8 has a pseudo-boehmite structure according to the method of example 1 and is characterized by XRD, and h values of PA8 calculated by XRD characterization are shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA8 were used to prepare the support Z8, P in Z8 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2. Prepared by using a carrier Z8The process for preparing the hydrogenation catalyst C8 comprises the following steps: 100g of the support Z8 are taken and 220 ml of a mixed aqueous solution consisting of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contains MoO) ₃ 230 g/L, 54 g/L NiO and 50g/L phosphoric acid are used for impregnating the carrier Z for 81 hours, drying is carried out for 3 hours at 120 ℃, and activation is carried out for 3 hours at 700 ℃ to obtain the hydrogenation catalyst C8. The spinel structure measurement Q of the hydrogenation catalyst and the content of its metal oxide are shown in table 3.

Example 9

Adding 1000 g of isopropanol-water azeotrope (the water content is 15 wt%) into a 2L three-neck flask with a stirring and reflux condenser pipe, adding 4.6mL of 85% concentrated phosphoric acid and 15g of ribonic acid, adding ammonia water to adjust the pH value to 5.1, heating to 60 ℃, slowly dropping 500 g of molten aluminum isopropoxide into the flask through a separating funnel, reacting for 2 hours, adding ammonia water to adjust the pH value to 8.5, refluxing for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating hydrous isopropanol while aging, filtering aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA9. The PA9 has a pseudo-boehmite structure according to the XRD characterization of the method of example 1, and the h value of the PA9 calculated by the XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA9 were used to prepare the support Z9, P in Z9 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z9 are taken and 110 ml of a mixed aqueous solution consisting of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contains MoO) ₃ 183 g/l, niO 44 g/l, phosphoric acid 60 g/l) was impregnated into the carrier Z for 91 hours, dried at 120 ℃ for 3 hours, and activated at 730 ℃ for 3 hours to obtain a hydrogenation catalyst C9. The additionThe spinel structure measurement Q of the hydrogen catalyst and the content of its metal oxide are shown in table 3.

Comparative example 5

The support DZ5 and the hydrogenation catalyst DC5 were prepared and tested accordingly as in example 9, except that the activation conditions were: activated at 430 ℃ for 3 hours.

Comparative example 6

The support DZ6 and the hydrogenation catalyst DC6 were prepared and tested accordingly as in example 9, except that the activation conditions were: activation at 820 ℃ for 3 hours.

Example 10

The carrier Z10 and the hydrogenation catalyst C10 were prepared according to the method of example 9, except that no ribonic acid was added to the three-necked flask, to obtain hydrated alumina PA10. The PA10 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of the PA10 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z10 ₂ O ₅ The contents of (b) and their pore volumes, specific surface areas and possibly several pore diameters are listed in Table 2.

Example 11

The carrier Z11 and the hydrogenation catalyst C11 were prepared according to the method of example 9, except that after the same amount of ribonic acid was added, ammonia was then added to adjust the pH to 8.5, and then heated to 60 ℃, and then 500 g of molten aluminum isopropoxide was slowly added dropwise to the flask through a separatory funnel to obtain hydrated alumina PA11. The PA11 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of PA11 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents of (A) are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z11 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 7

The supported DZ7 and the hydrogenation catalyst DC7 were prepared according to the method of example 9, except that concentrated phosphoric acid was not added to the three-necked flask, to obtain hydrated alumina CPA7. The method of example 1 was followed and characterized by XRD, and CPA7 had a pseudo-boehmite structure, and the XRD characterization calculated h values of CPA7 are shown in Table 1, and the relative crystallinity is also shown in Table 1. The hydroxyl on the surface of the alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector DZ7 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2. And, the activation conditions are controlled as follows: activated at 430 ℃ for 3 hours.

Example 12

Adding 1000 g of isopropanol-water azeotrope (the water content is 15 wt%) into a 2L three-neck flask with a stirring and reflux condenser pipe, adding 7.0mL of 85% concentrated phosphoric acid and 12g of ribonic acid, adding ammonia water to adjust the pH value to 6.2, heating to 60 ℃, slowly dropping 500 g of molten aluminum isopropoxide into the flask through a separating funnel, reacting for 5 hours, adding ammonia water to adjust the pH value to 8.5, refluxing for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating hydrous isopropanol while aging, filtering aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA12. The PA12 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of the PA12 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA12 were used to prepare the support Z12, P being present in the support Z12 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z12 are taken and 110 ml of a mixed aqueous solution consisting of tungsten oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contains MoO) ₃ 249 g/l, niO 59 g/l, phosphoric acid 70 g/l) was impregnated into the carrier Z for 121 hours, dried at 120 ℃ for 3 hours, and activated at 730 ℃ for 3 hours to obtain a hydrogenation catalyst C12. The spinel structure measurement Q of the hydrogenation catalyst and the content of its metal oxide are shown in table 3.

Example 13

The support Z13 and the hydrogenation catalyst C13 were carried out according to the method of example 12 and tested accordingly, except that the activation conditions were: activation is carried out for 3 hours at 630 ℃.

Example 14

The support Z14 and the hydrogenation catalyst C14 were carried out according to the method of example 12 and tested accordingly, except that the activation conditions were: activation is carried out for 3 hours at 780 ℃.

Example 15

The procedure of example 12 was followed for preparing a pseudo-boehmite containing phosphorus and a hydrogenation catalyst C15, except that the pseudo-boehmite containing phosphorus was prepared according to a typical method in "research on support Material for heavy oil hydrogenation catalyst": with 85% concentrated phosphoric acid added to 8.8mL of 57 g.L ^-1 3000mL of aluminum sulfate solution (D) and a concentration of 64 g.L ^-1 And carrying out precipitation reaction on 2500mL of sodium metaaluminate solution, wherein the neutralization pH is 8.0, the reaction time is 70min, then aging is carried out, the aging temperature is 90 ℃, the aging pH is 8.5, filtering is carried out after aging, a filter cake is beaten and washed for 2 times by deionized water, and the filter cake is dried for 24 hours at 120 ℃ to prepare the phosphorus-containing pseudo-boehmite PA15. The method of example 1 was followed and characterized by XRD, PA15 having pseudo-boehmite structure, and H-value of PA15 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector Z15 ₂ O ₅ Content of (A), and pore volume and specific surface area thereofAnd several pore diameters are listed in table 2.

Comparative example 8

The carrier DZ8 and the hydrogenation catalyst DC8 were prepared according to the method of example 10, except that a phosphorus-modified pseudoboehmite catalyst carrier material and a preparation method thereof were disclosed in CN 103721732A. Adding an aluminum sulfate solution with the alumina concentration of 50g/L and a sodium metaaluminate solution with the alumina concentration of 220g/L and the caustic ratio of 1.2 into a neutralization reaction kettle 1, controlling the pH value to be 7.0 and the temperature to be 55 ℃; the slurry of the neutralization reaction kettle 1 flows into a neutralization reaction kettle 2 through an overflow reaction pipe, and a sodium carbonate solution with the concentration of 150g/L is added into the neutralization reaction kettle 2, the pH value is controlled to be 9.5, and the reaction temperature is controlled to be 70 ℃; the slurry in the neutralization reaction kettle 2 flows into an aging reaction kettle through an overflow reaction pipe, the temperature of the slurry in the aging reaction kettle is 95 ℃, and the aging is carried out for 2 hours; calculating the volume of phosphoric acid solution with the phosphorus pentoxide concentration of 100g/L added into the aging reaction kettle according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, wherein the phosphorus pentoxide content of the added phosphoric acid is 4 percent of the alumina content; and after aging, washing and drying to obtain the phosphorus-containing pseudo-boehmite DPA8. DPA8 has a pseudoboehmite structure as characterized by XRD according to the method of example 1, and the h value of DPA8 calculated by XRD characterization is shown in Table 1, relative crystallinity and P ₂ O ₅ The contents of (A) are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1. P in vector DZ8 ₂ O ₅ The contents of (b) and their pore volumes, specific surface areas and possibly several pore diameters are listed in Table 2.

And, controlling the activation conditions to: activated at 430 ℃ for 3 hours.

Comparative example 9

The hydroxyl groups on the surface of the dry rubber powder CPA9 (produced by Changling catalyst Co., ltd.) were measured by infrared spectroscopy after baking at 600 ℃ for 4 hours (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

300 g of dry rubber powder CPA9 (produced by Changling catalyst Co., ltd.) and 10 g of sesbania powder (Henan Lanco-Kao)Sesbania gum factory) to obtain a mixture, mixing the mixture with 360 ml of aqueous solution containing 7g of nitric acid at room temperature, continuously kneading the mixture on a double-screw extruder to obtain plastic bodies, extruding the plastic bodies to form butterfly-shaped wet strips with the diameter of 1.4 mm, drying the butterfly-shaped wet strips at 120 ℃ for 4 hours, and roasting the butterfly-shaped wet strips at 600 ℃ for 4 hours to obtain a carrier DZ9. P in vector DZ9 ₂ O ₅ The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

110 ml of mixed aqueous solution consisting of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contains MoO) ₃ 249 g/l, niO 59 g/l, phosphoric acid 78 g/l) were impregnated into the support DZ9, followed by drying at 120 ℃ for 4 hours and activation at 400 ℃ for 3 hours to obtain a hydrogenation catalyst DC9.

TABLE 1

Note: m represents (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Value of (A)

TABLE 2

TABLE 3

As can be seen from the results in Table 1, the phosphorus-containing pseudoboehmite prepared by the preferred method of the present invention has a characteristic of 1.7. Ltoreq. H.ltoreq.3, preferably 2.2. Ltoreq. H.ltoreq.2.8, while various pseudoboehmite prepared by the prior art method as well as the non-preferred method of the present invention have h values of less than 1.7. In an IR characteristic spectrogram of alumina obtained by roasting the phosphorus-containing pseudo-boehmite prepared by the method at 600 ℃, hydroxyl has a characteristic (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) 1.9-2.8, preferably 2-2.7, and the hydroxyl group characteristics (I) in the IR characterization spectra of the alumina obtained by calcining the pseudoboehmite prepared by the prior art method and the non-preferred method of the invention at 600 ℃ ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ )<1.8。

As can be seen from the results in Table 3, the hydrogenation catalysts prepared by the process of the present invention are characterized by Q of 1 to 3, preferably Q of 1.1 to 2.5, whereas the catalysts prepared by the processes of the prior art and the comparative examples generally have Q of less than 1 or more than 3.

Test example 1

This test example is intended to illustrate the hydrogenation activity and reaction stability of the hydrogenation catalyst of the present invention.

The hydrogenation catalysts prepared in the above 100mL examples 1 to 15 and comparative examples 1 to 9 were crushed into particles with a diameter of 2 to 3 mm and then presulfided under the following conditions: the vulcanized oil adopts 5w percent of dimethyl disulfide/Jingmen normal first-line kerosene, and the liquid hourly volume space velocity of the vulcanized oil is 1.2h ^-1 Hydrogen partial pressure of 14.0MPa and hydrogen-oil volume ratio of 500, and vulcanizing at constant temperature of 360 ℃ for 3 hours; the evaluation was then carried out in a 100ml small fixed bed reactor (catalyst loading 100 ml). The raw material is inferior normal slag of a Shanghai petrochemical atmospheric and vacuum distillation unit (as a heavy oil raw material, the sulfur content is 3.5 weight percent, the nitrogen content is 0.19 weight percent, the carbon residue value is 11.2 weight percent, the nickel content is 21.4 mu g/g, and the vanadium content is 66.6 mu g/g), the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly volume space velocity is 0.6 hour ^-1 Hydrogen to oil volume ratio of 600And (5) carrying out hydrogenation activity performance test. Specifically, the products after 200h and 2000h of reaction were tested for the removal rate of (Ni + V), the desulfurization rate, the decarburization rate and the denitrification rate, and the results are shown in Table 4.

Wherein the calculation methods of the (Ni + V) removal rate, the desulfurization rate, the carbon residue removal rate and the denitrification rate are the same; the invention takes the removal (Ni + V) rate as an example to illustrate the calculation method, wherein the removal (Ni + V) rate = (Ni + V) content in raw material- (Ni + V) content in hydrogenated product)/(Ni + V) content in raw material.

The nickel and vanadium content in the oil sample was determined by inductively coupled plasma emission spectrometry (ICP-AES) (the instrument used was a PE-5300 model plasma photometer from PE corporation, USA, the specific method is described in petrochemical analysis method RIPP 124-90). The sulfur content in the oil sample is measured by an electric quantity method (the specific method is shown in petrochemical analysis method RIPP 62-90). The content of carbon residue in the oil sample is determined by a micro-method (the specific method is shown in petrochemical analysis method RIPP 149-90). The nitrogen content in the oil sample is determined by a chemiluminescence method (the specific method is shown in petrochemical analysis method RIPP SH 0704-Z).

TABLE 4

As can be seen from Table 4, the hydrogenation catalyst provided by the invention has better heteroatom removal effect under the same other conditions, thereby reflecting better hydrogenation activity; furthermore, as can be seen from the data measured after 200h and 2000h of reaction in table 4, the hydrogenation catalyst provided by the present invention has better reaction stability under the same conditions.

Test example 2

The desulfurization and denitrification activity of the hydrogenation catalyst of the invention is exemplified by example 1 and example 7, and comparative examples 1-2 and comparative example 9.

Respectively crushing the catalyst into 2-4 mm particles, and pre-vulcanizing on a 30 ml hydrogenation device, wherein the pre-vulcanizing conditions comprise: the sulfurated oil adopts 5w percent of carbon disulfide/cyclohexane, the hydrogen partial pressure is 6MPa, and the liquid hourly space velocity is0.8 hour ^-1 Hydrogen-oil volume ratio of 800, and vulcanizing at a constant temperature of 360 ℃ for 3 hours; then, the catalyst is evaluated, and the used raw oil is Shanghai catalytic diesel with 3150 mu g/g of sulfur content and 454 mu g/g of nitrogen content. The evaluation conditions were: the reaction temperature is 360 ℃, the hydrogen partial pressure is 6MPa, and the liquid hourly space velocity is 2 hours ^-1 The volume ratio of hydrogen to oil was 300. The results of the hydrodesulfurization and denitrification activity tests are shown in Table 5.

Wherein, the hydrodesulfurization activity of the catalyst is calculated according to 1.65 grade, the hydrodenitrogenation activity is calculated according to 1 grade reaction, and the calculation formulas are respectively as follows:

TABLE 5

As can be seen from the data in table 5, the hydrogenation catalyst provided by the present invention has higher desulfurization and denitrification activity compared to the existing catalysts.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A hydrogenation catalyst comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises at least one VIB group metal component and at least one VIII group metal component, and the carrier is phosphorus-containing alumina;

when the hydrogenation catalyst is measured by Diffuse Reflection Ultraviolet Visible Spectrum (DRUVS), the absorbances at 630nm and 500nm are respectively F ₆₃₀ And F ₅₀₀ And the ratio of the two Q = F ₆₃₀ /F ₅₀₀ Is 1 to 3;

in the IR spectrum of the phosphorus-containing alumina, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Is 1.9-2.8, wherein, I ₃₆₇₀ Is 3670cm ^-1 Peak height, I ₃₅₈₀ Is 3580cm ^-1 Peak height, I ₃₇₇₀ Is 3770cm ^-1 Peak height, I ₃₇₂₀ Is 3720cm ^-1 Peak height.

2. The hydrogenation catalyst of claim 1, wherein Q is 1.1 to 2.5.

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

4. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the support is present in an amount of from 30 to 99 wt.%, calculated as oxides, based on the total amount of the hydrogenation catalyst, of from 0.5 to 50 wt.% of the group VIB metal component and from 0.5 to 20 wt.% of the group VIII metal component.

5. The hydrogenation catalyst according to claim 4, wherein the carrier is present in an amount of 40 to 94 wt.%, the group VIB metal component is present in an amount of 5 to 45 wt.%, 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.

6. A hydrogenation catalyst according to any one of claims 1 to 3, wherein Al is present in the total amount of the phosphorus-containing alumina ₂ O ₃ In an amount of 94-99 wt.%; p ₂ O ₅ Is contained in an amount of 1 to 6% by weight.

7. The hydrogenation catalyst according to claim 6, wherein the total amount of the phosphorus-containing alumina is Al ₂ O ₃ In an amount of 95 to 98 wt.%; p ₂ O ₅ Is contained in an amount of 2 to 5 wt%.

8. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the phosphorus-containing alumina has an IR spectrum in which (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Is 2 to 2.7; wherein, I ₃₆₇₀ Is 3670cm ^-1 Peak height, I ₃₅₈₀ Is 3580cm ^-1 Peak height, I ₃₇₇₀ Is 3770cm ^-1 Peak height, I ₃₇₂₀ Is 3720cm ^-1 Peak height.

9. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the phosphorus-containing alumina is calcined from a phosphorus-containing pseudo-boehmite.

10. The hydrogenation catalyst according to claim 9, wherein h of the pseudo-boehmite containing phosphorus satisfies 1.7. Ltoreq. H.ltoreq.3, wherein h = D (031)/D (020), wherein D (031) represents a crystal grain size of a crystal face represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents a crystal grain size of a crystal face represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, wherein the 031 peak represents a peak having a2 θ of 34 to 43 ° in the XRD spectrum, wherein the 020 peak represents a peak having a2 θ of 10 to 15 ° in the XRD spectrum, D = K λ/(Bcos θ), K is a Scherrer constant, λ is a diffraction wavelength of the target material, B is a half-width of a diffraction peak, and 2 θ is a position of the diffraction peak.

11. The hydrogenation catalyst according to claim 10, wherein h of the pseudoboehmite satisfies 1.9. Ltoreq. H.ltoreq.3.

12. The hydrogenation catalyst according to claim 11, wherein h of the pseudoboehmite satisfies 2.2. Ltoreq. H.ltoreq.2.8.

13. A process for the preparation of a hydrogenation catalyst as claimed in any one of claims 1 to 12, which process comprises the steps of:

14. The method of claim 13, wherein the temperature of the activation is 610-780 ℃.

15. The method of claim 14, wherein the temperature of the activation is 630-750 ℃.

16. The method of claim 15, wherein the temperature of the activation is 650-730 ℃.

17. The production method according to any one of claims 13 to 16, wherein the activation temperature-rising rate of the activation is 50 to 600 ℃/hr.

18. The production method according to claim 17, wherein the activation temperature-raising rate of the activation is 100 to 550 ℃/hr.

19. The method of any one of claims 13-16, wherein the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

20. The preparation method of any one of claims 13 to 16, wherein the content of the phosphorus-containing alumina is 30 to 99 wt%, calculated as oxides, based on the total amount of the hydrogenation catalyst, the content of the group VIB metal component is 0.5 to 50 wt%, and the content of the group VIII metal component is 0.5 to 20 wt%.

21. The preparation method of claim 20, wherein the content of the phosphorus-containing alumina is 40-94 wt%, the content of the VIB group metal component is 5-45 wt% and the content of the VIII group metal component is 1-15 wt% calculated by oxide, based on the total amount of the hydrogenation catalyst.

22. The method of any one of claims 13-16, wherein the hydrogenation-active metal component is supported on the phosphorus-containing alumina by impregnating the phosphorus-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.

23. The method according to claim 22, wherein the drying temperature is 50 to 350 ℃ and the drying time is 1 to 12 hours.

24. The method according to claim 23, wherein the drying temperature is 80 to 250 ℃ and the drying time is 2 to 8 hours.

25. The production method according to any one of claims 13 to 16, wherein Al is based on the total amount of the phosphorus-containing alumina ₂ O ₃ In an amount of 94-99 wt.%; p ₂ O ₅ Is contained in an amount of 1 to 6% by weight.

26. The method according to claim 25, wherein Al is contained in the total amount of the phosphorus-containing alumina ₂ O ₃ In an amount of 95 to 98 wt.%; p is ₂ O ₅ Is contained in an amount of 2 to 5 wt%.

27. The production method according to any one of claims 13 to 16, wherein the production method of the phosphorus-containing alumina comprises the steps of:

(1-3) roasting the solid product obtained by ageing in the step (1-2) to obtain phosphorus-containing alumina;

28. The production method according to claim 27, wherein the precipitation reaction or the hydrolysis reaction of step (1-1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5.

29. The method of claim 27, wherein the precipitation reaction and the hydrolysis reaction are each independently at a temperature of 30-90 ℃.

30. The production method according to claim 27, wherein the conditions of the precipitation reaction 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 deg.C, and the reaction time is 2-30 hr.

31. The production method according to claim 30, wherein the conditions of the precipitation reaction 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.

32. The production method according to claim 27, wherein the grain growth regulator is a substance capable of regulating the growth rate of grains in a 020 crystal plane and a 031 crystal plane.

33. The production method according to claim 32, wherein the grain growth regulator is at least one of a polyhydric sugar alcohol and a carboxylate and a sulfate thereof.

34. The method of claim 33, wherein the grain growth regulator is selected from at least one of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, gluconate, and sulfate.

35. The method of claim 27, wherein the grain growth regulator is present in an amount of 1 to 10 wt.% based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the weight of alumina.

36. The method according to claim 35, wherein the grain growth regulator is used in an amount of 1.5 to 8.5 wt% based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the weight of alumina.

37. The method according to claim 36, wherein the grain growth regulator is used in an amount of 2 to 6 wt% based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the weight of alumina.

38. The method according to claim 27, wherein the grain growth regulator is used in an amount of 1 to 10 wt% based on the weight of the organic aluminum-containing compound in the hydrolysis reaction.

39. The method of claim 38, wherein the grain growth regulator is present in an amount of 1.5-8.5 wt.% based on the weight of the organic aluminum-containing compound in the hydrolysis reaction.

40. The preparation method according to claim 39, wherein the grain growth regulator is used in an amount of 2 to 6 wt% based on the weight of the organic aluminum-containing compound in the hydrolysis reaction.

41. The production method according to claim 27, 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.

42. The method according to claim 27, wherein the phosphorus-containing compound is used in an amount such that the obtained phosphorus-containing alumina contains P in an amount based on the total amount of the phosphorus-containing alumina ₂ O ₅ Is contained in an amount of 1 to 6% by weight.

43. The process according to claim 42, wherein the phosphorus-containing compound is used in an amount such that P is contained in the obtained phosphorus-containing alumina based on the total amount of the phosphorus-containing alumina ₂ O ₅ Is contained in an amount of 2 to 5 wt%.

44. The method according to claim 27, wherein the aging in the step (1-2) is carried out at a pH of 8 to 10.

45. The method of claim 27, wherein the temperature of aging is 50-95 ℃; the aging time is 0.5-8 hours.

46. The method of claim 45, wherein the temperature of aging is 55-90 ℃; the aging time is 2-6 hours.

47. The production method according to claim 27, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate.

48. The preparation method of claim 27, wherein the organic aluminum-containing compound is at least one of aluminum alkoxides which can be hydrolyzed with water to generate a precipitate of hydrated alumina.

49. The production method according to claim 27, wherein 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.

50. The method of claim 27, wherein the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.

51. Use of the hydrogenation catalyst according to any one of claims 1 to 12 or the hydrogenation catalyst produced by the production method according to any one of claims 13 to 50 in a hydrogenation reaction of hydrocarbon oil.