CN113559918B

CN113559918B - Hydrogenation catalyst, preparation method and application thereof

Info

Publication number: CN113559918B
Application number: CN202010352287.XA
Authority: CN
Inventors: 贾燕子; 聂红; 杨清河; 曾双亲; 刘学芬; 王轶凡; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2023-03-10
Anticipated expiration: 2040-04-28
Also published as: CN113559918A

Abstract

The invention relates to the technical field of hydrogenation catalysts, and discloses a hydrogenation catalyst, a preparation method and an application thereof, wherein the catalyst comprises a composite carrier and a hydrogenation active metal component loaded on the composite carrier, the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, and the composite carrier comprises solid acid and 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, and discloses a hydrogenation catalyst, and a preparation method and application thereof.

Background

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 kinds of hydroxyl groups on the surface.

Therefore, how to optimize the acting force between the matched metal and the carrier through the upgrading of the carrier property and the catalyst preparation process, improve the stability of the active phase of the catalyst, improve the diffusion performance and the scale holding capacity of the catalyst, and reduce the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process is the key for improving the activity stability 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. introducing phosphorus in the processes of gelatinizing, aging and washing, 2, introducing phosphorus in the process of forming or dipping and the like. CN102247882A discloses a method for preparing phosphorus modified alumina by adding a phosphorus-containing compound in the formation process of 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, but the method is liable to cause a decrease in specific surface area and pore volume.

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 liquid, 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: layered clay and silicon-containing alumina are taken as carriers, and one or more of molybdenum, tungsten, nickel and cobalt are taken as active components; molybdenum and/or tungsten compounds and/or nickel and/or cobalt compounds and deionized water or ammonia water are mixed to prepare active metal solution, the solution is sprayed and soaked on the carrier in an atomized state by adopting a saturated spraying and soaking method, then the carrier is dried for 1 to 8 hours at the temperature of between 80 and 150 ℃, and then the carrier is roasted for 2 to 6 hours in the air at the temperature of between 300 and 650 ℃, so that the catalyst is prepared. 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 defect that the hydrogenation activity of a hydrogenation catalyst in the prior art needs to be further improved, and provides a hydrogenation catalyst, 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 composite support containing a phosphorus-containing alumina and a solid acid and performing activation, and the conditions defining the activation include: the temperature is 600-800 ℃, the time is 1-10 hours, thereby preparing the specific hydrogenation catalyst, and the absorbances of the hydrogenation catalyst at 630nm and 500nm 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, a first aspect of the present invention provides a hydrogenation catalyst, which comprises a composite carrier and a hydrogenation-active metal component supported on the composite 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 composite carrier comprises a solid acid and a 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.

Preferably, Q is 1.1-2.5.

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

(1) Mixing pseudo-boehmite containing phosphorus and/or alumina containing phosphorus with solid acid, and then roasting to obtain a composite carrier;

(2) Loading a hydrogenation active metal component onto the composite carrier, followed by optional drying;

(3) Activating the solid product obtained in the step (2), 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 composite carrier containing the phosphorus-containing alumina and the solid acid, 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 loads the hydrogenation active metal component on the composite carrier and carries out specific activation treatment, so that the prepared hydrogenation catalyst has 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 composite carrier and a hydrogenation active metal component loaded on the composite carrier, wherein the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, and the composite carrier comprises a solid acid and 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.

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 to 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 composite carrier 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.

In the invention, the content 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 composite 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 composite carrier is 40 to 94 wt%, calculated as oxides, 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%. 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 present invention, the solid acid is preferably contained in an amount of 1 to 99 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 12 to 50 parts by weight, based on the total amount of the composite carrier. The preferable technical scheme of the invention is favorable for improving the hydrogenation activity of the prepared hydrogenation catalyst.

According to the present invention, the specific kind of the solid acid can be selected from a wide range as long as it can be used as a cracking active component; preferably, the solid acid is silica-alumina and/or molecular sieve.

According to the invention, the molecular sieve can be selected from a wide range, and can be zeolite with a large pore structure, such as at least one of faujasite, beta zeolite and omega zeolite; it may also be a zeolite having a mesoporous structure, such as at least one of zeolites having a mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, ZSM-57 zeolite structure; and may also be a zeolite having a small pore structure, such as a zeolite having the structure of an Erionite zeolite and/or a ZSM-34 zeolite; preferably, the molecular sieve is selected from at least one of faujasite, zeolite Beta, zeolite omega, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, ZSM-57 zeolite, erionite zeolite and ZSM-34 zeolite.

According to the present invention, preferably, the solid acid is selected from at least one of faujasite, zeolite Beta, ZSM-5 zeolite, mordenite and silica-alumina. The silica-alumina is preferably a silica-alumina having a pseudo-boehmite structure, which may be commercially available or prepared using any one of the prior art techniques. For example, the Siral series commercial silica-alumina produced by Condea, germany, has a pseudo-boehmite structure, and can be used as the solid acid component in the present invention. More preferably, the faujasite is a Y-type zeolite, more preferably at least one of HY zeolite, phosphorus-type Y zeolite REY, phosphorus-type HY zeolite REHY, ultrastable Y zeolite USY, partially amorphized USY, phosphorus-type ultrastable Y zeolite REUSY, titanium-containing Y zeolite, phosphorus-containing Y and ultrastable and HY type zeolites, and dealuminized Y type zeolites.

Preferably, the composite carrier contains phosphorus element, and Al is based on the total amount of the phosphorus-containing alumina 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 IR spectrum of the phosphorus-containing alumina is (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 model 870 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 of 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 0.5-1.6 ml/g, and the BET nitrogen adsorption method specific surface area is 270-480 square meters/g.

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 to the above-mentioned phosphorus-containing pseudo-boehmite 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, where h = D (031)/D (020), where D (031) represents a crystal grain size of a crystal plane 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 plane represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, where the 031 peak represents a peak of 34 to 43 ° 2 θ in the XRD spectrum, the 020 peak represents a peak of 10 to 15 ° 2 θ in the XRD spectrum, D = K λ/(Bcos θ), K is a Scherrer constant, λ is a diffraction wavelength of the target-type 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, and still more 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 satisfying 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, and the scanning speed was 2 DEG/min.

In the invention, the pseudo-boehmite containing phosphorus contains phosphorus and has a specific crystal structure, so that the hydrogenation catalyst prepared by taking the alumina containing phosphorus prepared from the pseudo-boehmite containing phosphorus as a carrier component 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 and IIIB 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 0.5-6 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 composite carrier containing a phosphorus-containing alumina and a solid acid. 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 present invention, the solid acid is preferably used in an amount such that the solid acid is contained in the composite carrier obtained in an amount of 1 to 99 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 12 to 50 parts by weight, based on the total amount of the composite carrier. The preferable technical scheme of the invention is favorable for improving the hydrogenation activity of the prepared hydrogenation catalyst.

In the present invention, the specific kind of the solid acid can be selected from a wide range as long as it can be used as a cracking active component; preferably, the solid acid is silica-alumina and/or molecular sieve. The types of the silica-alumina and the molecular sieve are the same as those of the silica-alumina and the molecular sieve of the first aspect, and are not described in detail herein.

According to a preferred embodiment of the present invention, the step (1) comprises: mixing pseudo-boehmite containing phosphorus and/or alumina containing phosphorus with solid acid, and then sequentially carrying out forming, drying and roasting to obtain the composite carrier.

In the present invention, the mixing manner, molding conditions, drying conditions and firing conditions of the pseudo-boehmite containing phosphorus and/or alumina containing phosphorus and the solid acid in the step (1) are not particularly limited and may be those conventionally used in the art. The mixing mode can be a simple stacking mode of putting the solid product and the solid acid at one position, or can be a mode of directly mixing the solid product and the solid acid in a stirrer or a grinder by stirring, or can be a mode of mixing the solid product, the solid acid and water under the condition of sufficient slurrying and then filtering, drying or not drying; when the mixing is carried out by any one of the prior arts, the uniformity to be achieved by the mixing can be controlled by those skilled in the art as necessary, and the present invention is not particularly limited. The forming method can be at least one of rolling ball, tabletting and extrusion forming, preferably extrusion forming, and then drying and roasting are carried out; in order to ensure that the molding is carried out smoothly, water, extrusion assistant and/or adhesive, and optionally pore-expanding agent, may be added, the types and amounts of the extrusion assistant, peptizer and pore-expanding agent are known to those skilled in the art, for example, common extrusion assistant may be selected from at least one of sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyvinyl alcohol, the peptizer may be organic acid and/or organic acid, and the pore-expanding agent may be at least one of starch, synthetic cellulose, polymeric alcohol and 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 preferably include: the drying temperature may be 40-350 deg.C, more preferably 100-200 deg.C; the drying time may be 1 to 24 hours, more preferably 2 to 12 hours. The conditions for the calcination preferably include: the roasting temperature can be 350-1000 ℃, and is more preferably 400-800 ℃; the calcination time may be 1 to 10 hours, more preferably 2 to 6 hours.

According to the present invention, there is no particular limitation on the group VIB metal component and the group VIII metal component, and the group VIB metal component is preferably Mo and/or W and the group VIII metal component is preferably Co and/or Ni.

The invention has wider selection range of the dosage of the composite carrier and the hydrogenation active metal component; preferably, the composite carrier and the hydrogenation active metal component are used in amounts such that the content of the composite carrier in the prepared hydrogenation catalyst is 30-99 wt%, based on the total amount of the hydrogenation catalyst, the content of the group VIB metal component is 0.5-50 wt%, and the content of the group VIII metal component is 0.5-20 wt%, calculated as oxides.

Further preferably, the composite carrier and the hydrogenation active metal component are used in amounts such that, in the prepared hydrogenation catalyst, based on the total amount of the hydrogenation catalyst, the content of the composite 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 on oxide. More preferably, the content of the composite carrier is 76-90 wt%, the content of the VIB group metal component is 8-18 wt% and the content of the VIII group metal component is 2-6 wt% calculated by oxide, based on the total amount of the hydrogenation catalyst.

The method for supporting the hydrogenation active metal component on the composite carrier in the present invention is not particularly limited as long as the hydrogenation active metal component is supported on the composite carrier, and may be any conventional method in the art, for example, a kneading method, a dry blending method, an impregnation method; preferably, the method for loading the hydrogenation active metal component on the composite carrier comprises the steps of impregnating the composite carrier with an impregnating solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then drying.

Further according to the invention, the group VIB metal compound and the group VIII metal compound are each independently selected from at least one of their soluble compounds (including the corresponding metal compounds soluble in water in the presence of a co-solvent). 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, and cobalt chloride, preferably cobalt nitrate and/or basic cobalt carbonate, for example cobalt, and 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, aluminates, molybdates, 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 nitrate, nickel acetate, basic nickel carbonate, nickel chloride, and nickel carbonate.

According to the invention, the invention may also contain organic additives during the catalyst preparation, such as during the preparation of the soluble compounds of the group VIB metal compounds and the group VIII metal compounds. 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 selected from at least one of 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 of 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-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid, and preferably at least one of ethylene glycol, glycerol, polyethylene glycol and citric acid; the nitrogen-containing organic 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 particularly limit the impregnation method and the impregnation time, and the impregnation method may be excess liquid impregnation, pore saturation impregnation, multiple impregnation, etc. depending on the amount of the impregnation liquid, and may be immersion method, spray impregnation, etc. depending on 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 present invention, the drying conditions in the method of supporting the hydrogenation active metal component on the composite carrier are not particularly limited, and preferably, the drying conditions include: the drying temperature is 50-350 ℃, the drying time is 1-12 hours, the preferred drying temperature is 80-250 ℃, and the drying time is 2-8 hours. 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.

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

(1) Mixing pseudo-boehmite containing phosphorus with solid acid, and then roasting to obtain a composite carrier;

The preparation method of the pseudo-boehmite containing phosphorus is not particularly limited as long as the performance of the catalyst is favorably improved; preferably, the preparation method of the pseudo-boehmite containing phosphorus comprises the following steps:

(1-1) contacting an inorganic aluminum-containing compound solution with acid or alkali to carry out precipitation reaction, or contacting an organic aluminum-containing compound with water to carry out 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;

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

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 lower pH condition is kept, the excessive growth of pseudo-boehmite grains 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 both phosphorus-containing 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) comprises: 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 for the precipitation reaction are selected from a wide range, and preferably, the conditions for 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 mode 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 amount of the grain growth regulator used in the hydrolysis reaction is 1 to 10 wt%, preferably 1.5 to 8.5 wt%, and more preferably 2 to 6 wt% based on the weight of the organic aluminum-containing compound.

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

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 is contained in the prepared pseudo-boehmite containing phosphorus, based on the total amount of the pseudo-boehmite containing phosphorus 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 present 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. Because of the low price, aluminum sulfate solutions and/or aluminum chloride solutions are preferred. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as 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 present invention, the organic aluminum-containing compound in step (1-1) may be at least one of various aluminum alkoxides which undergo a hydrolysis reaction with water to produce a precipitate of hydrated aluminum oxide, and may be, for example, at least one of aluminum isopropoxide, aluminum isobutylate, aluminum triisopropoxide, aluminum tributoxide and aluminum isooctanolate.

According to the present invention, the acid in step (1-1) may be various protonic acids or oxides that are acidic in an aqueous medium, for example, may be at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid, and preferably, the protonic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid. The carbonic acid may be generated in situ by passing carbon dioxide into the 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 present invention, the base used in step (1-1) may be a hydroxide or a salt hydrolyzed in an aqueous medium to make the aqueous solution alkaline, preferably, the hydroxide is at least one selected from the group consisting of ammonia, 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 that the pH value is 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 in 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 ℃.

According to the invention, any auxiliary agent which does not affect the performance of the hydrogenation catalyst or can improve the performance of the hydrogenation catalyst can be introduced, the auxiliary agent can be at least one of elements in groups IA, IIA, IIIA, IVA, VA, VIIA, IIB and IIIB and rare earth metal elements, preferably at least one of boron, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated by single element elements does not exceed 10 wt% based on the catalyst, and is preferably 0.5-6 wt%. The method of introducing the assistant in the present invention is not particularly limited, and for example, the assistant may be added during the precipitation reaction or hydrolysis reaction in the step (1-1), during the aging or washing in the step (1-2), or may be introduced by mixing, molding and calcining the assistant with the precursor of the inorganic aluminum-containing compound and/or the organic aluminum-containing compound in the step (1-1), or by preparing a solution containing the assistant, and then impregnating the composite support with the solution and calcining. In the introduction of the auxiliary, the calcination conditions are not particularly limited, and preferably, the calcination temperature is 200 to 800 ℃, more preferably 300 to 700 ℃, and the calcination time is 2 to 8 hours, more preferably 3 to 6 hours.

(1) Mixing phosphorus-containing alumina with solid acid, and then roasting to obtain a composite carrier;

Preferably, the phosphorus-containing alumina is obtained by roasting the phosphorus-containing pseudo-boehmite, and is preferably obtained by roasting the phosphorus-containing pseudo-boehmite prepared by the preferred method. The roasting conditions are the same as the corresponding roasting conditions in the first aspect, and are not described in detail herein.

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 value to 7-10.5, aging at 50-95 ℃ for 0.5-8 hours, filtering, washing, drying, and optionally roasting to obtain a solid product;

mixing the solid product with solid acid, and then sequentially carrying out forming, drying and roasting to obtain a composite carrier;

(2) Impregnating the composite carrier with an impregnation solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then optionally drying at 50-350 ℃ for 1-12 hours;

(3) And (3) activating the solid product obtained in the step (2) 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 when the hydrogenation catalyst is used are not particularly limited, and reaction conditions which are usual in the art can be adopted; preferably, the reaction temperature is 200-420 ℃, more preferably 220-400 ℃, the pressure is 2-18MPa, more preferably 2-16MPa, and the liquid hourly space velocity is 0.1-10 hours ^-1 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 reactor apparatus in the present invention for applying the hydrogenation catalyst 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 an ebullating 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 to perform 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 generalMeasured by Nicolet 870 type Fourier infrared spectrometer of Nicolet company in America. 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 at 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 composition of the catalyst is determined by X-ray fluorescence spectroscopy (namely XRF), and the specific method is shown in petrochemical analysis method RIPP133-90.

The content of alumina and the content of phosphorus oxide in the phosphorus-containing alumina are measured by adopting an X-ray fluorescence spectrometry, and the specific surface area and the pore volume are measured by adopting a mercury intrusion method.

The formation of the 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 serves to illustrate the hydrogenation catalyst and the process for its preparation according to the invention.

(1) Preparation of hydrated alumina PA1:

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 calculated for PA1 by XRD characterization are listed in Table 1. Relative crystallinity of PA1 and P ₂ O ₅ The contents are also shown in Table 1.

PA1 is roasted for 4 hours at 600 ℃ to obtain the phosphorus-containing alumina. The hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy. (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (A) are listed in Table 1.

(2) Preparing a composite carrier Z1:

100g of PA1 and 100g of Y-type molecular sieve (a product of ChangLing division of China petrochemical catalyst, 93 wt% of dry basis) are mixed and extruded into a trefoil wet strip with the circumcircle diameter of 1.6 mm, the wet strip is dried for 3 hours at 120 ℃, and then is roasted for 4 hours at 600 ℃ to obtain the composite carrier Z1. The pore volume, specific surface area and weight ratio of the solid acid of the composite carrier are shown in Table 2.

(3) Preparation of hydrogenation catalyst C1:

110 g of the composite carrier Z1 is taken, and 110 ml of mixed aqueous solution (containing MoO in the mixed aqueous solution) consisting of ammonium molybdate and nickel nitrate is used ₃ 240 g/l, niO 53 g/l) was impregnated into the support Z for 1 hour, dried at 110 ℃ for 4 hours, and activated at 650 ℃ for 3 hours to obtain a hydrogenation catalyst C1. The content of metal oxides in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are listed in table 3.

Comparative example 1

A composite support DZ1 and a hydrogenation catalyst DC1 were prepared and tested according to the method of example 1, except that the activation conditions were: activating at 420 ℃ for 3 hours.

Comparative example 2

A composite support DZ2 and a hydrogenation catalyst DC2 were prepared and tested according to the method of example 1, except that the activation conditions were: activation at 820 deg.C for 3 hours.

Example 2

A composite support Z2 and a hydrogenation catalyst C2 were prepared as in example 1, except that only aluminum sulfate solution was added8.0mL of phosphoric acid having a concentration of 85% by weight, but not including ribitol, gave hydrated alumina PA2. The method of example 1 was followed and characterized by XRD, PA2 had a pseudo-boehmite structure, 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.

Example 3

The composite carrier Z3 and the hydrogenation catalyst C3 were prepared according to 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 precipitation reaction was completed, 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 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.

Comparative example 3

A composite 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 of (A) 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.

Example 4

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

(1) Preparation of hydrated alumina PA4:

4000 mL of a solution of aluminum trichloride having a concentration of 45 g of alumina/l and containing 22.1mL of concentrated phosphoric acid having a concentration of 85% by weight and 2.52 g/l of sorbitol and 1000 mL of a solution of sodium metaaluminate having a concentration of 210 g of alumina/l and a caustic factor of 1.58 were co-currently charged in a 2-liter reaction tank to carry out a precipitation reaction at a reaction temperature of 80 ℃ with the flow rate of the reactants 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 filter cake after washing into 3 liters 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 ℃, drying the material for about 2 minutes, and drying 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 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.

(2) Preparing a composite carrier Z4:

100g of PA4 and 20g of ZSM-5 (a product of China petrochemical catalyst ChangLing division, a dry basis is 94 weight percent) calculated by alumina are mixed and extruded into butterfly-shaped wet strips with the circumscribed circle diameter of 1.5 mm, the wet strips are dried for 3 hours at 120 ℃, and are roasted for 4 hours at 560 ℃ to obtain the composite carrier Z4. The pore volume, specific surface area and weight ratio of the solid acid of the composite carrier are shown in Table 2.

(3) Preparation of hydrogenation catalyst C4:

100g of the composite carrier Z4 was taken, and 110 ml of a mixed aqueous solution (containing MoO in the mixed aqueous solution) consisting of ammonium molybdate and cobalt nitrate was used ₃ 157 g/l, coO 31 g/l) was impregnated into the support Z for 4 hours, then dried at 120 ℃ for 3 hours, and then activated at 650 ℃ for 3 hours to obtain a hydrogenation catalyst C4. The describedThe content of metal oxides in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are shown in Table 3.

Example 5

A composite carrier Z5 and a 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. The method of example 1 was followed and characterized by XRD, PA5 had a pseudoboehmite structure, and the h-value of PA5 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.

Example 6

A composite carrier Z6 and a 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 precipitation reaction was completed, 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 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.

Comparative example 4

A composite support DZ4 and a hydrogenation catalyst DC4 were prepared according to the method 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 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 shown in Table 1The content of solid acid in the composite carrier and the pore volume and specific surface area of the composite carrier are shown in table 2.

Example 7

(1) Preparation of hydrated alumina PA7:

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. The PA7 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of PA7 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.

(2) Preparing a composite carrier Z7:

weighing 100g of hydrated alumina PA7 and 30 g of silica-alumina (a product of Zhongpetrochemical catalyst ChangLing division, dry basis 80 wt.%), mixing, extruding into butterfly-shaped wet strips with the circumscribed circle diameter of 1.5 mm, drying the wet strips at 120 ℃ for 3 hours, and roasting at 570 ℃ for 4 hours to obtain the composite carrier Z3. The pore volume, specific surface area and weight ratio of solid acid of the composite carrier are shown in table 2.

(3) Preparation of hydrogenation catalyst C7:

taking 100g of composite carrier Z7, and adding 110 ml of mixed water consisting of ammonium metatungstate and nickel nitrateSolution (the mixed water solution contains MoO ₃ 102 g/l, niO 29 g/l) was impregnated into the support Z for 7 hours, dried at 110 ℃ for 4 hours, and activated at 650 ℃ for 3 hours to obtain hydrogenation catalyst C7. The content of metal oxide in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are shown in table 3.

Example 8

A composite support Z8 and a hydrogenation catalyst C8 were prepared according to the method of example 7, except that: and (2) in the precipitation reaction process of the step (1), regulating the flow rate of reactants to ensure that the neutralization pH value is 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. The weight ratio of the solid acids in the composite carrier Z4 and the pore volume and specific surface area thereof are shown in table 2. The content of metal oxide in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are shown in table 3.

Example 9

A composite carrier Z9 and a hydrogenation catalyst C9 were prepared according to the method of example 8, except that the aluminum sulfate solution contained no gluconic acid, to obtain hydrated alumina PA9. The method of example 1 was followed and characterized by XRD, PA9 had a pseudo-boehmite structure, and the h-value of PA9 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 (b) are shown in table 1, and the contents of solid acids in the composite carrier and the pore volume and specific surface area of the composite carrier are shown in table 2.

Example 10

A composite support Z10 and a hydrogenation catalyst C10 were prepared by following the procedure of example 8, except that the sodium metaaluminate solution was directly controlledThe flow rate ensures that the pH value of the reaction system is 9.5, and after the precipitation reaction is finished, sodium carbonate solution is not required to be added into the slurry to adjust the pH value, so that the hydrated alumina PA10 is obtained. 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 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.

Comparative example 5

A composite support DZ5 and a hydrogenation catalyst DC5 were prepared according to the method of example 8, except that concentrated phosphoric acid was not contained in the aluminum sulfate solution, to give hydrated alumina CPA5. According to the method of example 1, CPA5 has a pseudo-boehmite structure and the XRD characterization calculates that the h value of CPA5 is 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 content of solid acid in the composite carrier and the pore volume and specific surface area of the composite carrier are shown in Table 1 and Table 2, respectively.

Example 11

(1) Preparation of hydrated alumina PA11:

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 PA11. Characterization by XRD according to the method of example 1, PA11 with pseudothin waterThe structure of the aluminum-based alloy, calculated by XRD characterization, is shown in Table 1 as h value of PA11, 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.

(2) Preparing a composite carrier Z11:

100g of PA11 and 42.6g of Y-type molecular sieve (a product of ChangLing division of China petrochemical catalyst, 93 wt% of a dry base) calculated by alumina are mixed and extruded into butterfly-shaped wet strips with the circumscribed circle diameter of 1.5 mm, the wet strips are dried for 3 hours at 120 ℃, and are roasted for 4 hours at 570 ℃ to obtain the composite carrier Z11. The pore volume, specific surface area and weight ratio of the solid acid of the composite carrier are shown in Table 2.

(3) Preparation of hydrogenation catalyst C11:

100g of the composite carrier Z11 was taken, and 110 ml of a mixed aqueous solution (containing MoO) composed of ammonium metatungstate and cobalt nitrate was used ₃ 194 g/l, niO 55 g/l) was impregnated into the support Z for 1 hour, dried at 110 ℃ for 4 hours, and activated at 650 ℃ for 3 hours to obtain a hydrotreating catalyst C11. The content of metal oxide in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are shown in table 3.

Example 12

A composite support Z12 and a hydrogenation catalyst C12 were prepared according to the method of example 11, except that no ribonic acid was added to the three-necked flask to obtain hydrated alumina PA12. The method of example 1 was followed and characterized by XRD, and PA12 has a pseudoboehmite structure, and the h-value of PA12 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.

Example 13

A composite support Z13 and a hydrogenation catalyst C13 were prepared as in example 11, except that, after the same amount of ribonic acid was added, followed by addition ofAqueous ammonia was added to adjust the pH to 8.5, then heated to 60 ℃, and then 500 grams of molten aluminum isopropoxide was slowly added dropwise to the flask via a separatory funnel to give hydrated alumina PA13. PA13 has a pseudo-boehmite structure as characterized by XRD according to the method of example 1, and h values of PA13 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.

Comparative example 6

A composite support DZ6 and a hydrogenation catalyst DC6 were prepared by following the procedure of example 11, except that concentrated phosphoric acid was not added to the three-necked flask, to obtain hydrated alumina CPA6. According to the method of example 1, CPA6 has a pseudo-boehmite structure and the XRD characterization calculates that the h value of CPA6 is 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 (b) are shown in table 1, and the contents of solid acids in the composite carrier and the pore volume and specific surface area of the composite carrier are shown in table 2.

Comparative example 7

The support DZ7 and the hydrogenation catalyst DC7 were prepared and tested accordingly as in example 11, except that the activation conditions were: activated at 430 ℃ for 3 hours.

Comparative example 8

The support DZ8 and the hydrogenation catalyst DC8 were prepared and tested accordingly as in example 11, except that the activation conditions were: activation at 820 ℃ for 3 hours.

Example 14

(1) Preparation of hydrated alumina PA14:

into a2 l three-necked flask with stirring and reflux condenser, 1000 g of an isopropyl alcohol-water azeotrope (water content 15 wt.%) was added, followed by addition ofAdding 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 dripping 500 g of molten aluminum isopropoxide into a flask through a separating funnel, reacting for 5 hours, adding ammonia water to adjust the pH value to 8.5, refluxing and reacting for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating hydrous isopropanol while aging, filtering the aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA14. PA14 has a pseudo-boehmite structure as characterized by XRD according to the method of example 1, and h values of PA14 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.

(2) Preparing a composite carrier Z14:

100g of PA14 and 62g of Y-type molecular sieve (a product of China petrochemical catalyst ChangLing division, 93 wt% of dry basis) calculated by alumina are mixed and extruded into butterfly-shaped wet strips with the circumscribed circle diameter of 1.5 mm, the wet strips are dried for 3 hours at 120 ℃, and are roasted for 4 hours at 570 ℃, so that the composite carrier Z14 is obtained. The pore volume, specific surface area and weight ratio of the solid acid of the composite carrier are shown in Table 2.

(3) Preparation of hydrogenation catalyst C14:

110 g of the composite support Z14 was taken, and 110 ml of a mixed aqueous solution composed of ammonium molybdate and nickel nitrate (the mixed aqueous solution contained WO) ₃ 365 g/l, niO 91 g/l) was impregnated into the support Z for 14 hours, dried at 110 ℃ for 4 hours, and activated at 700 ℃ for 3 hours to obtain hydrogenation catalyst C14. The content of metal oxide in the hydrogenation catalyst and the Q value representing the content of spinel structure in the catalyst are shown in table 3.

Example 15

The support Z15 and the hydrogenation catalyst C15 were carried out according to the method of example 14 and tested accordingly, except that the activation conditions were: activation is carried out for 3 hours at 630 ℃.

Example 16

The procedure of example 14 was followed for support Z16 and hydrogenation catalyst C16 and the corresponding tests were carried out, except that the activation conditions were: activation is carried out for 3 hours at 780 ℃.

Example 17

The procedure of example 14 was repeated except that the carrier Z17 and the hydrogenation catalyst C17 were prepared in the same manner as in the preparation of pseudo-boehmite containing phosphorus according to the method typical in "research on Carrier Material for heavy oil hydrogenation catalyst" except that 8.8mL of 85% concentrated phosphoric acid having a concentration of 57 g.L was added ^-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 pulped 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 PA17. The PA17 has a pseudo-boehmite structure according to the XRD characterization of the method of example 1, and the h value of the PA17 calculated by the 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.

Example 18

A support Z18 and a hydrogenation catalyst C18 were prepared according to the method of example 14, except that a phosphorus-modified pseudoboehmite catalyst support 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 causticity 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 meanwhile, 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; according to the mass of alumina added in the reaction process of the neutralization reaction kettle 1, calculating the volume of phosphoric acid solution with the concentration of the phosphorus pentoxide of 100g/L added into the aging reaction kettle, and adding the phosphoric acid into the aging reaction kettleThe content of phosphorus oxide is 4 percent of the content of aluminum oxide; and washing and drying after aging to obtain the pseudo-boehmite containing phosphorus. The characterization by XRD according to the method of example 1 shows that PA18 has a pseudo-boehmite structure, and the h value of PA18 calculated by XRD characterization is shown in Table 1, and the relative crystallinity is 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.

TABLE 1

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

TABLE 2

As can be seen from the results in Table 1, the phosphorus-containing pseudoboehmite prepared by the preferred method provided by the present invention has the characteristic of 1.7. Ltoreq. H.ltoreq.3, preferably 2.2. Ltoreq. H.ltoreq.2.8, while various pseudoboehmite prepared by non-preferred methods and methods of the prior art have h values less than 1.7. In an IR characteristic spectrogram of alumina obtained by roasting the phosphorus-containing pseudo-boehmite prepared by the optimal 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 non-preferred method and the method in the prior art are adopted to prepare the pseudoboehmite, and the alumina is obtained after roasting at 600 DEG CIn the IR characterization spectrum of (2), the hydroxyl group is characterized by (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ )<1.8。

Test example 1

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

The following hydrodesulfurization test and hydrodenitrogenation test were performed on the 4mL portions of the hydrogenation catalysts prepared in examples 1 to 18 and comparative examples 1 to 8, respectively, using a WFSP3050 continuous high-pressure reactor manufactured by Ware instruments of Tianjin, city. The catalyst was presulfided prior to testing. The prevulcanization conditions include: the vulcanized oil adopts cyclohexane containing 5w percent of carbon disulfide, and the liquid hourly volume space velocity of the vulcanized oil is 1.2h ^-1 The hydrogen partial pressure is 6MPa, the volume ratio of hydrogen to oil is 500, and the vulcanization is carried out for 3 hours at the constant temperature of 360 ℃.

The hydrodesulfurization test method comprises the following steps: taking n-decane solution with the mass content of 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) of 1 percent as raw material oil, then carrying out reaction for 5 hours under the conditions of 6MPa,350 ℃, the volume ratio of hydrogen to oil of 300 and the oil inlet flow of 8mL/h, then carrying out reaction for 6 hours, then sampling, analyzing a sample by using an HS-500 type high-frequency infrared sulfur and nitrogen detector, and expressing the activity by the desulfurization rate (average value of 10 samples) of 4,6-DMDBT, wherein the results are shown in Table 3.

The hydrodenitrogenation test method comprises the following steps: an n-heptane solution with the mass content of quinoline (Q) of 1% is used as raw material oil, then under the conditions of 4.0MPa,340 ℃, 400 volume ratio of hydrogen to oil and 8mL/h of oil inlet flow, after the reaction is stable for 3h, a sample is sampled after the reaction is carried out for 4h, the sample is analyzed by a HS-500 type high-frequency infrared sulfur and nitrogen measuring instrument, the activity is expressed by the denitrification rate of Q (the average value of 10 samples), and the result is shown in Table 3.

The desulfurization (nitrogen) rate X of the reaction was calculated by the following formula:

test example 2

This test example is intended to illustrate the hydrogenation activity of the hydrogenation catalyst of the present invention for aromatics.

Hydrogenation activity of aromatic hydrocarbonsThe test method comprises the following steps: the catalytic performance of the hydrogenation catalysts prepared in examples 1 to 18 and comparative examples 1 to 8 was evaluated using tetrahydronaphthalene as a model compound. The specific method comprises the following steps: crushing the catalyst into particles with the diameter of 0.3-0.45 mm, filling 2mL of the catalyst into a fixed bed reactor, and firstly vulcanizing the catalyst before introducing oil, wherein the vulcanization conditions are as follows: heating to 60 ℃ under the condition that the hydrogen partial pressure is 4MPa, and then introducing CS ₂ Heating n-hexane solution with content of 5 wt% to 300 deg.C, maintaining the temperature for 4 hr, and keeping the liquid hourly volume space velocity of vulcanized oil at 1.2 hr ^-1 Hydrogen to oil volume ratio 400. After the vulcanization is finished, raw oil (namely, an n-octane solution with the tetrahydronaphthalene content of 5.61 weight percent) is introduced for reaction under the following reaction conditions: the temperature is 390 ℃, the pressure is 4.0MPa, the volume ratio of hydrogen to oil is 1000, and the liquid hourly space velocity is 2 hours ^-1 。

The catalytic activity of the catalyst was calculated using the following formula:

aromatics hydroconversion activity = {1- [ (total amount of tetrahydronaphthalene in product + total amount of naphthalene in product)/total amount of tetrahydronaphthalene in feedstock ] } × 100%.

TABLE 3

As can be seen from Table 3, the hydrogenation catalyst provided by the invention has better hydrodesulfurization activity, denitrification activity and aromatic hydrogenation activity under the same other conditions.

From the results in table 3 it can be seen that the hydrogenation catalysts prepared by the process provided by the present invention are characterized by a Q of 1 to 3, preferably a Q of 1.1 to 2.5, whereas the catalysts prepared by the prior art processes and the comparative processes generally have a Q of less than 1 or greater than 3.

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 composite carrier and a hydrogenation active metal component loaded on the composite 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 composite carrier comprises a solid acid and 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 from 1.1 to 2.5.

3. The 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 composite carrier has a content of 30 to 99 wt.%, calculated as oxides, based on the total amount of the hydrogenation catalyst, of the group VIB metal component and of the group VIII metal component of 0.5 to 20 wt.%.

5. The hydrogenation catalyst according to claim 4, wherein the composite carrier comprises 40-94 wt%, calculated as oxides, 5-45 wt% of the group VIB metal component and 1-15 wt% of the group VIII metal component, based on the total amount of the hydrogenation catalyst.

6. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the solid acid is contained in an amount of 1 to 99 parts by weight based on the total amount of the composite carrier.

7. The hydrogenation catalyst according to claim 6, wherein the solid acid is contained in an amount of 5 to 80 parts by weight, based on the total amount of the composite carrier.

8. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the solid acid is silica-alumina and/or a molecular sieve.

9. The hydrogenation catalyst according to claim 8, wherein the molecular sieve is selected from at least one of faujasite, zeolite Beta, zeolite omega, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, ZSM-57 zeolite, erionite zeolite and ZSM-34 zeolite.

10. The hydrogenation catalyst according to claim 9, wherein the solid acid is selected from at least one of faujasite, zeolite Beta, ZSM-5 zeolite, mordenite and silica-alumina.

11. The hydrogenation catalyst of claim 10, wherein the faujasite is a Y-type zeolite.

12. The hydrogenation catalyst according to any one of claims 1 to 3, wherein the composite carrier contains phosphorus element, and 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.

13. The hydrogenation catalyst according to claim 12, wherein the composite carrier contains phosphorus element, and the total amount of the phosphorus-containing alumina is taken as a reference, and the Al element is 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%.

14. 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.

15. A hydrogenation catalyst according to any one of claims 1 to 3, wherein the phosphorus-containing alumina has a nitrogen adsorption pore volume of 0.5 to 1.6 ml/g and a BET nitrogen adsorption specific surface area of 270 to 480 m/g.

16. 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.

17. The hydrogenation catalyst according to claim 16, wherein 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 grain size of a crystal plane represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents a grain size of a crystal plane 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/(Bco 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.

18. The hydrogenation catalyst according to claim 17, wherein h of the pseudoboehmite satisfies 1.9. Ltoreq. H.ltoreq.3.

19. The hydrogenation catalyst according to claim 17 or 18, wherein h of the pseudoboehmite satisfies 2.2. Ltoreq. H.ltoreq.2.8.

20. A hydrogenation catalyst according to claim 17 or 18, wherein the relative crystallinity of the pseudo-boehmite containing phosphorus is in the range of from 45 to 77%.

21. A method for preparing a hydrogenation catalyst according to any one of claims 1 to 20, characterized in that it comprises the following steps:

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

22. The method of claim 21, wherein the temperature of the activation is 610-780 ℃.

23. The production method according to claim 21 or 22, wherein the temperature of the activation is 630 to 750 ℃.

24. The method of claim 21 or 22, wherein the temperature of the activation is 650-730 ℃.

25. The production method according to claim 21 or 22, wherein the activation temperature-raising rate of the activation is 50 to 600 ℃/hr.

26. The production method according to claim 25, wherein the activation temperature-raising rate of the activation is 100 to 550 ℃/hr.

27. The production method according to claim 21 or 22, wherein the solid acid is used in an amount such that the solid acid is contained in an amount of 1 to 99 parts by weight based on the total amount of the composite carrier.

28. The production method according to claim 27, wherein the solid acid is used in an amount such that the solid acid is contained in an amount of 5 to 80 parts by weight, based on the total amount of the composite carrier, in the produced composite carrier.

29. The production method according to claim 21 or 22, wherein the solid acid is silica-alumina and/or a molecular sieve.

30. The method of claim 29, wherein the molecular sieve is selected from at least one of faujasite, zeolite Beta, zeolite omega, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, ZSM-57 zeolite, erionite zeolite, and ZSM-34 zeolite.

31. The production method according to claim 29, wherein the solid acid is selected from at least one of faujasite, zeolite Beta, ZSM-5 zeolite, mordenite, and silica-alumina.

32. The production method according to claim 30 or 31, wherein the faujasite is a Y-type zeolite.

33. The production method according to claim 21 or 22, wherein the step (1) includes: mixing the phosphorus-containing pseudo-boehmite and/or the phosphorus-containing alumina with a solid acid, and then sequentially carrying out molding, drying and roasting to obtain the composite carrier.

34. The production method according to claim 21 or 22, wherein the conditions of the calcination of step (1) include: the temperature is 350-1000 ℃, and the time is 1-10 hours.

35. The method of claim 34, wherein the firing conditions of step (1) include: the temperature is 400-800 ℃ and the time is 2-6 hours.

36. The method of claim 21 or 22, wherein the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni.

37. The preparation method of claim 21 or 22, wherein the composite carrier and the hydrogenation active metal component are used in amounts such that the hydrogenation catalyst is prepared in an amount of 30 to 99 wt%, based on the total amount of the hydrogenation catalyst, of the composite carrier, the group VIB metal component is 0.5 to 50 wt%, and the group VIII metal component is 0.5 to 20 wt%, calculated as oxides.

38. The preparation method of claim 37, wherein the composite carrier and the hydrogenation active metal component are used in amounts such that the hydrogenation catalyst is prepared in an amount of 40-94 wt%, the group VIB metal component is 5-45 wt% and the group VIII metal component is 1-15 wt%, calculated as oxides, based on the total amount of the hydrogenation catalyst.

39. The preparation method according to claim 21 or 22, wherein the method for loading the hydrogenation active metal component on the composite carrier comprises impregnating the composite carrier with an impregnation solution containing at least one group VIB metal compound and at least one group VIII metal compound, followed by drying.

40. The method of claim 39, wherein the drying conditions include: the drying temperature is 50-350 ℃, and the drying time is 1-12 hours.

41. The method of claim 40, wherein the drying conditions include: the drying temperature is 80-250 ℃, and the drying time is 2-8 hours.

42. The production method according to claim 21 or 22, wherein the production method of the pseudo-boehmite containing phosphorus comprises the steps of:

(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;

43. The method of claim 42, wherein the phosphorus-containing alumina is obtained by calcining the phosphorus-containing pseudoboehmite.

44. The production method according to claim 42, 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.

45. The method of claim 42, wherein the precipitation reaction and the hydrolysis reaction are each independently at a temperature of 30-90 ℃.

46. The production method according to claim 42, 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.

47. The production method according to claim 42, 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.

48. The production method according to claim 42, 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.

49. The production method according to claim 42, wherein the grain growth regulator is at least one of a polyhydric sugar alcohol and a carboxylate and a sulfate thereof.

50. The preparation method of claim 49, wherein the grain growth regulator is selected from at least one of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, gluconate, and sulfate.

51. The production method according to claim 42, wherein the grain growth regulator is used in an amount of 1 to 10% by weight based on the weight of the inorganic aluminum-containing compound in the precipitation reaction.

52. The method according to claim 51, 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.

53. The method of claim 52, wherein the grain growth regulator is present in an amount of 2-6 wt.% based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the weight of alumina.

54. The method according to claim 42, 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.

55. The method according to claim 54, wherein the grain growth regulator is used in an amount of 1.5-8.5 wt% based on the weight of the organic aluminum-containing compound in the hydrolysis reaction.

56. The method according to claim 55, wherein the grain growth regulator is used in an amount of 2-6 wt.% based on the weight of the organic aluminum-containing compound in the hydrolysis reaction.

57. The production method according to claim 42, wherein 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.

58. The process as claimed in claim 42, wherein the phosphorus-containing compound is used in such an amount that the amount of P in the pseudo-boehmite containing phosphorus to be produced is P based on the total amount of the pseudo-boehmite containing phosphorus ₂ O ₅ Is 1 to 6 wt%.

59. The process as claimed in claim 58, wherein the phosphorus-containing compound is used in such an amount that P represents the total amount of pseudo-boehmite containing phosphorus in the pseudo-boehmite produced ₂ O ₅ Is contained in an amount of 2 to 5 wt%.

60. The method of claim 42, wherein the aging in the step (1-2) is carried out at a pH of 8 to 10.

61. The method of claim 42, wherein the temperature of aging is 50-95 ℃; the aging time is 0.5-8 hours.

62. The method of claim 61, wherein the aging temperature is 55-90 ℃; the aging time is 2-6 hours.

63. The production method according to claim 42, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate.

64. The preparation method of claim 42, wherein the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrolysis reaction with water and generate precipitation of hydrated alumina.

65. The production method according to claim 42, 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.

66. The method as claimed in claim 42, wherein the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.

67. Use of the hydrogenation catalyst of any one of claims 1 to 20 or the hydrogenation catalyst prepared by the preparation method of any one of claims 21 to 66 in a hydrogenation reaction of hydrocarbon oil.