阅读说明：本技术 加氢催化剂及其制备方法和应用 (Hydrogenation catalyst, preparation method and application thereof ) 是由 贾燕子 曾双亲 杨清河 王轶凡 刘学芬 聂鑫鹏 于 2020-04-28 设计创作，主要内容包括：本发明涉及加氢催化剂技术领域,公开了加氢催化剂及其制备方法和应用,所述加氢催化剂包括载体和负载在所述载体上的加氢活性金属组分,所述加氢活性金属组分含有至少一种VIB族金属组分以及至少一种VIII族金属组分,所述载体为含磷氧化铝,该含磷氧化铝的IR谱图中,(I-(3670)+I-(3580))/(I-(3770)+I-(3720))为1.9-2.8；其中,I-(3670)为3670cm～(-1)处峰高,I-(3580)为3580cm～(-1)处峰高,I-(3770)为3770cm～(-1)处峰高,I-(3720)为3720cm～(-1)处峰高。与现有技术相比,本发明提供的加氢催化剂由于在特定的含磷氧化铝载体上负载加氢活性金属组分,所述特定的含磷氧化铝具有IR谱图满足上述特征,所述加氢活性金属组分含有至少一种VIB族金属组分以及至少一种VIII族金属组分,因而获得更优异的加氢性能。(The invention relates to the technical field of hydrogenation catalystsThe hydrogenation catalyst comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, the carrier is phosphorus-containing alumina, and in an IR spectrogram of the phosphorus-containing alumina, (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. Compared with the prior art, the hydrogenation catalyst provided by the invention has the advantages that the hydrogenation active metal component is loaded on the specific phosphorus-containing alumina carrier, the specific phosphorus-containing alumina has an IR spectrogram which meets the characteristics, and the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, so that more excellent hydrogenation performance is obtained.)

1. A hydrogenation catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises at least one VIB group metal component and at least one VIII group metal component, the carrier is phosphorus-containing alumina, and in the IR spectrogram of the phosphorus-containing alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height.

2. The hydrogenation catalyst according to claim 1, wherein (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Is 2 to 2.7;

preferably, the nitrogen adsorption method of the phosphorus-containing alumina has the pore volume of 0.7-1.6 ml/g, the BET nitrogen adsorption method specific surface area of 250-380 square meters/g, and the diameters of several pores can be 8-16 nanometers;

preferably, Al is based on the total amount of the phosphorus-containing alumina₂O₃In an amount of 94 to 99 wt.%, preferably 95 to 98 wt.%; p₂O₅In an amount of1 to 6% by weight, preferably 2 to 5% by weight.

3. The hydrogenation catalyst of claim 1, wherein the phosphorus-containing alumina is obtained by calcining phosphorus-containing pseudo-boehmite;

preferably, h of the phosphorus-containing pseudo-boehmite satisfies 1.7 ≦ h ≦ 3, wherein h ═ D (031)/D (020), 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 grains, 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 grains, the 031 peak represents a peak having a2 θ of 34 to 43 ° in the XRD spectrum, the 020 peak represents a peak having a2 θ of 10 to 15 ° in the XRD spectrum, D ═ K λ/(Bcos θ), K is a Scherrer constant, λ is a diffraction wavelength of the target material, B is a half-width of the diffraction peak, and 2 θ is a position of the diffraction peak; more preferably, h of the pseudoboehmite satisfies 1.9. ltoreq. h.ltoreq.3, preferably satisfies 2.2. ltoreq. h.ltoreq.2.8;

preferably, the relative crystallinity of the pseudo-boehmite containing phosphorus is 45-77%.

4. A hydrogenation catalyst according to any one of claims 1-3, wherein the group VIB metal component is Mo and/or W, the group VIII metal component is Co and/or Ni;

preferably, the content of the carrier is 30-99 wt%, and 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 oxide, based on the total amount of the hydrogenation catalyst;

further preferably, the content of the carrier is 40-94 wt%, the content of the group VIB metal component is 5-45 wt% and the content of the group VIII metal component is 1-15 wt% calculated by oxide, based on the total amount of the hydrogenation catalyst.

5. A method for preparing a hydrogenation catalyst, the method comprising the steps of:

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

(2) aging the obtained hydrated alumina containing phosphorus under the condition that the pH value is 7-10.5;

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

(4) loading a hydrogenation active metal component on phosphorus-containing alumina;

the precipitation reaction or the hydrolysis reaction in the step (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 hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.

6. The production method according to claim 5, wherein the precipitation reaction or the hydrolysis reaction of step (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;

preferably, the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30-90 ℃;

preferably, the conditions of the precipitation reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 10-60 minutes, preferably 10-30 minutes; 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.

7. The production method according to claim 5 or 6, 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;

preferably, the grain growth regulator is at least one of a polyhydric sugar alcohol and a carboxylate and a 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;

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;

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

8. The production method according to claim 5 or 6, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate;

preferably, the phosphorus-containing compound is used in an amount such that P is present in the resulting phosphorus-containing alumina based on the total amount of phosphorus-containing alumina₂O₅The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

9. The production method according to any one of claims 5 to 8, wherein the aging of step (2) is carried out at a pH of 8 to 10;

preferably, the temperature of the aging is 50-95 ℃, preferably 55-90 ℃; the aging time is 0.5 to 8 hours, preferably 2 to 6 hours.

10. The production method according to any one of claims 5 to 9, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate;

the organic aluminum-containing compound is at least one of alkoxy aluminum which can generate hydrolysis reaction with water and generate hydrated alumina precipitate;

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

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

11. The production method according to any one of claims 5 to 10, wherein the conditions for the calcination in the step (3) include: the temperature is 350-1000 ℃, preferably 400-800 ℃, and the time is 1-10 hours, preferably 2-6 hours;

preferably, the group VIB metal component is Mo and/or W, and the group VIII metal component is Co and/or Ni;

preferably, the content of the phosphorus-containing alumina is 30-99 wt%, 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% calculated by oxide, based on the total amount of the hydrogenation catalyst;

further preferably, the content of the phosphorus-containing alumina is 40-94 wt%, the content of the VIB group metal component is 5-45 wt% and the content of the VIII group metal component is 1-15 wt% calculated by oxides, based on the total amount of the hydrogenation catalyst;

preferably, the method for loading the hydrogenation active metal component on the phosphorus-containing alumina comprises the steps of impregnating the phosphorus-containing alumina with an impregnating solution containing at least one group VIB metal compound and at least one group VIII metal compound, and then drying and roasting;

preferably, the drying conditions include: the drying temperature is 80-200 ℃, preferably 100-150 ℃; the drying time is 1 to 8 hours, preferably 2 to 6 hours;

preferably, the conditions of the calcination include: the roasting temperature is 200-700 ℃, and preferably 350-600 ℃; the calcination time is from 1 to 10 hours, preferably from 2 to 8 hours.

12. Use of the hydrogenation catalyst according to any one of claims 1 to 4 or the hydrogenation catalyst produced by the production method according to any one of claims 5 to 11 in a hydrogenation reaction of hydrocarbon oil.

Technical Field

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

Background

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

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 the 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 and match the acting force between the metal and the carrier by upgrading the carrier property and the catalyst preparation process, the stability of the active phase of the catalyst is improved, the diffusion performance and the scale capacity of the catalyst are improved, and meanwhile, the damage, aggregation and poisoning of the active phase structure of the catalyst in the reaction process are reduced, so that the method is a key technology for improving the activity stability of the catalyst.

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

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. The method for introducing phosphorus is divided according to the forming process of alumina, and can comprise the following steps: introducing phosphorus in the preparation process of the pseudo-boehmite, such as the gelling, aging and washing processes; phosphorus or the like is introduced during the molding process or the impregnation process. CN102247882B discloses a method for preparing phosphorus modified alumina by adding phosphorus-containing compound during the formation 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.

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 residual oil hydrodesulfurization performance of the catalyst is to be further improved and the catalyst is highly acidic, rapidly deactivated in the heavy oil hydrogenation reaction, and thus is not suitable for the heavy oil hydrogenation reaction.

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

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

Disclosure of Invention

The invention aims to overcome the 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 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 in 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 be 4-7, and then regulating the pH to be 7-10.5 for aging, so as to prepare the specific phosphorus-containing alumina, wherein in the IR spectrogram of the phosphorus-containing alumina, (I) is₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9 to 2.8, preferably 2 to 2.7; it is composed ofIn (I)₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height. The hydrogenation catalyst prepared by taking the specific phosphorus-containing alumina as a carrier and loading a hydrogenation active metal component on the carrier has good hydrogenation activity.

In order to achieve the above object, the first aspect of the present invention provides a hydrogenation catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component comprises at least one group VIB metal component and at least one group VIII metal component, the carrier is a phosphorus-containing alumina, and the phosphorus-containing alumina has an IR spectrum of (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height.

Preferably, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Is 2-2.7.

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

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

(2) aging the obtained hydrated alumina containing phosphorus under the condition that the pH value is 7-10.5;

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

(4) loading a hydrogenation active metal component on phosphorus-containing alumina;

the precipitation reaction or the hydrolysis reaction in the step (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 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 an application of the hydrogenation catalyst of the first aspect or the hydrogenation catalyst prepared by the preparation method of the second aspect in a hydrogenation reaction of hydrocarbon oil.

Compared with the prior art, the hydrogenation catalyst provided by the invention has the advantages that the specific phosphorus-containing alumina carrier is loaded with the hydrogenation active metal component, and the specific phosphorus-containing alumina has an IR spectrum (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1The hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, so that more excellent hydrogenation activity is obtained. The specific phosphorus-containing alumina provides excellent diffusion performance and scale capacity for the hydrogenation catalyst, and simultaneously can avoid the layer drop inactivation of the active phase of the hydrogenation catalyst, so that the hydrogenation catalyst has excellent reaction stability.

The preparation method of the hydrogenation catalyst provided by the invention has the advantages that the phosphorus-containing compound, the grain growth regulator and the pH value in the preparation process are added in a segmented control manner, so that the obtained phosphorus-containing alumina has specific surface hydroxyl distribution, and in the IR spectrogram of the phosphorus-containing alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1The peak height is more suitable for being used as a catalyst carrier, and the obtained hydrogenation catalyst has more excellent hydrogenation activity. For example, the hydrogenation catalyst prepared in example 1 was used at a reaction temperature of 380 deg.C, a hydrogen partial pressure of 15 MPa, and a liquid hourly space velocity of 0.6 hrTime of flight^-1Carrying out tests on hydrogenation (Ni + V) removal performance, desulfurization performance, carbon residue removal and denitrification performance under the condition that the volume ratio of hydrogen to oil is 600, wherein the (Ni + V) removal rate of the product obtained after reaction for 200 hours is 85%, the desulfurization rate is 90%, the carbon residue removal rate is 61%, and the denitrification rate is 69%; under the condition that other conditions are completely the same, after the hydrogenation catalyst prepared in the comparative example 1 is adopted to react for 200 hours, the (Ni + V) removal rate of the obtained product is 72 percent, the desulfurization rate is 75 percent, the carbon residue removal rate is 39 percent, and the denitrification rate is 38 percent; the former has a removal rate at least 13% higher than that of the latter, even 31% higher than that of the latter, and the former has better reaction stability.

Detailed Description

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

The invention provides a hydrogenation catalyst, which comprises a carrier and a hydrogenation active metal component loaded on the carrier, wherein the hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component, the carrier is phosphorus-containing alumina, and in an IR spectrogram of the phosphorus-containing alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height.

In the present invention, the IR spectrum is obtained by measurement with a Nicolet 870 type Fourier Infrared spectrometer, Nicolet corporation, USA. The method specifically comprises the following steps: pressing the sample into a self-supporting sheet, placing the self-supporting sheet in an infrared cell, treating the sample for 3 hours at 450 ℃ under a vacuum condition, and measuring the infrared spectrum of the sample. According to the spectrum 3670cm^-1Peak height, 3580cm^-1Treating peakHigh, 3770cm^-1Peak height, 3720cm^-1Calculation of the value of the peak height (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The value of (c). Prior art alumina Supports (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Generally lower than 1.8.

Preferably, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Is 2-2.7.

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

The hydrogenation catalyst provided by the invention contains phosphorus element, and preferably, based on the total amount of the phosphorus-containing alumina, Al₂O₃In an amount of 94 to 99 wt.%, preferably 95 to 98 wt.%; p₂O₅The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

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 ℃, preferably 500-750 ℃, and the time is 1-10 hours, preferably 2-6 hours.

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

In the present invention, for different diffraction peaks, B and 2 θ both take the values of the corresponding peaks, for example, when calculating D (031), 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 which meets the specification has specific hydroxyl distribution, and is more favorable for improving the hydrogenation activity of the hydrogenation catalyst prepared by taking the phosphorus-containing alumina as a carrier. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.

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

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

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

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

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

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

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. The hydrogenation catalyst provided by the invention can be used alone or combined with other catalysts when used for hydrogenation reaction of hydrocarbon oil.

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

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

(2) aging the obtained hydrated alumina containing phosphorus under the condition that the pH value is 7-10.5;

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

(4) loading a hydrogenation active metal component on phosphorus-containing alumina;

the precipitation reaction or the hydrolysis reaction in the step (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 hydrogenation active metal component contains at least one VIB group metal component and at least one VIII group metal component.

According to the production process provided by the present invention, the solid product is the pseudoboehmite according to the aforementioned first aspect of the present invention.

According to the preparation method provided by the invention, the precipitation reaction or the hydrolysis reaction is carried out under the conditions that the grain growth regulator and the phosphorus-containing compound exist and the pH value is 4-7, so that the precipitation of phosphorus-containing hydrated alumina can be met, the pH condition is kept lower, the pseudo-boehmite grain growth under high pH value is prevented from being too fast, and the joint regulation effect of phosphorus and the growth regulator on the pseudo-boehmite growth 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) 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) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5. So that the precipitation reaction or hydrolysis reaction is carried out at the preferable pH value, which is more favorable for improving the hydrogenation activity of the prepared hydrogenation catalyst in heavy oil hydrogenation.

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

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

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

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

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

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

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

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

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

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

In order to better exert the regulating effect of the phosphorus-containing compound on the grain growth, the phosphorus-containing compound is preferably used in such an amount that P in the prepared phosphorus-containing alumina is present based on the total amount of the phosphorus-containing alumina₂O₅The content of (B) is 1 to 6% by weight, preferably 2 to 5% by weight.

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

According to the preparation method provided by the invention, in the step (1), the inorganic aluminum-containing compound is preferably an aluminum salt and/or an aluminate. Correspondingly, the inorganic aluminum-containing compound can also be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution can be various aluminum salt solutions, such as an aqueous solution of one or more of aluminum sulfate, aluminum chloride and aluminum nitrate. Aluminum sulfate solution and/or aluminum chloride solution is preferred because of low cost. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as a sodium aluminate solution and/or a potassium aluminate solution. Sodium aluminate solution is preferred because of its availability and low cost. The aluminate solutions may also be used alone or in admixture. The concentration of the inorganic aluminum-containing compound solution is not particularly limited, and preferably, the concentration of the inorganic aluminum-containing compound solution is 20 to 200 g/l in terms of alumina.

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

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

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

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

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

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

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

The aging conditions other than pH in step (2) are selected in a wide range according to the present invention, and preferably, the temperature of 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.

The invention also includes the steps of separating, washing and drying the aged product after the aging reaction. 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 100-350 deg.C, preferably 120-300 deg.C.

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

In the preparation method provided by the present invention, the calcination conditions in step (3) are not particularly limited, and preferably, the calcination conditions in step (3) include: the temperature is 350-1000 ℃, preferably 400-800 ℃, and the time is 1-10 hours, preferably 2-6 hours;

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

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

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

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

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

According to the preparation method provided by the invention, the catalyst can also contain organic additives in the preparation process of the catalyst, such as the preparation process of soluble compounds of the VIB group metal compound and the VIII group metal compound. The method for introducing the organic additive is not particularly limited, and the organic additive may be introduced in any manner, for example, may be introduced together with the group VIII metal, may be introduced together with the group VIB metal element, may be introduced after introducing the group VIII and/or group VIB metal element, or may be introduced before introducing the group VIII and/or group VIB element. The invention is not particularly limited to the type of the organic additive, the organic additive is at least one selected from oxygen-containing and/or nitrogen-containing organic substances, the oxygen-containing organic substances are selected from organic alcohol and/or organic acid, and the nitrogen-containing organic substances are selected from at least one selected from organic amine and organic amine salt; specifically, the oxygen-containing organic matter is selected from at least one of ethylene glycol, glycerol, polyethylene glycol (molecular weight 200-; 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 production method provided by the present invention, the drying conditions in the method for supporting the hydrogenation active metal component on the phosphorus-containing alumina are not particularly limited, and preferably, the drying conditions include: the drying temperature is 80-200 ℃, preferably 100-150 ℃; the drying time is from 1 to 8 hours, preferably from 2 to 6 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.

According to the preparation method provided by the invention, the roasting conditions in the method for loading the hydrogenation active metal component on the phosphorus-containing alumina are wide in range, and preferably, the roasting conditions comprise: the roasting temperature is 200-700 ℃, and preferably 350-600 ℃; the calcination time is from 1 to 10 hours, preferably from 2 to 8 hours.

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

According to the preparation method provided by 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, fluorine, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated by single element elements is not more than 10 wt% and is preferably 0.5-6 wt% based on the catalyst. 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), or during the aging or washing in the step (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), or may be introduced by preparing a solution containing the assistant, and then impregnating the phosphorus-containing alumina with the solution and calcining. In the introduction of the auxiliary agent, the calcination conditions are not particularly limited, and preferably, the calcination temperature is 200-800 ℃, more preferably 300-700 ℃, and the calcination time is 2-8 hours, more preferably 3-6 hours.

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

(1) adding an inorganic aluminum-containing compound solution containing 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;

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

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

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

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

In a third aspect, the present invention provides an application of the hydrogenation catalyst of the first aspect or the hydrogenation catalyst prepared by the preparation method of 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 presulfided with sulfur, hydrogen sulfide or sulfur-containing raw materials in the presence of hydrogen at the temperature of 140 ℃ and 400 ℃. The prevulcanisation can be carried out either ex situ or in situ.

In the present invention, the hydrogenation conditions for the application of the hydrogenation catalyst are not particularly limited, and the reaction conditions generally used in the art may be employed; preferably, the reaction temperature is 200-420 ℃, more preferably 220-400 ℃, the pressure is 2-18MPa, more preferably 2-16MPa, and the liquid hourly space velocity is 0.1-10 h^-1More preferably 0.15 to 6 hours^-1The hydrogen-oil volume ratio is 50 to 5000, and more preferably 50 to 4000.

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

The application object of the hydrogenation catalyst is not particularly limited, and the hydrogenation catalyst can be directly used for processing various hydrocarbon oil raw materials 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 using CuKa radiation, 44 kV, 40 mA, scanning speed 2^°In terms of a/minute. According to the Scherrer formula: k λ/(Bcos θ) (D is the crystal grain size, λ is the diffraction wavelength of the target material, B is the half-value width of the corrected diffraction peak, and 2 θ is the position of the diffraction peak), the crystal grain size of (020) is calculated by using the parameter that 2 θ is the peak of 10 to 15 °, D (020) is the crystal grain size, and 2 θ is 34 to 43^°The peak parameter (031) indicates the grain size D (031), and h is calculated as D (031)/D (020).

The IR spectrum is obtained by measuring with a Nicolet 870 type Fourier infrared spectrometer of Nicolet company in the United states. The method specifically comprises the following steps: pressing the sample into a self-supporting sheet, placing the self-supporting sheet in an infrared cell, treating the sample for 3 hours at 450 ℃ under a vacuum condition, and measuring the infrared spectrum of the sample. According to the spectrum 3670cm^-1Peak height, 3580cm^-1Peak height, 3770cm^-1Peak height, 3720cm^-1Calculation of the value of the peak height (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The value of (c).

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.

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 PA1 has a pseudo-boehmite structure.

The h values calculated by XRD characterization for PA1 are listed in Table 1. Relative crystallinity of PA1 and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

1000 g of the PA1 and 30g of sesbania powder (produced by Shunhun corporation, Fengsheng county, Jiangsu province) are uniformly mixed, 920 ml of aqueous solution containing 28g of nitric acid is added for mixing, then a butterfly-shaped wet strip with the outer diameter of 1.7mm is extruded on a plunger type extruding machine, the butterfly-shaped wet strip is dried for 4 hours at the temperature of 120 ℃, and then is roasted for 3 hours at the temperature of 600 ℃, and the carrier Z1 is obtained. P in vector Z1₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z1 was taken and 110 ml of a mixed aqueous solution (containing MoO in the form of a mixed aqueous solution) consisting of ammonium molybdate, nickel nitrate and citric acid was added₃434 g/l, NiO 78 g/l and citric acid 160 g/l) was impregnated into the support Z11 hours, dried at 110 ℃ for 4 hours and calcined at 420 ℃ for 3 hours to obtain hydrogenation catalyst C1. Metal oxide (MoO) in the hydrogenation catalyst₃And NiO) are shown in table 3.

Comparative example 1

A carrier DZ1 and a hydrogenation catalyst DC1 were prepared by following the procedure of example 1, except that 8.0mL of phosphoric acid having a concentration of 85% by weight was added to the aluminum sulfate solution without ribitol, to obtain hydrated alumina CPA 1. According to the method of example 1, CPA1 has pseudo-boehmite structure and H value of CPA1 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. The pore volume, specific surface area and optionally pore diameter of support DZ1 are listed in table 2.

Comparative example 2

A carrier DZ2 and a hydrogenation catalyst DC2 were prepared by following the procedure of example 1, except that the flow rate of the aqueous ammonia solution was directly controlled so that the pH of the reaction system became 8.7, and after the completion of the precipitation reaction, it was not necessary to add aqueous ammonia to the slurry to adjust the pH, thereby obtaining hydrated alumina CPA 2. According to the method of example 1, CPA2 has pseudo-boehmite structure and H value of CPA2 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ2₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 3

A carrier DZ3 and a hydrogenation catalyst DC3 were prepared by following the procedure of example 1, except that 6.0 g of ribitol was added to the aluminum sulfate solution without containing concentrated phosphoric acid, to obtain hydrated alumina CPA 3. According to the method of example 1, CPA3 has pseudo-boehmite structure and H value of CPA3 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ3₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 2

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

Into a 2-liter reaction tank were introduced, in parallel, 4000 mL of a solution of aluminum trichloride having a concentration of 45 g of alumina per liter and containing 85% by weight of concentrated phosphoric acid 22.1mL and sorbitol 4.52 g/liter and 1000 mL of a solution containing aluminum trichloridePrecipitating 210 g of aluminum oxide/liter and sodium metaaluminate solution with caustic coefficient of 1.58, adjusting the reaction temperature to 80 ℃, regulating the flow of reactants to ensure that the neutralization pH value is 4.0, and keeping the reaction time for 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. Adding the qualified filter cake after washing into 3.0L of deionized water, stirring to obtain slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer within the range of 100-110 ℃, and drying the materials for about 2 minutes to obtain the hydrated alumina PA 2. The PA2 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA2 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

The support Z2 was prepared according to the method of example 1, except that PA2 was used instead of PA1 and the calcination temperature was 650 ℃. P in vector Z2₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the carrier Z2 was taken, and 110 ml of a mixed aqueous solution (containing MoO in the mixed aqueous solution) consisting of ammonium molybdate, cobalt nitrate and ammonia water was used₃201 g/l, CoO 40 g/l, ammonia 50 g/l) was impregnated into the carrier Z21 hours, followed by drying at 120 ℃ for 3 hours and then calcining at 400 ℃ for 3 hours to obtain hydrogenation catalyst C2. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Comparative example 4

The support DZ4 and the hydrogenation catalyst DC4 were prepared by following the procedure of example 2, except that sorbitol was not contained in the aluminum trichloride solution, to give hydrated alumina CPA 4. According to the method of example 1, by using XRD characterization, CPA4 has pseudo-boehmite structure, and H value column of CPA4 is calculated by XRD characterizationIn Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ4₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 5

A carrier DZ5 and a hydrogenation catalyst DC5 were prepared by following the procedure of example 2, 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, it was not necessary to add ammonia water to the slurry to adjust the pH, thereby obtaining hydrated alumina CPA 5. According to the method of example 1, CPA5 has pseudo-boehmite structure and H value of CPA5 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ5₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 6

The support DZ6 and hydrogenation catalyst DC6 were prepared according to the method of example 2, except that concentrated phosphoric acid was not contained in the aluminum trichloride solution, to give hydrated alumina CPA 6. According to the method of example 1, CPA6 has pseudo-boehmite structure and H value of CPA6 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ6₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 3

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

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 PA 3. The PA3 has a pseudo-boehmite structure, as 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 P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Weighing 1 kg of carrier PA3, 30g of sesbania powder (produced by Shunhun commerce, Inc. in Fengsheng county) and 30g of hydroxypropyl methyl cellulose, uniformly mixing, adding 1.2 l of 1% nitric acid aqueous solution, uniformly mixing, continuously kneading on a double-screw extruder to obtain a plastic body, extruding into wet butterfly-shaped strips with the diameter of 1.1 mm, drying the wet butterfly-shaped strips at 110 ℃ for 2 hours, and roasting at 620 ℃ for 3 hours to obtain the carrier Z3. P in vector Z3₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z3 was taken and 220 ml of a mixed aqueous solution of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contained MoO)₃230 g/l, 54 g/l of NiO and 50g/l of phosphoric acid) is impregnated into the carrier Z31 hours, dried for 3 hours at 120 ℃ and calcined for 3 hours at 400 ℃ to obtain the hydrogenation catalyst C3. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Example 4

Support Z4 and hydrogenation catalyst C4 were prepared according to the method of example 3, except that during the precipitation reaction, the reactant flow was adjusted so that the neutralization pH was 7. The hydrated alumina PA4 was obtained. The PA4 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA4 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA4 were used to prepare the vector Z4, P in Z4₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2. The process for preparing the hydrogenation catalyst C4 by adopting the carrier Z4 comprises the following steps: 100g of the support Z4 was taken and 220 ml of a mixed aqueous solution of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contained MoO)₃230 g/l, 54 g/l of NiO and 50g/l of phosphoric acid) is impregnated into the carrier Z41 hours, dried for 3 hours at 120 ℃ and calcined for 3 hours at 400 ℃ to obtain the hydrogenation catalyst C4. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Comparative example 7

The procedure of example 4 was followed with DZ7 as the support and DC7 as the hydrogenation catalyst, except that the aluminum sulfate solution contained no gluconic acid, to give hydrated alumina CPA 7. According to the method of example 1, CPA7 has pseudo-boehmite structure and H value of CPA7 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ7₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 8

Preparation of the support DZ8 and hydrogenation catalysis according to the method of example 4The difference of the agent DC8 is that the flow of sodium metaaluminate solution is directly controlled to make the pH value of the reaction system be 9.5, and after the precipitation reaction is finished, the pH value of the slurry does not need to be adjusted by adding sodium carbonate solution, so that the hydrated alumina CPA8 is obtained. According to the method of example 1, CPA8 has pseudo-boehmite structure and H value of CPA8 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ8₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 9

The support DZ9 and hydrogenation catalyst DC9 were prepared according to the method of example 4, except that concentrated phosphoric acid was not contained in the aluminum sulfate solution, to give hydrated alumina CPA 9. According to the method of example 1, CPA9 has pseudo-boehmite structure and H value of CPA9 calculated by XRD characterization is shown in Table 1, and 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ9₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 5

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

Adding 1000 g of isopropanol-water azeotrope (the water content is 15 weight percent) into a 2L three-neck flask with a stirring and reflux condenser pipe, adding 4.6mL of 85 percent concentrated phosphoric acid and 15g of ribonic acid, adding ammonia water to adjust the pH value to 5.1, heating to 60 ℃, slowly dripping 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 the aged hydrated alumina,drying at 120 deg.C for 24 hr to obtain hydrated alumina PA 5. The PA5 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA5 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA5 were used to prepare the vector Z5, P in Z5₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the support Z5 was taken and 110 ml of a mixed aqueous solution of molybdenum oxide, basic nickel carbonate and phosphoric acid (the mixed aqueous solution contained MoO)₃183 g/l, NiO 44 g/l, phosphoric acid 60 g/l) was impregnated into the support Z51 hours, dried at 120 ℃ for 3 hours, and calcined at 430 ℃ for 3 hours to obtain a hydrogenation catalyst C5. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Comparative example 10

The support DZ9 and hydrogenation catalyst DC9 were prepared according to the method of example 5, except that no ribonic acid was added to the three-necked flask to give hydrated alumina CPA 10. According to the method of example 1, CPA10 has pseudo-boehmite structure and H value of CPA10 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ9₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 11

The support DZ11 and the hydrogenation catalyst DC11 were prepared as in example 5, except that after the same amount of ribonic acid was added, ammonia was then added to adjust the pH to 8.5, then heated to 60 ℃ and 500 grams of molten aluminum isopropoxide was passed through a separatory funnelSlowly added dropwise to the flask to give hydrated alumina CPA 11. According to the method of example 1, CPA11 has pseudo-boehmite structure and H value of CPA11 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ11₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 12

The support DZ12 and hydrogenation catalyst DC12 were prepared according to the method of example 5, except that concentrated phosphoric acid was not added to the three-necked flask to obtain hydrated alumina CPA 12. According to the method of example 1, CPA12 has pseudo-boehmite structure and H value of CPA12 calculated by XRD characterization is shown in Table 1, and 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ12₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 6

This example is intended to illustrate the pseudo-boehmite containing phosphorus and the alumina containing phosphorus provided by the present invention and the preparation thereof.

Adding 1000 g of isopropanol-water azeotrope (the water content is 15 weight percent) into a 2L three-neck flask with a stirring and reflux condenser pipe, adding 7mL of 85 percent 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 the flask through a separating funnel, reacting for 5 hours, adding ammonia water to adjust the pH value to 8.5, refluxing for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating hydrous isopropanol while aging, filtering aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA 6. Characterization by XRD according to the method of example 1, PA6 has pseudo-thin waterThe structure of the aluminum-based alloy is characterized by XRD, and h values of PA6 calculated by XRD are shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Using the procedure of example 1, 1000 g of PA6 were used to prepare vector Z6, vector Z6 containing P₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

100g of the carrier Z6 was taken, and 110 ml of a mixed aqueous solution composed of tungsten oxide, basic nickel carbonate and ammonia water (the mixed aqueous solution contained WO)₃466 g/l, 50g/l of NiO and 70 g/l of ammonia water) is soaked in the carrier Z61 hours, dried for 3 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain the hydrogenation catalyst C6. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Comparative example 13

The procedure of example 5 was followed for DZ13 support and DC13 hydrogenation catalyst, except that pseudo-boehmite containing phosphorus was prepared according to a typical method in "research on support materials for heavy oil hydrogenation catalyst": with 85% concentrated phosphoric acid added to 8.8mL of 57 g.L^-13000mL of aluminum sulfate solution (D) and a concentration of 64 g.L^-1And carrying out precipitation reaction on 2500mL of sodium metaaluminate solution, wherein the neutralization pH is 8.0, the reaction time is 70min, then aging is carried out, the aging temperature is 90 ℃, the aging pH is 8.5, filtering is carried out after aging, a filter cake is beaten and washed for 2 times by deionized water, and the filter cake is dried for 24 hours at 120 ℃ to prepare the phosphorus-containing pseudo-boehmite CPA 13. According to the method of example 1, CPA13 has pseudo-boehmite structure and H value of CPA13 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ13₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Comparative example 14

The carrier DZ14 and the hydrogenation catalyst DC14 were prepared according to the method of example 5, except that a phosphorus-modified pseudoboehmite catalyst carrier material and a preparation method thereof were disclosed in CN 103721732A. Adding an aluminum sulfate solution with the alumina concentration of 50g/L and a sodium metaaluminate solution with the alumina concentration of 220g/L and the caustic ratio of 1.2 into a neutralization reaction kettle 1, controlling the pH value to be 7.0 and the temperature to be 55 ℃; the slurry of the neutralization reaction kettle 1 flows into a neutralization reaction kettle 2 through an overflow reaction pipe, and a sodium carbonate solution with the concentration of 150g/L is added into the neutralization reaction kettle 2, the pH value is controlled to be 9.5, and the reaction temperature is controlled to be 70 ℃; the slurry in the neutralization reaction kettle 2 flows into an aging reaction kettle through an overflow reaction pipe, the temperature of the slurry in the aging reaction kettle is 95 ℃, and the aging is carried out for 2 hours; calculating the volume of phosphoric acid solution with the phosphorus pentoxide concentration of 100g/L added into the aging reaction kettle according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, wherein the phosphorus pentoxide content of the added phosphoric acid is 4 percent of the alumina content; and washing and drying after aging to obtain the pseudo-boehmite containing phosphorus. According to the method of example 1, CPA14 has pseudo-boehmite structure and H value of CPA14 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The 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+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1. P in vector DZ14₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

Example 7

100g of the support Z1 prepared in example 1 were taken and 110 ml of an aqueous mixture of molybdenum oxide, nickel hydroxycarbonate and phosphoric acid, which contains MoO₃249 g/l, NiO 59 g/l, phosphoric acid 78 g/l) was impregnated into the carrier Z12 hours, dried at 120 ℃ for 4 hours, and calcined at 450 ℃ for 3 hours to obtain hydrogenation catalyst C7. The content of metal oxides in the hydrogenation catalyst is shown in table 3.

Comparative example 15

Mixing the dry glue powderCPA15 (manufactured by Changling catalyst Co., Ltd.) was calcined at 600 ℃ for 4 hours and then its surface hydroxyl group was measured by infrared spectroscopy (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

300 g of dry rubber powder CPA15 (produced by Changling catalyst company) and 10 g of sesbania powder (produced by Henan Lanco sesbania gum factory) are uniformly mixed to obtain a mixture, the mixture is mixed with 360 ml of aqueous solution containing 7g of nitric acid at room temperature, then the mixture is continuously kneaded on a double-screw extruder to form a plastic body, and then the plastic body is extruded into butterfly-shaped wet strips with the diameter of 1.4 mm, and the butterfly-shaped wet strips are dried at 120 ℃ for 4 hours and then are roasted at 600 ℃ for 4 hours to obtain a carrier DZ 15. P in vector DZ15₂O₅The contents of (A) and their pore volumes, specific surface areas and possibly several pore diameters are shown in Table 2.

The mixed aqueous solution containing the metal compound in example 7 was used to impregnate the support DZ15, which was then dried at 120 ℃ for 4 hours and calcined at 400 ℃ for 3 hours to obtain hydrogenation catalyst DC 15.

TABLE 1

Note: m represents (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Value of (A)

TABLE 2

TABLE 3

As can be seen from the results in Table 1, the pseudo-boehmite containing phosphorus prepared by the method of the present invention has a characteristic of 1.7. ltoreq. h.ltoreq.3, preferably 2.2. ltoreq. h.ltoreq.2.8, while the various pseudo-boehmite prepared by the methods of the prior art and the methods of the comparative examples have h values of less than 1.7. In an IR characteristic spectrogram of alumina obtained by roasting the phosphorus-containing pseudo-boehmite prepared by the method at 600 ℃, hydroxyl has a characteristic (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-2.8, preferably 2-2.7, and the hydroxyl group characteristics (I) in the IR characteristic spectrum of alumina obtained by calcining the pseudoboehmite prepared by the method of the prior art and the method in the comparative example at 600 DEG C₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀)<1.8。

Test example 1

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

The hydrogenation catalysts prepared in the above 100mL examples 1 to 7 and comparative examples 1 to 15 were crushed into particles with a diameter of 2 to 3 mm and then presulfided under the following conditions: the vulcanized oil adopts Jingmen normal first-line kerosene containing 5w percent of dimethyl disulfide, and the liquid hourly volume space velocity of the vulcanized oil is 1.2h^-1Hydrogen partial pressure is 14.0MPa, hydrogen-oil volume ratio is 400, and the vulcanization is carried out for 3 hours at the constant temperature of 360 ℃; evaluation was then carried out in a 100ml small fixed-bed reactor (catalyst loading 100 ml). The raw material is the inferior slag of the Jinling petrochemical atmospheric and vacuum distillation device (the content of sulfur element is 2.9 weight percent, the content of nitrogen element is 0.38 weight percent, the value of carbon residue is 8.2 weight percent, the content of nickel is 31.4 mu g/g, the content of vanadium is 61.6 mu g/g), the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly volume space velocity is 0.6 hour^-1And carrying out a hydrogenation activity performance test under the condition that the volume ratio of hydrogen to oil is 600. Specifically, the product after 200h of reaction was tested for its (Ni + V) removal rate, desulfurization rate, decarburization rate and denitrification rate, and the results are shown in Table 4.

Wherein the calculation methods of the (Ni + V) removal rate, the desulfurization rate, the carbon residue removal rate and the denitrification rate are the same; the present invention exemplifies a calculation method by taking the removal rate of (Ni + V), i.e., (Ni + V content in the feedstock- (Ni + V) content in the hydrogenated product)/(Ni + V) content in the feedstock.

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

TABLE 4

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

Test example 2

The desulfurization and denitrification activity of the hydrogenation catalyst of the invention is exemplified by example 1, comparative example 1 and comparative example 15.

The catalysts C1, DC1 and DC15 are respectively crushed into 2-4 mm particles, and are presulfurized on a 30 ml hydrogenation device, wherein the presulfurization conditions comprise: the sulfurated oil adopts 5w percent of carbon disulfide/cyclohexane, the hydrogen partial pressure is 6MPa, and the liquid hourly space velocity is 0.8 hour^-1Hydrogen-oil volume ratio of 800, and vulcanizing at a constant temperature of 360 ℃ for 3 hours; then, catalysts C1, DC1 and DC15 were evaluated, and the raw oils used thereforIs Qingdao firewood with the sulfur content of 7690 mug/g and the nitrogen content of 489 mug/g. The evaluation conditions were: the reaction temperature is 350 ℃, the hydrogen partial pressure is 6MPa, and the liquid hourly space velocity is 2 hours^-1The volume ratio of hydrogen to oil was 300. The results of the hydrodesulfurization and denitrogenation activity tests are shown in Table 5.

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

TABLE 5

Example numbering	Catalyst numbering	Hydrodesulfurization activity,% of	Hydrodenitrogenation activity,%
				Example 1	C1	151	130
Comparative example 1	DC1	100	100
				Comparative example 15	DC15	96	97

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

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features 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.