CN113562751B

CN113562751B - Modified pseudo-boehmite, preparation method thereof, modified alumina and hydrogenation catalyst

Info

Publication number: CN113562751B
Application number: CN202010351480.1A
Authority: CN
Inventors: 贾燕子; 李大东; 曾双亲; 杨清河; 赵新强; 邓中活
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-04-28
Filing date: 2020-04-28
Publication date: 2023-05-09
Anticipated expiration: 2040-04-28
Also published as: CN113562751A

Abstract

The invention relates to the field of pseudo-boehmite preparation, and discloses modified pseudo-boehmite, a preparation method thereof, modified alumina and a hydrogenation catalyst, wherein h of the modified pseudo-boehmite is more than or equal to 1.7 and less than or equal to 4, h=D (031)/D (020), D (031) represents the grain size of a crystal face represented by 031 peak in an XRD spectrogram of pseudo-boehmite crystal grains, D (020) represents the grain size of a crystal face represented by 020 peak in the XRD spectrogram of pseudo-boehmite crystal grains, 031 peak is a peak with 2 theta of 34-43 DEG in the XRD spectrogram, 020 peak is a peak with 2 theta of 10-15 DEG in the XRD spectrogram, D=Kλ/(Bcosθ), K is Scherrer constant, λ is the diffraction wavelength of a target material, B is the half-peak width of the diffraction peak, and 2 theta is the position of the diffraction peak. Compared with the prior art, the modified pseudo-boehmite provided by the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 4, so that the modified alumina obtained by roasting the modified pseudo-boehmite is more suitable for being used as a hydrogenation catalyst carrier, and the obtained catalyst has more excellent hydrogenation activity.

Description

Modified pseudo-boehmite, preparation method thereof, modified alumina and hydrogenation catalyst

Technical Field

The invention relates to the field of pseudo-boehmite preparation, in particular to modified pseudo-boehmite, a preparation method thereof, modified alumina and a hydrogenation catalyst.

Background

Since the catalyst support serves to provide a diffusion path for reactants and products and an attachment site for the formation of a reactive phase during the catalytic reaction, the adsorption of the reactants and products and the interaction with the active components on the surface of the support can have an important impact on the performance of the catalyst. These interactions have a close relationship with the specific surface area of the alumina support and the number and types of hydroxyl groups on the surface. Meanwhile, in the hydrotreating process of heavy distillate oil, as the raw material contains a large number of reactant molecules with complex structure, large molecular diameter and rich heteroatom quantity, and the catalyst activity is continuously reduced due to the influence of metal deposition and carbon deposition in the reaction process, the catalyst is required to have good reactivity, and meanwhile, excellent diffusion performance and scale-tolerant capability are required, so that the pore structure of the catalyst carrier can have important influence on the catalyst performance. Therefore, the alumina carrier with high pore volume, large specific surface area and special surface hydroxyl distribution plays an important role in the preparation process of the heavy oil hydrogenation catalyst.

Alumina, particularly gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. The precursor of alumina is hydrated alumina, such as pseudo-boehmite, and the particle size, morphology, crystallinity, impurity crystal content and the like of the alumina carrier have influence on the properties of pore volume, pore distribution, specific surface area and the like. In the prior art, alumina carriers meeting specific requirements can be obtained by modulating the properties of particle size, morphology, crystallinity and the like of hydrated alumina.

Pseudo-boehmite as a raw material for alumina carriers is generally prepared by the following method: (1) alkali precipitation, i.e., neutralization of the acidified aluminum salt with alkali. Precipitating alumina monohydrate from the acidified aluminum salt solution with a base, and then aging, washing, drying and the like to obtain a pseudo-boehmite product, which is commonly called as a base precipitation (acid method), such as a method for neutralizing aluminum trichloride with ammonia water; (2) Acid precipitation, i.e. neutralization of aluminates with strong acids or aluminium salts of strong acids. The acid is used to precipitate alumina monohydrate from aluminate solution, then the pseudo-boehmite product is obtained through the processes of aging, washing, drying and the like, and the method is commonly called acid precipitation (alkaline method) and comprises the following steps: CO ₂ A method for neutralizing sodium metaaluminate by gas, and a method for neutralizing sodium metaaluminate by aluminum sulfate; (3) The hydrolysis of alkoxy aluminium is carried out on the alkoxy aluminium and water to generate alumina monohydrate, and then the alumina monohydrate is aged, filtered and dried to obtain the pseudo-boehmite product. The preparation process of pseudo-boehmite generally comprises the processes of grain formation (neutralization precipitation or hydrolysis process), grain growth (aging process), washing, drying and the like. Therefore, the process conditions of grain generation and grain growth can influence the quantity and growth speed of grain generation, the preparation process of various pseudo-boehmite provides respective process conditions, and the grain size and crystallinity of the product are controlled so as to achieve the purpose of controlling the physical properties of the product, such as pore volume, specific surface area and the like.

The pore structure, surface acidity and thermal stability of the carrier can be changed by introducing phosphorus into the alumina, so that the activity of the hydrogenation catalyst can be improved.

The method is that firstly pseudo-boehmite powder is used for preparing an alumina carrier through molding and roasting, and then phosphorus is introduced into the alumina carrier through an impregnation method to prepare phosphorus modified alumina. The heat stability of the alumina can be improved by adopting an impregnation method to prepare phosphorus modified activated alumina, but the alumina is impregnated by phosphoric acid, part of the alumina is dissolved in phosphoric acid solution and reacts with phosphate to generate aluminum phosphate, and the aluminum phosphate is deposited in alumina pore channels and can block the pore channels, so that the specific surface area and the pore volume are reduced.

One method is to add a phosphorus-containing compound during the molding of pseudo-boehmite, followed by calcination of the molded compound to produce phosphorus-modified alumina. CN103721732a discloses a phosphorus-added modified pseudo-boehmite catalyst carrier material and a preparation method. Adding an aluminum sulfate solution with the alumina concentration of 45-55g/L and a sodium metaaluminate solution with the alumina concentration of 200-250g/L and the caustic ratio of 1.1-1.3 into a neutralization reaction kettle 1, controlling the pH value to be 6.0-8.0 and the temperature to be 50-70 ℃; the slurry of the neutralization reaction kettle 1 flows into the neutralization reaction kettle 2 through an overflow reaction pipe, and sodium carbonate solution with the concentration of 100-200g/L is added into the neutralization reaction kettle 2, the pH value is controlled to be 8.5-10.0, and the reaction temperature is controlled to be 50-70 ℃; 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 80-95 ℃, and the aging is carried out for 2 hours; according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, calculating the volume of a phosphoric acid solution with the phosphorus pentoxide concentration of 50-150g/L added into the aging reaction kettle, wherein the phosphorus pentoxide content of the added phosphoric acid is 3-5% of the alumina content; and (5) washing and drying after the aging is finished to obtain the phosphorus-containing pseudo-boehmite.

Although the above documents disclose various methods for producing phosphorus-containing pseudo-boehmite, and the properties of the pseudo-boehmite obtained are excellent in some respects, the properties of the catalyst are still further improved when the alumina produced therefrom is used as a catalyst support.

Disclosure of Invention

The invention aims to overcome the defect that the hydrogenation activity of a catalyst needs to be further improved when alumina prepared from pseudo-boehmite in the prior art is used as a catalyst carrier, and provides a modified pseudo-boehmite, a preparation method thereof, modified alumina and a hydrogenation catalyst. The catalyst obtained by adopting the carrier prepared from the modified pseudo-boehmite provided by the invention has better hydrogenation activity.

The inventor of the present invention found in the research process that in the preparation process of pseudo-boehmite, by adding a phosphorus-containing compound and a nonmetallic auxiliary element into raw materials, adding a grain growth regulator in the precipitation reaction or hydrolysis reaction process, controlling the pH of the precipitation reaction or hydrolysis reaction to be 4-7, and then adjusting the pH to 7-10.5 for aging, the adjustment of the grain growth mode is enhanced, so that a modified pseudo-boehmite product with h being less than or equal to 1.7 and less than or equal to 4, preferably with h being less than or equal to 1.9 and less than or equal to 4, more preferably with h being less than or equal to 2.2 and less than or equal to 3.5 can be prepared, and the hydrogenation activity of a catalyst using the modified alumina obtained after roasting the modified pseudo-boehmite as a carrier can be effectively improved. The phosphorus-containing pseudo-boehmite prepared by the prior art is generally 0.85-1.65 because h is not controlled. The modified pseudo-boehmite has the characteristic that h is more than or equal to 1.7 and less than or equal to 4, preferably 1.9 and less than or equal to 4, and more preferably 2.2 and less than or equal to 3.5, so that the hydrogenation performance of the catalyst can be improved when the modified pseudo-boehmite is used as a precursor of a carrier of the hydrogenation catalyst.

In order to achieve the above object, a first aspect of the present invention provides a modified pseudo-boehmite containing a phosphorus element and a nonmetallic auxiliary element, wherein h of the modified pseudo-boehmite satisfies 1.7.ltoreq.h.ltoreq.4, 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 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 pseudo-boehmite crystal grains, 031 represents a peak in the XRD spectrum in which 2θ is 34 to 43 °, 020 represents a peak in the XRD spectrum in which 2θ is 10 to 15 °, d=kλ/(bcosθ), K is a Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-width of the diffraction peak, and 2θ is a position of the diffraction peak.

Preferably, the h of the modified pseudo-boehmite is 1.9-4, preferably 2.2-3.5.

The second aspect of the invention provides a method for preparing a modified pseudo-boehmite, comprising the steps of:

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

(2) Aging the modified hydrated alumina obtained in the previous step under the condition that the pH value is 7-10.5;

The precipitation reaction or the hydrolysis reaction in the step (1) is carried out in the presence of a grain growth regulator, a phosphorus-containing compound and a non-metal auxiliary compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes.

In a third aspect, the present invention provides a modified alumina obtained by calcining a modified pseudo-boehmite, which is the modified pseudo-boehmite according to the first aspect or the modified pseudo-boehmite obtained by the method according to the second aspect.

In a fourth aspect, the present invention provides a modified alumina comprising phosphorus element and a nonmetallic aid element, wherein the modified alumina has an IR spectrum of (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) 1.9-3.5, wherein I ₃₆₇₀ 3670cm ^-1 Peak height, I ₃₅₈₀ 3580cm ^-1 Peak height, I ₃₇₇₀ 3770cm ^-1 Peak height, I ₃₇₂₀ 3720cm ^-1 Peak height.

In a fifth aspect, the present invention provides a hydrogenation catalyst comprising a support and an active metal component supported on the support, the support being a modified alumina as described in the foregoing third or fourth aspect.

Compared with the prior art, the modified pseudo-boehmite provided by the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 4, so that the modified alumina obtained by roasting the modified pseudo-boehmite is more suitable for being used as a heavy oil hydrogenation catalyst carrier, and the obtained catalyst has more excellent hydrogenation activity and high stability. The preparation method of the modified pseudo-boehmite provided by the invention has the characteristics that h is more than or equal to 1.7 and less than or equal to 4 by adding the phosphorus-containing compound, the non-metal auxiliary compound, the grain growth regulator and the sectional control of the pH value in the preparation process. The modified aluminum oxide of the modified pseudo-boehmite after roasting has specific surface hydroxyl group distribution, In the IR spectrum of the modified alumina, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) 1.9 to 3.5; wherein I is ₃₆₇₀ 3670cm ^-1 Peak height, I ₃₅₈₀ 3580cm ^-1 Peak height, I ₃₇₇₀ 3770cm ^-1 Peak height, I ₃₇₂₀ 3720cm ^-1 The peak is high, the catalyst is more suitable for being used as a catalyst carrier, and the obtained catalyst has more excellent heavy oil hydrogenation activity and high stability.

Detailed Description

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

According to a first aspect of the invention, there is provided a modified pseudo-boehmite comprising a phosphorus element and a non-metal additive element, wherein h of the modified pseudo-boehmite satisfies 1.7.ltoreq.h.ltoreq.4, 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 grain, D (020) represents a crystal grain size of a crystal plane represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, the 031 peak is a peak in the XRD spectrum in which 2θ is 34-43 °, the 020 peak is a peak in which 2θ is 10-15 °, d=kλ/(bcosθ), K is a Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-peak width of the diffraction peak, and 2θ is a position of the diffraction peak.

In the present invention, for different diffraction peaks, B and 2θ each take the value of the corresponding peak, for example, when D (031) is calculated, D (031) =kλ/(Bcos θ), where B is the half-peak width of the 031 diffraction peak and 2θ is the position of the 031 diffraction peak; when D (020) is calculated, D (020) =kλ/(bcosθ), where B is the half-width of the 020 diffraction peak and 2θ is the position of the 020 diffraction peak. In the invention, the nonmetallic auxiliary elements do not include phosphorus.

Preferably, the h of the modified pseudo-boehmite is more preferably more than or equal to 1.9 and less than or equal to 4, and more preferably more than or equal to 2.2 and less than or equal to 3.5. Within this preferred range, the hydrogenation activity of the resulting catalyst is more excellent.

h, the modified pseudo-boehmite which meets the requirements has specific hydroxyl distribution, and is more beneficial to improving the desulfurization performance of the catalyst. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.

The relative crystallinity of the modified pseudo-boehmite provided by the invention (based on commercial SB powder of Condea company) is generally in the range of 45-77%, preferably 65-77%.

Preferably, the nonmetallic auxiliary elements include fluorine element and/or silicon element.

The modified pseudo-boehmite provided by the invention contains phosphorus element and nonmetallic auxiliary agent element, preferably, based on the total dry basis of the modified pseudo-boehmite, al ₂ O ₃ The content of (2) is 79 to 98.9 wt%, preferably 85 to 97.5 wt%; p (P) ₂ O ₅ The content of said nonmetallic aid element is from 1 to 6% by weight, preferably from 2 to 5% by weight, and the content of said nonmetallic aid element is from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight.

In the invention, when the nonmetallic auxiliary agent element is F element, the content of the nonmetallic auxiliary agent element is calculated by the F element; when the nonmetallic auxiliary agent element is Si element, the content of the nonmetallic auxiliary agent element is SiO ₂ And (5) counting.

In the invention, the crystal structure of the modified pseudo-boehmite is measured by a D5005X-ray diffractometer of Siemens of Germany, and the CuK alpha radiation, 44 kilovolts, 40 milliampere and the scanning speed is 2 ^° /min.

The modified pseudo-boehmite provided by the invention contains phosphorus element and nonmetallic auxiliary agent element, has a specific crystal structure, and the catalyst containing the carrier prepared from the modified pseudo-boehmite provided by the invention shows excellent hydrogenation activity and high stability.

In the method provided by the invention, the precipitation reaction or the hydrolysis reaction is carried out under the condition that the pH is 4-7 in the presence of the grain growth regulator, the phosphorus-containing compound and the nonmetallic auxiliary agent-containing compound, so that the precipitation of the modified hydrated alumina can be met, the lower pH condition is maintained, the excessive growth of the modified pseudo-boehmite grains under the high pH condition is avoided, and the common regulation effect of the phosphorus and the growth regulator on the growth of the modified pseudo-boehmite is enhanced. The grain growth of the modified pseudo-boehmite in the whole process of generation and aging of the modified hydrated alumina is carried out in the presence of phosphorus-containing compounds, nonmetallic auxiliary compounds and grain regulators, so that the prepared modified pseudo-boehmite has a special crystal structure and is particularly suitable for serving as a carrier precursor of a heavy oil hydrogenation catalyst.

According to one embodiment of the invention, step (1) comprises: the inorganic aluminum-containing compound solution, the phosphorus-containing compound, the non-metal auxiliary compound, the grain growth regulator and the acid or alkali are contacted to carry out precipitation reaction, or the organic aluminum-containing compound, the phosphorus-containing compound, the non-metal auxiliary compound, the grain growth regulator and the water are subjected to hydrolysis reaction; 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 and a non-metal auxiliary compound at a pH of 4 to 6.5. So that the precipitation reaction or the hydrolysis reaction is carried out at the above preferable pH, which is more beneficial to improving the activity of the prepared carrier in heavy oil hydrogenation.

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

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

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

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

In the present invention, the manner of adding 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 precipitation reaction is not particularly limited, and is preferably 1 to 10% by weight, more preferably 1.5 to 8.5% by weight, still more preferably 2 to 6% by weight, based on the weight of the inorganic aluminum-containing reactant.

Preferably, the grain growth regulator is used in the hydrolysis reaction in an amount of 1 to 10% by weight, preferably 1.5 to 8.5% by weight, and more preferably 2 to 6% by weight, based on the weight of the organic aluminum-containing compound, based on the alumina.

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

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

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

In order to better exert the effect of regulating the grain growth by the phosphorus-containing compound and the nonmetallic auxiliary compound, the phosphorus-containing compound and the nonmetallic auxiliary compound are preferably used in such an amount that the total dry basis of the modified pseudo-boehmite in the prepared modified pseudo-boehmite is taken as the reference, P ₂ O ₅ The content of said nonmetallic aid element is from 1 to 6% by weight, preferably from 2 to 5% by weight, and the content of said nonmetallic aid element is from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight.

The nonmetallic aid-containing compound of the present invention is not particularly limited, and may be a nonmetallic aid-containing compound known in the art; preferably, the non-metallic auxiliary comprises a fluorine-containing compound and/or a silicon-containing compound.

Preferably, the fluorine-containing compound is at least one of ammonium fluoride, ammonium bifluoride, hydrofluoric acid, sodium fluoride and calcium fluoride.

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

It is noted that the grain growth regulator, the phosphorus-containing compound and the nonmetallic auxiliary compound are added during the precipitation reaction or the hydrolysis reaction, so that the growth speed of grains on a 020 crystal plane and a 031 crystal plane is more favorably regulated, and h is more favorably 1.7-4, preferably 1.9-4, and more preferably 2.2-3.5. The grain growth regulator and the phosphorus-containing compound and the non-metal auxiliary compound are added during the precipitation reaction or the hydrolysis reaction, so that the aging reaction carried out later is also carried out in the presence of the grain growth regulator and the phosphorus-containing compound and the non-metal auxiliary compound. Preferably, no grain growth regulator and no phosphorus-containing compound or non-metal auxiliary compound are additionally added during the aging process.

According to the method provided by the invention, the inorganic aluminium-containing compound is preferably an aluminium salt and/or an aluminate. Accordingly, the inorganic aluminum-containing compound solution may be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution may be various aluminum salt solutions, for example, may be an aqueous solution of one or more of aluminum sulfate, aluminum chloride, and aluminum nitrate. Because of its low cost, aluminum sulfate solution and/or aluminum chloride solution are preferred. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solution is preferred because of its ease of availability and low cost. The aluminate solutions may also be used alone or in mixtures.

The concentration of the inorganic aluminum-containing compound solution is not particularly limited, and preferably the concentration of the inorganic aluminum-containing compound solution is 20 to 200 g/l in terms of aluminum oxide.

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

The alkali can be hydroxide or salt which is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, preferably, the hydroxide is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from at least one of sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate. The base may be introduced in the form of a solution, and the concentration of the alkali solution is not particularly limited, and preferably OH ^- The concentration of (2) is 0.2-4 mol/L. When sodium metaaluminate and/or potassium metaaluminate are used as the base, the amounts of the grain growth regulator and the phosphorus-containing compound are calculated, and the corresponding amounts of alumina in sodium metaaluminate and/or potassium metaaluminate are also considered.

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

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

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

The aging condition in the step (2) is selected in a wide range, so long as the aging condition is ensured to be performed under the condition that the pH is 7-10.5. Since the precipitation reaction or the hydrolysis reaction in step (1) is carried out at a pH of 4 to 7, it is preferable to introduce a base to adjust the pH of the aging reaction before aging is carried out. The manner and kind of introduction of the base may be as described above.

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

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

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

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 compound, a nonmetallic auxiliary compound and a grain growth regulator and an alkaline solution or an acid solution in parallel flow or intermittently into a reaction vessel for precipitation reaction to obtain modified hydrated alumina slurry; or adding a phosphorus-containing compound, a non-metal auxiliary compound and a grain growth regulator into deionized water to carry out hydrolysis reaction with aluminum alkoxide to obtain modified hydrated alumina slurry, and carrying out precipitation reaction or hydrolysis reaction under the condition that the pH is 4-7, preferably 4-6.5 by using an acid solution or an alkali solution;

(2) Adding alkaline solution into the modified alumina hydrate slurry obtained in the step (1) to adjust the pH to 7-10.5, and aging for 0.5-8 hours at 50-95 ℃;

(3) Filtering and washing the product obtained in the step (2);

(4) And (3) drying the product obtained in the step (3) to obtain the modified pseudo-boehmite provided by the invention.

In a preferred embodiment of the present invention, the modified alumina is obtained by sequentially performing optional molding, drying and calcination of the modified pseudo-boehmite.

The molding conditions, drying conditions and baking conditions are not particularly limited, and may be conventional in the art. The molding method can be at least one of rolling ball, tabletting and extrusion molding, preferably extrusion molding, and then drying and roasting; the shape after molding can be clover, butterfly, cylinder, hollow cylinder, four-leaf, five-leaf, sphere, etc. In order to ensure that the molding is carried out smoothly, water, an extrusion aid and/or an adhesive can be added, and a pore-expanding agent can be optionally added, wherein the types and the amounts of the extrusion aid, the peptizing agent and the pore-expanding agent are well known to those skilled in the art, for example, common extrusion aid can be at least one selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene alcohol, the peptizing agent can be organic acid and/or organic acid, and the pore-expanding agent can be at least one selected from starch, synthetic cellulose, polyalcohol and surfactant. Wherein the synthetic cellulose is preferably at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymeric alcohol is preferably at least one of polyethylene glycol, polypropylene glycol and polyvinyl alcohol; the surfactant is preferably at least one of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and acrylic alcohol copolymer and maleic acid copolymer with molecular weight of 200-10000. The drying conditions preferably include: the drying temperature is 40-350 ℃, more preferably 100-200 ℃; the drying time is 1 to 24 hours, more preferably 2 to 12 hours.

The conditions of the firing are not particularly limited in the present invention, and preferably the conditions of the firing include: the temperature is 350-1000deg.C, preferably 400-800deg.C, and the time is 1-10 hr, preferably 2-6 hr.

In a fourth aspect, the present invention provides a modified alumina comprising phosphorus element and a nonmetallic aid element, wherein the modified alumina has an IR spectrum of (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) 1.9 to 3.5, preferably 2 to 3.3; wherein I is ₃₆₇₀ 3670cm ^-1 Peak height, I ₃₅₈₀ 3580cm ^-1 Peak height, I ₃₇₇₀ 3770cm ^-1 Peak height, I ₃₇₂₀ 3720cm ^-1 Peak height. The nonmetallic auxiliary elements are the same as those provided in the first aspect of the present invention, and will not be described here again.

According to a fourth aspect of the present invention, there is provided a modified alumina obtained by calcining a modified pseudo-boehmite, wherein the modified pseudo-boehmite is the modified pseudo-boehmite according to the first aspect or the modified pseudo-boehmite obtained by the method according to the second aspect.

The modified alumina provided by the invention has specific surface hydroxyl distribution, and is used as a carrier for a heavy oil hydrogenation catalyst, so that the catalyst has higher hydrogenation activity and high stability.

The IR spectrumMeasured by a Nicolet model 870 Fourier infrared spectrometer of Nicolet company in the United states. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram ^-1 Peak height at 3580cm ^-1 Peak height at 3770cm ^-1 Peak height at 3720cm ^-1 Calculation of the value of peak height (I ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Is a value of (2). Alumina carrier of the prior art (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Typically lower than 1.8.

According to the present invention, preferably, the modified alumina has a nitrogen adsorption pore volume of 0.7 to 1.6 ml/g, a BET nitrogen adsorption specific surface area of 250 to 380 square meters/g, and a pore diameter of 8 to 16 nm. The diameter of the holes refers to the diameter corresponding to the highest point of the hole distribution curve. The modified alumina provided by the invention has larger pore volume and specific surface area.

The modified alumina provided by the invention can be used as various adsorbents, catalyst carriers and matrixes of catalysts.

In a fifth aspect, the present invention provides a hydrogenation catalyst comprising a support and an active metal component supported on the support, the support being a modified alumina as described in the third or fourth aspect above.

According to the present invention, the kind and the content of the active metal component are not particularly limited, and may be those commonly used in the art for hydrocarbon oil hydrotreating catalysts; preferably, the active metal component is selected from a group VIB metal component and/or a group VIII metal component. The present invention is not particularly limited with respect to the group VIB metal component, which is preferably Mo and/or W, and the group VIII metal component, which is preferably Co and/or Ni.

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

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

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

The hydrogenation catalyst provided by the invention can also contain any auxiliary agent which does not influence the performance of the hydrogenation catalyst or can improve the performance of the hydrogenation catalyst, for example, at least one of IIA, IIIA, IVA, VA, VIIA, IIB, IIIB group elements and rare earth metal elements, preferably at least one of boron, fluorine, silicon, zinc, calcium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated as the simple substance element is not more than 10 weight percent, preferably 0.5-6 weight percent based on the catalyst.

The method for producing the hydrogenation catalyst is not particularly limited, and the hydrogenation active metal component may be supported on a composite catalyst by any method known in the art, for example, kneading, dry mixing, or dipping; preferably, the method of supporting the hydrogenation-active metal component on a phosphorus-containing alumina comprises impregnating the phosphorus-containing alumina with an impregnating solution comprising at least one group VIB metal compound and at least one group VIII metal compound, followed by drying and calcination. Further, the method and time of the impregnation are not particularly limited, and the impregnation method may be excessive liquid impregnation, pore saturation impregnation, multiple impregnation and the like according to the amount of the impregnation liquid, and may be soaking, spray impregnation and the like according to the manner of the impregnation; the impregnation time is preferably 0.5 to 3 hours. Further, by adjusting and controlling the concentration, amount or amount of support of the impregnation liquid, a specific amount of hydrogenation catalyst can be prepared, as is well known to those skilled in the art.

According to the present invention, the drying conditions and the calcination conditions in the method for supporting the hydrogenation-active metal component on the catalyst are not particularly limited, and preferably the drying conditions include: the drying temperature is 80-200deg.C, preferably 100-150deg.C; the drying time is 1 to 8 hours, preferably 2 to 6 hours. The drying mode is not particularly limited in the present invention, and the drying may be at least one of drying, forced air drying, spray drying and flash drying. Preferably, the conditions of calcination include: the roasting temperature is 200-700 ℃, preferably 350-600 ℃; the calcination time is 1 to 10 hours, preferably 2 to 8 hours. According to the present invention, the atmosphere for the firing and the drying is not particularly limited, and may be at least one of air, oxygen and nitrogen, preferably air.

According to a preferred embodiment of the present invention, the preparation method of the hydrogenation catalyst comprises: impregnating the modified alumina with an impregnating solution containing an active metal component, then drying at 80-200 ℃ for 1-8 hours, and then roasting at 200-700 ℃ for 1-10 hours.

The hydrogenation catalyst provided by the invention can be used alone or in combination with other catalysts.

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

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

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

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

The present invention will be described in detail by examples. In the following examples, XRD was measured on a SIMENS D5005 type X-ray diffractometer, with CuK alpha radiation, 44 kilovolts, 40 milliamps, scan speed of 2 ^° /min. According to the Scherrer formula: d=kλ/(bcosθ) (D is the grain size, λ is the diffraction wavelength of the target material, B is the half-width of the corrected diffraction peak, and 2θ is the position of the diffraction peak), the grain size of (020) is calculated as D (020) with the parameters of the 2θ as 10-15 ° peak, the grain size of (031) is calculated as D (031) with the parameters of the 2θ as 34-43 ° peak, and h=d (031)/D (020) is calculated.

The IR spectrum was measured by a Nicolet 870 Fourier infrared spectrometer from Nicolet corporation, USA. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram ^-1 Peak height at 3580cm ^-1 Peak height at 3770cm ^-1 Peak height at 3720cm ^-1 Calculation of the value of peak height (I ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Is a value of (2).

Example 1

This example is intended to illustrate the modified pseudo-boehmite, modified alumina (i.e., support) and hydrogenation catalysts provided by the present invention and methods of making the same.

(1) Preparation of hydrated alumina PA1:

in a 2L reaction tank, 5000 mL of aluminum oxide with the concentration of 60 g/L, 8.0mL of aluminum sulfate solution containing 6.0 g of ribitol, 85 wt% of concentrated phosphoric acid, 4g of ammonium fluoride and 6 wt% of ammonia water solution are added in parallel to carry out precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into slurry to enable the pH value of the slurry to be 8.7, the slurry is aged for 120 minutes at 70 ℃ and then filtered, a filter cake is pulped and washed for 2 times by deionized water, and the filter cake is dried for 24 hours at 120 ℃ to obtain modified hydrated aluminum oxide PA1, and the PA1 has a pseudo-boehmite structure by adopting XRD.

The h values calculated by XRD characterization to give PA1 are listed in Table 1. Relative crystallinity of PA1 and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1.

The PA1 is roasted for 4 hours at 600 ℃ to obtain the alumina. The hydroxyl groups on the alumina surface were measured by infrared spectroscopy. (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

(2) Preparation of a modified alumina support Z1:

1000 g of the above-mentioned alumina hydrate PA1 and 30 g of sesbania powder (produced by Henan Orchiku sesbania gum plant) were taken and mixed uniformly, then 930 ml of an aqueous solution containing 20g of nitric acid was added, and a butterfly-shaped wet strip having an outer diameter of 1.4mm was extruded on a plunger type strip extruder, and then the butterfly-shaped wet strip was dried at 120℃for 4 hours and then calcined at 600℃for 3 hours, to obtain a carrier Z1.

(3) Preparation of hydrogenation catalyst C1:

110 g of the support Z1 are taken and 110 ml of a mixed solution consisting of ammonium molybdate and nickel nitrate (the mixed solution contains MoO ₃ 320 g/l, niO 81 g/l) impregnated the support Z1 1 hours, dried at 110 ℃ for 4 hours, and calcined at 400 ℃ for 3 hours to give hydrogenation catalyst C1.

Comparative example 1

Pseudo-boehmite DPA1, a support DZ1 and a hydrogenation catalyst DC1 were prepared as in example 1, except that only 8.0mL of 85 wt% phosphoric acid was added to the aluminum sulfate solution without ribitol and ammonium fluoride to obtain alumina hydrate CPA1. CPA1 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA1, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 2

Pseudo-boehmite DPA2, a carrier DZ2 and a hydrogenation catalyst DC2 were prepared in the same manner as in example 1 except that ammonium fluoride was not added to the aluminum sulfate solution, the flow rate of the aqueous ammonia solution was directly controlled to adjust the pH of the reaction system to 8.7, and after the precipitation reaction was completed, it was not necessary to add aqueous ammonia to the slurry to adjust the pH to obtain hydrated alumina CPA2. CPA2 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA2, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 3

Pseudo-boehmite DPA3, a support DZ3 and a hydrogenation catalyst DC3 were prepared as in example 1, except that 6.0 g of ribitol was added to the aluminum sulfate solution without concentrated phosphoric acid and ammonium fluoride to obtain hydrated alumina CPA3. The XRD characterization was performed as in example 1, CPA3 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Example 2

This example is illustrative of the modified pseudo-boehmite, modified alumina and hydrogenation catalyst provided by the invention and methods of making the same.

(1) Preparation of hydrated alumina PA2:

in a2 liter reaction tank, 4000 mL of an alumina/liter solution containing 85 wt% concentrated phosphoric acid 22.1mL, silica sol 29 g, sorbitol 4.52 g/liter and 1000 mL of a sodium metaaluminate solution containing 210 g of alumina/liter and having a caustic coefficient of 1.58 were added in parallel to carry out precipitation reaction, the reaction temperature was 80 ℃, the flow rate of the reactants was adjusted so that the neutralization pH was 4.0, and the reaction residence time was 15 minutes; dilute ammonia water with the concentration of 5 weight percent is added into the obtained slurry to adjust the pH of the slurry to 9.0, the temperature is raised to 85 ℃, the aging is carried out for 3 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20 liters of deionized water (the temperature is 85 ℃) is added on a filter cake to wash the filter cake for about 30 minutes. And adding the qualified filter cake into 3 liters of deionized water, stirring to form slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer to be in the range of 100-110 ℃, and drying the material for about 2 minutes to obtain the hydrated alumina PA2. As characterized by XRD in accordance with the method of example 1, PA2 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA2, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the modified alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

(2) Preparation of vector Z2:

carrier Z2 was prepared by the method of step (2) in example 1 above, except that PA2 was extruded into butterfly strips having a phi of 1.5 mm to give carrier Z2.

(3) Preparation of hydrogenation catalyst C2:

100 g of the support Z2 were taken and 110 ml of a mixed solution consisting of ammonium molybdate and nickel nitrate (the mixed solution contains MoO ₃ 231 gPer liter, niO 56 g/liter) impregnated the support Z2 1 hours, then dried at 120 ℃ for 3 hours, and calcined at 420 ℃ for 3 hours to give hydrogenation catalyst C2.

Comparative example 4

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 2, except that the solution of aluminum trichloride contained no sorbitol and no silica sol, yielding alumina hydrate CPA4. CPA4 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA4, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 5

Pseudo-boehmite, a carrier and a hydrogenation catalyst were prepared in the same manner as in example 2 except that the alumina trichloride solution contained no silica sol, and the flow rate of the sodium metaaluminate solution was directly controlled so that the pH of the reaction system was 9.0, and after the completion of the precipitation reaction, it was not necessary to add ammonia water to the slurry to adjust the pH to obtain alumina hydrate CPA5. CPA5 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA5, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 6

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 2, except that concentrated phosphoric acid and silica sol were not contained in the aluminum trichloride solution, to obtain alumina hydrate CPA6. The XRD characterization was performed as in example 1, CPA6 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Example 3

(1) Preparation of hydrated alumina PA3:

in a 2L reactor, adding 3000 mL of 60 g alumina/L, 4.5 g gluconic acid, 6g hydrofluoric acid, 3.5mL aluminum sulfate solution containing 85 wt% concentrated phosphoric acid and 1000 mL sodium metaaluminate solution containing 200 g alumina/L and 1.58 caustic coefficient in parallel flow, precipitating reaction, the reaction temperature is 55 ℃, the flow rate of reactants is regulated to neutralize pH value to 6.5, the reaction stays for 15 minutes, then adding 100 g/L sodium carbonate solution into the obtained slurry, regulating the pH value of the slurry to 9.5, heating to 75 ℃, aging for 5 hours, filtering by a vacuum filter, after the filtering is finished, adding 20L deionized water (temperature is 85 ℃) to the filter cake for flushing the filter cake for about 30 minutes. The filter cake was dried at 120℃for 24 hours to give hydrated alumina PA3. As characterized by XRD in accordance with the method of example 1, PA3 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA3, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the modified alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

(2) Preparation of vector Z3:

the carrier Z3 was prepared by the method of step (2) in example 1 above, except that PA3 was extruded into butterfly strips having a diameter of 1.6 mm to give carrier Z3.

(3) Preparation of hydrogenation catalyst C3:

100 g of the carrier Z3 were taken and 110 ml of a mixed solution composed of ammonium metatungstate and nickel nitrate (the mixed solution contains WO ₃ 427 g/l, niO 46 g/l) impregnated with the support Z3 1 hours, dried at 110 ℃ for 4 hours, and calcined at 400 ℃ for 3 hours to give hydrogenation catalyst C3.

Example 4

The procedure of example 3 was followed except that during the precipitation reaction, the reactant flow was adjusted so that the neutralization pH was 7. Hydrated alumina PA4 is obtained. As characterized by XRD in accordance with the procedure of example 1, PA4 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA4, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the modified alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 7

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 4, except that the aluminum sulfate solution contained no gluconic acid, hydrofluoric acid, to give hydrated alumina CPA7. CPA7 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA7, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 8

Pseudo-boehmite, a carrier and a hydrogenation catalyst were prepared according to the method of example 4, except that hydrofluoric acid was not added to the aluminum sulfate solution, and the flow rate of the sodium metaaluminate solution was directly controlled so that the pH of the reaction system was 9.5, and after the precipitation reaction was completed, it was not necessary to add a sodium carbonate solution to the slurry to adjust the pH, thereby obtaining alumina hydrate CPA8. CPA8 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA8, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 9

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 4, except that concentrated phosphoric acid, hydrofluoric acid were not contained in the aluminum sulfate solution, to obtain alumina hydrate CPA9. The XRD characterization was performed as in example 1, CPA9 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Example 5

(1) Preparation of hydrated alumina PA5:

into a 2 liter three-neck flask with a stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content: 15 wt%) was added, 4.6mL of 85% concentrated phosphoric acid, 20 g of silica, 15g of ribonucleic acid were added, the pH was adjusted to 5.1 by adding ammonia water, then heated to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, after reacting for 2 hours, the pH was adjusted to 8.5 by adding ammonia water, after reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aging was carried out at 80 ℃ for 6 hours, aqueous isopropyl alcohol was distilled off while aging was carried out, and after the aged hydrated alumina was filtered, dried at 120 ℃ for 24 hours, to obtain hydrated alumina PA5. As characterized by XRD in example 1, PA5 had pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA5, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the modified alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

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

Comparative example 10

According to the embodiment5, except that no ribonic acid and silica were added to the three-necked flask to obtain alumina hydrate CPA10. CPA10 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA10, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 11

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared as in example 5 except that silica was not added to a three-necked flask, and after the same amount of ribonucleic acid was added, then ammonia water was added to adjust the pH to 8.5, then heated to 60 ℃, and then 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel to obtain alumina hydrate CPA11. CPA11 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA11, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Comparative example 12

Pseudo-boehmite, a support, and a hydrogenation catalyst were prepared in the same manner as in example 5 except that concentrated phosphoric acid and silica were not added to a three-necked flask to obtain alumina hydrate CPA12. The XRD characterization was performed as in example 1, CPA12 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Example 6

Into a 2 liter three-neck flask with stirring and reflux condenser, 1000 g of isopropyl alcohol-water azeotrope (water content 15 wt%) was added, 7.0mL of 85% concentrated phosphoric acid, 20g of ammonium fluoride, 12g of ribonucleic acid were added, the pH was adjusted to 6.2 by adding ammonia water, heating to 60 ℃, 500 g of melted aluminum isopropoxide was slowly dropped into the flask through a separating funnel, after reacting for 5 hours, the pH was adjusted to 8.5 by adding ammonia water, after reflux reaction for 20 hours, dehydrated isopropyl alcohol was distilled off, aging was carried out at 80 ℃ for 6 hours, aqueous isopropyl alcohol was distilled off while aging was carried out, and after the aged hydrated alumina was filtered, it was dried at 120 ℃ for 24 hours to obtain hydrated alumina PA6. As characterized by XRD in accordance with the method of example 1, PA6 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA6, relative crystallinity and P ₂ O ₅ And the content of non-metallic auxiliary agents are also listed in table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

The PA6 was used to prepare support Z6 and hydrogenation catalyst C6 as in example 1.

Comparative example 13

The phosphorus-containing pseudo-boehmite is prepared according to the typical method in heavy oil hydrogenation catalyst carrier material research, and the concentration of 8.8mL of 85% concentrated phosphoric acid is 57 g.L ^-1 3000mL of aluminum sulfate solution with a concentration of 64 g.L ^-1 2500mL of sodium metaaluminate solution is subjected to precipitation reaction, the neutralization pH value is 8.0, the reaction time is 70min, then the aging is carried out, the aging temperature is 90 ℃, the aging pH value is 8.5, the filtering is carried out after the aging, the filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried at 120 ℃ for 24 hours to prepare the phosphorus-containing pseudo-boehmite CPA13. CPA13 has a pseudo-boehmite structure as characterized by XRD in accordance with the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA13, relative crystallinity and P ₂ O ₅ The content of (2) is also shown in Table 1. Roasting at 600 deg.c for 4 hr, and infrared spectrum to obtain hydroxyl radical on the surface of phosphorus-containing aluminaMeasurement, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

The CPA13 was prepared as described in example 1 to obtain DZ13 and DC13.

Comparative example 14

According to CN103721732A, a phosphorus-added modified pseudo-boehmite catalyst carrier material and a preparation method thereof are disclosed. 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 the neutralization reaction kettle 2 through an overflow reaction pipe, meanwhile, sodium carbonate solution with the concentration of 150g/L is added into the neutralization reaction kettle 2, the pH is controlled to be 9.5, and the reaction temperature is controlled to be 70 ℃; the slurry in the neutralization reaction kettle 2 flows into an aging reaction kettle through an overflow reaction pipe, the temperature of the slurry in the aging reaction kettle is 95 ℃, and the aging is carried out for 2 hours; according to the mass of the alumina added in the reaction process of the neutralization reaction kettle 1, calculating the volume of a phosphoric acid solution with 100g/L phosphorus pentoxide concentration added into the aging reaction kettle, wherein the phosphorus pentoxide content of the added phosphoric acid is 4% of the alumina content; and (5) washing and drying after the aging is finished to obtain the phosphorus-containing pseudo-boehmite. The XRD characterization was performed as in example 1, CPA14 having pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1, and the relative crystallinity is also shown in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

The CPA14 was prepared as described in example 1 to obtain DZ14 and DC14.

Example 7

Modified pseudo-boehmite, modified alumina and a hydrogenation catalyst were prepared in the same manner as in example 1 except that 17g of silica sol was further added to the aluminum sulfate solution to obtain alumina hydrate PA7. As characterized by XRD in accordance with the procedure of example 1, PA8 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA7, relative crystallinity and P ₂ O ₅ Non-metallic auxiliary agentsThe contents are likewise listed in Table 1. After roasting at 600 ℃ for 4 hours, measuring the hydroxyl groups on the surface of the phosphorus-containing alumina by using infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

Example 8

Modified pseudo-boehmite, modified alumina, and a hydrogenation catalyst were prepared in the same manner as in example 5 except that 15g of ammonium fluoride was added to the three-necked flask without adding silica to the flask, to obtain modified pseudo-boehmite PA8.

The XRD characterization was carried out as described in example 1, and PA8 had a pseudo-boehmite structure, and the h values calculated by XRD characterization to give PA10 are shown in Table 1, and the relative crystallinity is also shown in Table 1. After baking at 600 ℃ for 4 hours, the hydroxyl groups on the surface of the alumina are measured by infrared spectrum, (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) The values of (2) are listed in Table 1.

TABLE 1

Note that: m represents (I) ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) Values of (2)

As can be seen from the results of Table 1, the modified pseudo-boehmite prepared by the method provided by the invention has the characteristic that h is less than or equal to 1.7 and less than or equal to 4, preferably 2.2 and less than or equal to 3.5, and the h values of the pseudo-boehmite prepared by the prior art method and the method in the comparative example are all less than 1.7. As can be seen from the results in Table 1, the modified pseudo-boehmite prepared by the method of the invention is roasted at 600 ℃ to obtain an IR characterization spectrum of modified alumina, wherein the hydroxyl group has the characteristics (I ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ ) From 1.9 to 3.5, preferably from 2 to 3.3, by calcining at 600℃in the presence of pseudoboehmite prepared by the methods of the prior art and those of the comparative examplesIn the IR characterization spectrum of the obtained alumina, the hydroxyl characteristics (I ₃₆₇₀ +I ₃₅₈₀ )/(I ₃₇₇₀ +I ₃₇₂₀ )<1.8。

Test example 1

The catalyst was evaluated on a 100ml small fixed bed reactor using inferior heavy oil (inferior residuum having 2.5 wt% of sulfur element, 0.52 wt% of nitrogen element, 32. Mu.g/g of Ni, 24. Mu.g/g of V, and 9.7 wt% of carbon residue) as a raw material.

The hydrogenation catalysts prepared in examples 1 to 8 and comparative examples 1 to 14, 100mL, were crushed into particles having a diameter of 2 to 3 mm, and then subjected to presulfiding under the following conditions: the sulfide oil adopts Qingdao normal first-line kerosene containing 5w percent of dimethyl disulfide, and the liquid hourly space velocity of the sulfide oil is 1.2h ^-1 The hydrogen partial pressure is 14.0MPa, the hydrogen oil volume ratio is 600, and the constant temperature is carried out for 3 hours at 360 ℃. Then at 380 ℃ the reaction temperature, the hydrogen partial pressure is 15 MPa and the liquid hourly space velocity is 0.6 hour ^-1 The sample analysis was carried out after 100 hours of reaction at a hydrogen oil volume ratio of 600, and the catalyst loading was 100 ml to evaluate the hydrogenation activity and stability of the catalyst, and the results are shown in table 2.

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

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

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

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

TABLE 2

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As can be seen from Table 2, when the modified alumina prepared by roasting the modified pseudo-boehmite provided by the invention is used as a hydrogenation catalyst carrier, the catalyst has better hydrogenation activity under the same other conditions, and can be seen to have good stability.

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

Claims

1. A modified pseudo-boehmite is characterized in that the modified pseudo-boehmite contains phosphorus element and nonmetallic auxiliary agent element, and the modified pseudo-boehmite is characterized in thathMeets 1.7-lesshNot more than 4, whereinhD (031)/D (020), wherein D (031) represents the grain size of a crystal plane represented by a 031 peak in the XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents the grain size of a crystal plane represented by a 020 peak in the XRD spectrum of the pseudo-boehmite crystal grain, 031 peak is a peak of 34-43 ° in the XRD spectrum, 020 peak is a peak of 10-15 ° in the XRD spectrum, d=kλ/(bcosθ), K is Scherrer constant, λ is the diffraction wavelength of the target material, B is the half-peak width of the diffraction peak, and 2θ is the position of the diffraction peak; the nonmetallic auxiliary agent element comprises fluorine element and/or silicon element; the content of the nonmetallic auxiliary agent element is 0.1-15 wt%.

2. The modified pseudo-boehmite according to claim 1 wherein the modified pseudo-boehmitehMeets 1.9 to less than or equal toh≤4。

3. The modified pseudo-boehmite according to claim 1 or 2, wherein the modified pseudo-boehmitehMeets the requirement of 2.2 to less than or equal toh≤3.5。

4. The modified pseudo-boehmite according to claim 1 or 2, wherein,

based on the total dry basis of the modified pseudo-boehmite, al ₂ O ₃ Is 79 to 98.9 wt.%; p (P) ₂ O ₅ The content of (2) is 1-6 wt%.

5. The modified pseudo-boehmite according to claim 4 wherein,

based on the total dry basis of the modified pseudo-boehmite, al ₂ O ₃ The content of (2) is 85-97.5 wt%; p (P) ₂ O ₅ The content of the nonmetallic auxiliary agent element is 2-5 weight percent, and the content of the nonmetallic auxiliary agent element is 0.5-10 weight percent.

6. The modified pseudo-boehmite according to claim 1 or 2, wherein the relative crystallinity of the modified pseudo-boehmite is 45-77%.

7. A process for the preparation of a modified pseudo-boehmite according to any one of claims 1-6 comprising the steps of:

The precipitation reaction or the hydrolysis reaction in the step (1) is carried out in the presence of a grain growth regulator, a phosphorus-containing compound and a non-metal auxiliary compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth speed of grains on different crystal faces; the non-metal-containing auxiliary compound comprises a fluorine-containing compound and/or a silicon-containing compound; the dosages of the phosphorus-containing compound and the nonmetallic auxiliary compound are such that the content of the nonmetallic auxiliary element in the prepared modified pseudo-boehmite is 0.1-15% by weight based on the total dry basis of the modified pseudo-boehmite;

the substance capable of adjusting the growth rate of the crystal grains on different crystal planes is a substance capable of adjusting the growth rate of the crystal grains on a 020 crystal plane and a 031 crystal plane;

the substance capable of regulating the growth rate of the crystal grains on the 020 crystal face and the 031 crystal face is at least one of polyhydric sugar alcohol and carboxylate thereof;

the base is a hydroxide or a salt which hydrolyzes in an aqueous medium to make the aqueous solution alkaline.

8. The production process according to claim 7, 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 and a non-metal auxiliary compound at a pH of 4 to 6.5.

9. The production method according to claim 7 or 8, wherein the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30 to 90 ℃.

10. The production method according to claim 7 or 8, wherein the conditions of the precipitation reaction include: the reaction temperature is 40-90 ℃ and the reaction time is 10-60 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 2-30 hours.

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

12. The production method according to claim 7 or 8, wherein the grain growth regulator is at least one selected from the group consisting of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid and ribonate.

13. The production method according to claim 7 or 8, wherein the grain growth regulator is used in an amount of 1 to 10% by weight based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on aluminum oxide.

14. The production method according to claim 13, wherein the grain growth regulator is used in an amount of 1.5 to 8.5% by weight based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the aluminum oxide.

15. The production method according to claim 14, wherein the grain growth regulator is used in an amount of 2 to 6% by weight based on the weight of the inorganic aluminum-containing compound in the precipitation reaction, based on the aluminum oxide.

16. The production method according to claim 7 or 8, wherein the grain growth regulator is used in an amount of 1 to 10% by weight based on the weight of the organic aluminum-containing compound in the hydrolysis reaction, based on aluminum oxide.

17. The production method according to claim 16, wherein the crystal grain growth regulator is used in an amount of 1.5 to 8.5% by weight based on the weight of the organic aluminum-containing compound in the hydrolysis reaction, based on alumina.

18. The production method according to claim 17, wherein the grain growth regulator is used in an amount of 2 to 6% by weight based on the weight of the organic aluminum-containing compound in the hydrolysis reaction, based on alumina.

19. The production method according to claim 7 or 8, wherein the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, diammonium phosphate, sodium phosphate, and potassium phosphate.

20. The process according to claim 7 or 8, wherein the phosphorus-containing compound and the nonmetallic auxiliary compound are used in such an amount that P is based on the total dry weight of the modified pseudo-boehmite in the modified pseudo-boehmite ₂ O ₅ Content of (3)1-6 wt%.

21. The process according to claim 20, wherein the phosphorus-containing compound and the nonmetallic auxiliary compound are used in such an amount that P is based on the total amount of the dry matter of the modified pseudo-boehmite in the modified pseudo-boehmite ₂ O ₅ The content of the nonmetallic auxiliary agent element is 2-5 weight percent, and the content of the nonmetallic auxiliary agent element is 0.5-10 weight percent.

22. The production method according to claim 7 or 8, wherein the fluorine-containing compound is at least one of ammonium fluoride, ammonium bifluoride, hydrofluoric acid, sodium fluoride, and calcium fluoride.

23. The production method according to claim 7 or 8, wherein the silicon-containing compound is at least one selected from the group consisting of silicon oxide, silica sol, water glass, and sodium silicate.

24. The preparation method according to claim 7 or 8, wherein the aging in step (2) is performed at a pH of 8 to 10.

25. The preparation method according to claim 7 or 8, wherein the temperature of the aging is 50-95 ℃; the aging time is 0.5-8 hours.

26. The method of claim 25, wherein the aging temperature is 55-90 ℃; the aging time is 2-6 hours.

27. The production method according to claim 7 or 8, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate;

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

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

the hydroxide or the salt which is hydrolyzed in the water medium to make the water solution alkaline is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.

28. A modified alumina obtained by firing a modified pseudo-boehmite according to any one of claims 1 to 6.

29. A modified alumina containing phosphorus element and non-metal auxiliary element, wherein in the IR spectrum of the modified alumina, (I) ₃₆₇₀ +I ₃₅₈₀ ）/（I ₃₇₇₀ +I ₃₇₂₀ ) 1.9 to 3.5; wherein I is ₃₆₇₀ 3670 and 3670 cm ^-1 Peak height, I ₃₅₈₀ 3580 cm ^-1 Peak height, I ₃₇₇₀ 3770 cm ^-1 Peak height, I ₃₇₂₀ 3720 and 3720 cm ^-1 Peak height.

30. A modified alumina according to claim 29, wherein in the IR spectrum of the modified alumina, (I ₃₆₇₀ +I ₃₅₈₀ ）/（I ₃₇₇₀ +I ₃₇₂₀ ) 2-3.3; wherein I is ₃₆₇₀ 3670 and 3670 cm ^-1 Peak height, I ₃₅₈₀ 3580 cm ^-1 Peak height, I ₃₇₇₀ 3770 cm ^-1 Peak height, I ₃₇₂₀ 3720 and 3720 cm ^-1 Peak height.

31. The modified alumina of claim 29 or 30, which is calcined from a modified pseudo-boehmite, wherein the modified pseudo-boehmite is a modified pseudo-boehmite according to any one of claims 1-6.

32. A hydrogenation catalyst comprising a support and an active metal component supported on the support, the support being a modified alumina according to any one of claims 28 to 31.

33. The hydrogenation catalyst of claim 32, wherein the active metal component comprises a group VIB metal component and a group VIII metal component.

34. The hydrogenation catalyst of claim 33 wherein the catalyst is selected from the group consisting of,

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