CN113562751A

CN113562751A - Modified pseudo-boehmite, preparation method thereof, modified alumina and hydrogenation catalyst

Info

Publication number: CN113562751A
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: 2021-10-29
Anticipated expiration: 2040-04-28
Also published as: CN113562751B

Abstract

The invention relates to the field of pseudo-boehmite preparation, and discloses a modified pseudo-boehmite, a preparation method thereof, modified alumina and a hydrogenation catalyst, wherein h of the modified pseudo-boehmite satisfies that h is more than or equal to 1.7 and less than or equal to 4, wherein h is D (031)/D (020), D (031) represents the grain size of a crystal face represented by a 031 peak in an XRD spectrogram of a pseudo-boehmite grain, D (020) represents the grain size of a crystal face represented by a 020 peak in the XRD spectrogram of the pseudo-boehmite grain, the 031 peak refers to a peak with 2 theta of 34-43 degrees in the XRD spectrogram, the 020 peak refers to a peak with 2 theta of 10-15 degrees in the XRD spectrogram, D is K lambda/(Bcos theta), K is a Scherrer constant, lambda is the diffraction wavelength of a target material, B is the half-width of the diffraction peak, and 2 theta is the position of the diffraction peak. Compared with the prior art, the modified pseudoboehmite 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 pseudoboehmite 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 preparation of pseudo-boehmite, in particular to modified pseudo-boehmite, a preparation method thereof, modified alumina and a hydrogenation catalyst.

Background

Since the catalyst carrier plays a role in providing a diffusion path for reactants and products and providing attachment sites for the formation of a reactive active phase during the catalytic reaction, the adsorption of the carrier surface with the reactants and products and the interaction with the active component have an 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. Meanwhile, in the heavy distillate oil hydrotreating process, the raw materials contain a large number of reactant molecules with complex structures, large molecular diameters and rich heteroatom numbers, and the activity of the catalyst is continuously reduced due to the influence of metal deposition and carbon deposition in the reaction process, so that the catalyst is required to have good reaction activity and also have excellent diffusion performance and scale holding capacity, and therefore, the pore structure of the catalyst carrier can also play an important role in the performance of the catalyst. 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, especially gamma-alumina, is often used as a carrier for catalyst preparation due to its good pore structure, specific surface and thermal stability. The precursor of the alumina is hydrated alumina, such as pseudo-boehmite, and the particle size, morphology, crystallinity, heterocrystal content and the like of the alumina have influence on the properties of the alumina carrier, such as pore volume, pore distribution, specific surface area and the like. In the prior art, an alumina carrier which can meet specific requirements can be obtained by modulating the properties of the hydrated alumina, such as particle size, morphology, crystallinity and the like.

Pseudo-boehmite as a raw material of an alumina carrier is generally prepared by the following method: (1) alkali precipitation, i.e. neutralization of acidified aluminium salt with alkali. Precipitating alumina monohydrate from acidified aluminum salt solution by alkali, and obtaining a pseudoboehmite product through aging, washing, drying and other processes, wherein the process is commonly called alkali precipitation (acid process), such as a process of neutralizing aluminum trichloride by ammonia water; (2) acid precipitation, i.e. neutralization of the aluminate with a strong acid or an aluminum salt of a strong acid. Precipitation of alumina monohydrate from aluminate solutions with acid followed by aging, washing, drying and the like to give pseudoboehmite is commonly referred to as acid precipitation (alkaline process), the most common method currently comprising: CO 2₂A method for neutralizing sodium metaaluminate with gas, a method for neutralizing sodium metaaluminate with aluminum sulfate; (3) the hydrolysis of alkoxy aluminium is carried out by hydrolyzing alkoxy aluminium with water to generate hydrated alumina, aging, filtering and drying to obtain pseudo-boehmite. The preparation process of the pseudo-boehmite generally comprises the processes of grain generation (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 the generated grains, and the preparation process of various pseudo-boehmite provides respective process conditions and controls the grain size and the crystallinity of products so as to achieve the aim of controlling the grain size and the crystallinity of the productsThe physical properties such as the pore volume and the specific surface area of the product are controlled.

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.

One method is to prepare an alumina carrier by molding and roasting pseudo-boehmite powder, and then introduce phosphorus on the alumina carrier by an impregnation method to prepare phosphorus modified alumina. The phosphorus modified activated alumina prepared by the impregnation method can improve the thermal stability of the alumina, but the alumina is impregnated by phosphoric acid, part of the alumina is dissolved in phosphoric acid solution and reacts with phosphate radical to generate aluminum phosphate, and the aluminum phosphate is deposited in alumina pores and blocks the pores, so that the specific surface area and the pore volume are reduced.

One method is to add a phosphorus-containing compound during the formation of pseudo-boehmite and then calcine the formed compound to prepare phosphorus-modified alumina. CN103721732A discloses a phosphorus-modified pseudo-boehmite catalyst carrier material and a preparation method thereof. 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 a 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; calculating the volume of phosphoric acid solution with the phosphorus pentoxide concentration of 50-150g/L added into the aging reaction kettle according to the mass of the added alumina in the reaction process of the neutralization reaction kettle 1, wherein the phosphorus pentoxide content of the added phosphoric acid is 3% -5% of the alumina content; and washing and drying after aging to obtain the pseudo-boehmite containing phosphorus.

Although the above-mentioned documents disclose various methods for preparing pseudo-boehmite containing phosphorus and the properties of the obtained pseudo-boehmite are excellent in some respects, the properties of the catalyst are to be further improved when alumina prepared from them 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 invention finds that in the process of research, in the preparation process of the pseudoboehmite, the adjustment of the crystal grain growth mode is enhanced by adding a phosphorus-containing compound and a non-metal auxiliary element into the raw materials, adding a crystal grain growth regulator in the process of a precipitation reaction or a hydrolysis reaction, controlling the pH of the precipitation reaction or the hydrolysis reaction to be 4-7, and then adjusting the pH to be 7-10.5 for aging, so that a modified pseudoboehmite product with h being more than or equal to 1.7 and less than or equal to 4 can be prepared, preferably h being more than or equal to 1.9 and less than or equal to 4, more preferably h being more than or equal to 2.2 and less than or equal to 3.5, and the hydrogenation activity of a catalyst taking modified alumina obtained after roasting the modified pseudoboehmite as a carrier can be effectively improved. The above-mentioned pseudo-boehmite containing phosphorus prepared by the prior art is not controlled for h, which is generally 0.85-1.65. The modified pseudoboehmite of the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 4, 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, so when being used as a precursor of a carrier of a hydrogenation catalyst, the hydrogenation performance of the catalyst can be improved.

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 non-metal promoter element, wherein h of the modified pseudo-boehmite satisfies 1.7. ltoreq. h.ltoreq.4, wherein h ═ D (031)/D (020), D (031) denotes a crystal grain size of a crystal face represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grains, D (020) denotes a crystal grain size of a crystal face represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grains, the 031 peak denotes a peak having a2 θ of 34 to 43 ° in the XRD spectrum, the 020 peak denotes 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 a target material, B is a half width of a diffraction peak, and 2 θ is a position of the diffraction peak.

Preferably, h of the modified pseudoboehmite satisfies 1.9. ltoreq. h.ltoreq.4, preferably satisfies 2.2. ltoreq. h.ltoreq.3.5.

The second aspect of the invention provides a preparation method of modified pseudo-boehmite, which comprises the following steps:

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

(2) aging the obtained modified hydrated alumina 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 under the conditions that a grain growth regulator, a phosphorus-containing compound and a nonmetal-containing auxiliary agent compound exist and 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 third aspect of the present invention provides a modified alumina obtained by calcining modified pseudoboehmite, wherein the modified pseudoboehmite is the modified pseudoboehmite of the first aspect or the modified pseudoboehmite prepared by the method of the second aspect.

The fourth aspect of the invention provides a modified alumina, which contains phosphorus element and non-metallic auxiliary agent element, wherein in the IR spectrogram of the modified alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Is 1.9-3.5, wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height.

In a fifth aspect, the present invention provides a hydrogenation catalyst, which comprises a carrier and an active metal component supported on the carrier, wherein the carrier is the modified alumina described in the third or fourth aspect.

Compared with the prior art, the modified pseudoboehmite 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 thatThe modified alumina after roasting the modified pseudoboehmite is more suitable to be 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 characteristic 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-containing auxiliary compound, the grain growth regulator and the sectional control of the pH in the preparation process. The modified alumina of the calcined modified pseudo-boehmite has specific surface hydroxyl distribution, and in the IR spectrogram of the modified alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-3.5; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1The catalyst has high peak height, is more suitable to be used as a catalyst carrier, and has more excellent heavy oil hydrogenation activity and high stability.

Detailed Description

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

The first aspect of the invention provides a modified pseudo-boehmite containing a phosphorus element and a non-metal 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 the crystal grain size of a crystal face represented by a 031 peak in an XRD spectrogram of a pseudo-boehmite grain, D (020) represents the crystal grain size of a crystal face represented by a 020 peak in the XRD spectrogram of the pseudo-boehmite grain, the 031 peak refers to a peak with 2 theta of 34-43 DEG in the XRD spectrogram, the 020 peak refers to a peak with 2 theta of 10-15 DEG in the XRD spectrogram, D ═ K λ/(Bcos θ), K is a Scherrer constant, λ is the diffraction wavelength of a target material, B is the half-width of the diffraction peak, and 2 θ is the position of the diffraction peak.

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. In the present invention, the non-metallic additive element does not include a phosphorus element.

Preferably, h of the modified pseudoboehmite satisfies 1.9. ltoreq. h.ltoreq.4, more preferably 2.2. ltoreq. h.ltoreq.3.5. Within the preferred range, the hydrogenation activity of the resulting catalyst is more excellent.

h, the modified alumina prepared by roasting the modified pseudo-boehmite which meets the specification 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 modified pseudoboehmite provided by the invention has relative crystallinity (based on commercial SB powder of Condea company) generally in the range of 45-77%, preferably in the range of 65-77%.

Preferably, the non-metallic additive element comprises fluorine element and/or silicon element.

The modified pseudo-boehmite provided by the invention contains phosphorus element and non-metal auxiliary agent element, and preferably, based on the total dry basis of the modified pseudo-boehmite, Al₂O₃In an amount of from 79 to 98.9% by weight, preferably from 85 to 97.5% by weight; p₂O₅Is 1 to 6 weight percent, preferably 2 to 5 weight percent, and the content of the non-metal auxiliary agent element is 0.1 to 15 weight percent, preferably 0.5 to 10 weight percent.

In the invention, when the non-metal auxiliary agent element is an F element, the content of the non-metal auxiliary agent element is calculated by the F element; when the non-metal auxiliary agent element is Si element, the content of the non-metal auxiliary agent element is SiO₂And (6) counting.

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

The modified pseudo-boehmite provided by the invention contains phosphorus element and nonmetal auxiliary agent element, and has a specific crystal structure, and the catalyst containing the carrier prepared from the modified pseudo-boehmite provided by the invention has 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 a grain growth regulator, a phosphorus-containing compound and a nonmetal-containing auxiliary compound, so that the precipitation of the modified hydrated alumina can be met, the lower pH condition is kept, the too fast growth of the modified pseudo-boehmite grains under high pH is avoided, and the joint regulation effect of phosphorus and the growth regulator on the growth of the modified pseudo-boehmite is enhanced. The generation and aging of the modified hydrated alumina are carried out in the presence of a phosphorus-containing compound, a nonmetal-containing auxiliary compound and a grain regulator, 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 an embodiment of the present invention, the step (1) comprises: contacting an inorganic aluminum-containing compound solution, a phosphorus-containing compound, a non-metal-containing auxiliary agent 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 non-metal-containing auxiliary agent 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 and a non-metal containing adjuvant compound at a pH of 4 to 6.5. So that the precipitation reaction or hydrolysis reaction is carried out at the above-mentioned preferable pH, which is more favorable for improving the activity of the prepared carrier in the hydrogenation of heavy oil.

The conditions other than pH of the precipitation reaction and hydrolysis reaction are not particularly limited. 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 for 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 the modified 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 crystal grain growth regulator can be various substances which can generate strong adsorption with hydrated alumina, and preferably, the crystal grain growth regulator is at least one of polyhydric sugar alcohol and carboxylate and sulfate thereof; further preferably, the grain growth regulator is selected from at least one of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, gluconate, and sulfate. The gluconate, the gluconate and the sulfate can be soluble salts thereof, for example, one or more of potassium salt, sodium salt and lithium salt.

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

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

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

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

In the present invention, the adding manner of the phosphorus-containing compound and the nonmetal auxiliary compound is not particularly limited, and the phosphorus-containing compound (or prepared into a phosphorus-containing compound aqueous solution) and the nonmetal auxiliary compound (or prepared into a nonmetal auxiliary compound aqueous solution) may be added separately, or the phosphorus-containing compound (or its aqueous solution) and the nonmetal auxiliary compound (or prepared into its aqueous solution) 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 nonmetal auxiliary compound may be reacted, as long as the precipitation reaction or hydrolysis reaction is performed in the presence of the phosphorus-containing compound and the nonmetal auxiliary compound. The preparation method provided by the invention can ensure the regulating effect of the phosphorus-containing compound and the nonmetal-containing auxiliary 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 and the nonmetal-containing auxiliary compound on the grain growth, the phosphorus-containing compound and the nonmetal-containing auxiliary compound are preferably used in such amounts that the modified pseudo-boehmite prepared has P based on the total dry basis of the modified pseudo-boehmite₂O₅Is 1 to 6 weight percent, preferably 2 to 5 weight percent, and the content of the non-metal auxiliary agent element is 0.1 to 15 weight percent, preferably 0.5 to 10 weight percent.

The non-metal additive-containing compound of the present invention is not particularly limited, and may be a compound containing a non-metal additive known in the art; preferably, the non-metallic additive 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 silica, silica sol, water glass and sodium silicate.

It is noted that, in the research process, the crystal grain growth regulator, the phosphorus-containing compound and the non-metal-containing auxiliary compound are added in the precipitation reaction or the hydrolysis reaction, which is more beneficial to regulating the growth speed of the crystal grains on the 020 crystal plane and the 031 crystal plane, so that h is equal to or greater than 1.7 and equal to or less than 4, preferably equal to or greater than 1.9 and equal to or less than 4, and more preferably equal to or greater than 2.2 and equal to or less than 3.5. And adding a grain growth regulator, a phosphorus-containing compound and a non-metal-containing auxiliary compound in the process of 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, the phosphorus-containing compound and the non-metal-containing auxiliary compound. Preferably, no additional grain growth regulator, phosphorus-containing compound and non-metal-containing auxiliary compound are added in the aging process.

According to the process provided by the present invention, the inorganic aluminum-containing compound is preferably an aluminum salt and/or an aluminate. Correspondingly, the inorganic aluminum-containing compound solution can 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 200g/l in terms of alumina.

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

The alkali can be hydroxide or salt which is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, and 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 selected fromThe solution is introduced in the form of a solution, the concentration of the alkali solution is not particularly limited, and OH is preferred^-The concentration of (A) is 0.2-4 mol/l. 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.

According to the method provided by the invention, the organic aluminum-containing compound can be at least one of various aluminum alkoxides which can generate hydrolysis reaction with water to generate precipitation of hydrated alumina, and can be at least one of aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxyde and aluminum isooctanolate.

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 manner and kind of the base to be introduced may be as described above.

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.

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, a non-metal additive 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 modified hydrated alumina slurry; or, adding a phosphorus-containing compound, a non-metal-containing auxiliary compound and a grain growth regulator into deionized water to perform hydrolysis reaction with aluminum alkoxide to obtain modified hydrated alumina slurry, and performing precipitation reaction or hydrolysis reaction under the condition that the pH 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 modified hydrated alumina slurry obtained in the step (1) to adjust the pH value to 7-10.5, and aging at 50-95 ℃ for 0.5-8 hours;

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

(4) and (4) drying the product obtained in the step (3) to obtain the modified pseudoboehmite provided by the invention.

In a preferred embodiment of the present invention, the modified alumina is obtained by subjecting modified pseudoboehmite to optional molding, drying and calcination in this order.

The molding conditions, drying conditions and firing conditions are not particularly limited in the present invention, and may be those conventionally used in the art. The forming method can be at least one of rolling ball, tabletting and extrusion forming, preferably extrusion forming, and then drying and roasting are carried out; the molded shape can be clover, butterfly, cylinder, hollow cylinder, four-leaf, five-leaf, spherical, etc. In order to ensure that the molding is carried out smoothly, water, extrusion aids and/or adhesives and optionally pore-expanding agents can be added, the types and the amounts of the extrusion aids, peptizers and the pore-expanding agents are well known to those skilled in the art, for example, common extrusion aids can be selected from at least one of sesbania powder, methyl cellulose, starch, polyvinyl alcohol and polyvinyl alcohol, the peptizers can be organic acids and/or organic acids, and the pore-expanding agents can be at least one of starch, synthetic cellulose, polymeric alcohol and surfactants. 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 preferably include: the drying temperature is 40-350 ℃, and more preferably 100-200 ℃; the drying time is 1 to 24 hours, more preferably 2 to 12 hours.

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 400-800 ℃ and the time is 1-10 hours, preferably 2-6 hours.

The fourth aspect of the invention provides a modified alumina, which contains phosphorus element and non-metallic auxiliary agent element, wherein in the IR spectrogram of the modified alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9 to 3.5, preferably 2 to 3.3; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height. The non-metallic additive elements are the same as those provided in the first aspect of the present invention, and are not described herein again.

According to a fourth aspect of the present invention, there is provided a modified alumina obtained by calcining modified pseudoboehmite, wherein the modified pseudoboehmite is the modified pseudoboehmite according to the first aspect or the modified pseudoboehmite 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 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). Prior art alumina Supports (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) Generally lower than 1.8.

According to the invention, preferably, the nitrogen adsorption method pore volume of the modified alumina is 0.7-1.6 ml/g, the BET nitrogen adsorption method specific surface area is 250-380 square meters/g, and the optional pore diameter is 8-16 nanometers. The diameters of the small holes refer to the diameter corresponding to the highest point of a curve in a hole distribution curve. 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 a substrate of various adsorbents, catalyst carriers and catalysts.

According to the present invention, the kind and 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 group VIB metal component and the group VIII metal component are not particularly limited in the present invention, and the group VIB metal component is preferably Mo and/or W, and the group VIII metal component is preferably Co and/or Ni.

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

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

According to the present invention, the present invention may also contain organic additives during the preparation of the hydrogenation catalyst, such as during the preparation of the soluble compounds of the group VIB metal compound and the group VIII 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.

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, for example, at least one of group IIA, IIIA, IVA, VA, VIIA, IIB and IIIB 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 by simple substance elements is not more than 10 wt%, preferably 0.5-6 wt% based on the catalyst.

The method for preparing the hydrogenation catalyst in the present invention is not particularly limited as long as the hydrogenation active metal component is supported on the composite catalyst, and may be any conventional method in the art, for example, kneading method, dry mixing method, 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. Further, the present invention does not particularly limit the impregnation method and the impregnation time, and the impregnation method may be excess liquid impregnation, pore saturation impregnation, multiple impregnation, etc. depending on the amount of the impregnation liquid, and may be immersion method, spray impregnation, etc. depending on the manner of the impregnation; the impregnation time is preferably 0.5 to 3 hours. Further, by adjusting and controlling the concentration, amount or carrier amount of the impregnation solution, a specific content of the hydrogenation catalyst can be prepared, which is well known to those skilled in the art.

According to the present invention, the drying conditions 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 80-200 ℃, 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. Preferably, the conditions of 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. According to 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, preferably air.

According to a preferred embodiment of the present invention, the method for preparing the hydrogenation catalyst comprises: dipping the modified alumina in dipping solution containing active metal components, 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 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: d ═ 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) was calculated as D (020) using the parameter that 2 θ was the 10-15 ° peak, and the crystal grain size of (031) was calculated as D (031) using the parameter that 2 θ was the 34-43 ° peak, respectively, and h ═ D (031)/D (020) was calculated.

The IR spectrum is measured by Nicolet 870 type Fourier infrared spectrometer of Nicolet company in USAAnd (4) obtaining the product. 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).

Example 1

This example serves to illustrate the modified pseudoboehmite, modified alumina (i.e., support) and hydrogenation catalyst provided by the present invention and the methods for their preparation.

(1) Preparation of hydrated alumina PA 1:

5000 mL of aluminum sulfate solution with the concentration of 60 g of alumina/l, ribitol 6.0 g of the aluminum sulfate solution, 85 wt% of concentrated phosphoric acid 8.0mL of the aluminum sulfate solution and 4g of ammonium fluoride 6 wt% of the aluminum sulfate solution are added into a 2L reaction tank in parallel for precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia solution is controlled to ensure that the pH value of the 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 modified hydrated alumina PA1 which is characterized by XRD, wherein PA1 has a pseudo-thin diaspore structure.

The h values calculated by XRD characterization for PA1 are listed in Table 1. Relative crystallinity of PA1 and P₂O₅And the content of the non-metallic additive are also shown in table 1.

PA1 was calcined at 600 ℃ for 4 hours to give alumina. The hydroxyl groups on the surface of the alumina were measured by infrared spectroscopy. (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) Preparation of modified alumina carrier Z1:

1000 g of the hydrated alumina PA1 and 30 g of sesbania powder (produced by Henan Lankao sesbania glue works) are taken and mixed uniformly, 930 ml of aqueous solution containing 20g of nitric acid is added, a butterfly-shaped wet strip with the outer diameter of 1.4mm is extruded on a plunger type strip extruding machine, then 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 ℃, so as to obtain the carrier Z1.

(3) Preparation of hydrogenation catalyst C1:

110 g of the support Z1 were taken, and 110 ml of a mixed solution (containing MoO) composed of ammonium molybdate and nickel nitrate was used₃320 g/l and NiO 81 g/l) was impregnated into the support Z11 hours, dried at 110 ℃ for 4 hours, and calcined at 400 ℃ for 3 hours to obtain hydrogenation catalyst C1.

Comparative example 1

Pseudo-boehmite DPA1, carrier DZ1 and hydrogenation catalyst DC1 were prepared according to 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 and ammonium fluoride, 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 P₂O₅And the content of the non-metallic additive 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.

Comparative example 2

Pseudo-boehmite DPA2, a carrier DZ2 and a hydrogenation catalyst DC2 were prepared according to the method of 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, the pH was adjusted without adding aqueous ammonia to the slurry to obtain 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 P₂O₅And the content of the non-metallic additive 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.

Comparative example 3

Preparation of mimetics according to example 1Boehmite DPA3, support DZ3 and hydrogenation catalyst DC3, except that only ribitol 6.0 g, but no concentrated phosphoric acid, ammonium fluoride, was added to the aluminum sulfate solution to give 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, 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.

Example 2

This example is intended to illustrate the modified pseudoboehmite, modified alumina and hydrogenation catalyst provided in accordance with the present invention and the methods for their preparation.

(1) Preparation of hydrated alumina PA 2:

4000 mL of an aluminum trichloride solution having a concentration of 45 g of alumina/l and containing 85 wt% of concentrated phosphoric acid 22.1mL, 29 g of silica sol, 4.52 g/l of sorbitol and 1000 mL of a sodium metaaluminate solution having 210 g of alumina/l and a caustic factor of 1.58 were co-currently charged into a 2-l reaction tank to perform a precipitation reaction at a reaction temperature of 80 ℃, a reactant flow rate was adjusted so that a neutralization pH value was 4.0, and a reaction residence time was 15 minutes; and adding dilute ammonia water with the concentration of 5 weight percent into the obtained slurry to adjust the pH value of the slurry to 9.0, heating to 85 ℃, aging for 3 hours, then filtering by using a vacuum filter, and after filtering, additionally adding 20 liters of deionized water (the temperature is 85 ℃) into a filter cake to flush the filter cake for about 30 minutes. And adding the qualified filter cake after washing into 3 liters of deionized water, stirring to form 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 P₂O₅And the content of the non-metallic additive are also shown in table 1. The hydroxyl on the surface of the modified alumina is measured by infrared spectrum after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) Preparation of vector Z2:

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

(3) Preparation of hydrogenation catalyst C2:

100g of the support Z2 was taken, and 110 ml of a mixed solution (containing MoO) composed of ammonium molybdate and nickel nitrate was used₃231 g/l, NiO 56 g/l) was impregnated into the support Z21 hours, then oven 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 according to the procedure of example 2, except that sorbitol and silica sol were not contained in the aluminum trichloride solution, to obtain hydrated alumina CPA 4. According to the method of example 1, CPA4 has pseudo-boehmite structure and H value of CPA4 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.

Comparative example 5

Pseudo-boehmite, a carrier and a hydrogenation catalyst were prepared according to the method of example 2, except that the solution of aluminum trichloride 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, 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.

Comparative example 6

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared according to the method of example 2, except that concentrated phosphoric acid and silica sol were not contained in the aluminum trichloride solution, to obtain 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, 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.

Example 3

(1) Preparation of hydrated alumina PA 3:

3000mL of an aluminum sulfate solution with a concentration of 60 g of alumina/l and a content of gluconic acid of 4.5 g/l, 6g of hydrofluoric acid and 3.5mL of concentrated phosphoric acid with 85 wt% and 1000 mL of a sodium metaaluminate solution with 200g of alumina/l and a caustic factor of 1.58 are added in parallel in a2 l reaction tank to carry out precipitation reaction at a reaction temperature of 55 ℃, the flow rate of reactants is adjusted so that the neutralization pH value is 6.5, the reaction is kept for 15 minutes, then a sodium carbonate solution with a concentration of 100g/l is added to the obtained slurry, the pH of the slurry is adjusted to 9.5, the temperature is raised to 75 ℃, the aging is carried out for 5 hours, then the filtration is carried out by using a vacuum filter, and after the filtration is finished, 20 l of deionized water (temperature 85 ℃) is 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 P₂O₅And the content of the non-metallic additive are also shown in table 1. The hydroxyl on the surface of the modified alumina is measured by infrared spectrum after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) Preparation of vector Z3:

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

(3) Preparation of hydrogenation catalyst C3:

100g of the carrier Z3 was taken, and 110 ml of a mixed solution of ammonium metatungstate and nickel nitrate (the mixed solution contained WO)₃427 g/l, NiO 46 g/l) was impregnated into the support Z31 hours, dried at 110 ℃ for 4 hours, and calcined at 400 ℃ for 3 hours to obtain hydrogenation catalyst C3.

Example 4

The procedure of example 3 was followed except that during the precipitation reaction, the flow of reactants 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 P₂O₅And the content of the non-metallic additive are also shown in table 1. The hydroxyl on the surface of the modified alumina is measured by infrared spectrum after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Comparative example 7

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared according to the procedure of example 4, except that the aluminum sulfate solution contained no gluconic acid, hydrofluoric acid, to obtain 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.

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 catalyst to the reaction systemSodium carbonate solution is added to the slurry to adjust the pH to obtain hydrated alumina CPA 8. 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.

Comparative example 9

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared according to the procedure of example 4, except that concentrated phosphoric acid and hydrofluoric acid were not contained in the aluminum sulfate solution, to obtain 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.

Example 5

(1) Preparation of hydrated alumina PA 5:

adding 1000 g of an isopropanol-water azeotrope (the water content is 15 wt%) into a 2-liter three-neck flask with a stirring and reflux condenser pipe, adding 4.6mL of 85% concentrated phosphoric acid, 20g of silicon oxide and 15g of ribonic acid, adding ammonia water to adjust the pH 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 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 5. The PA5 has a pseudo-boehmite structure, 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 toDegree of crystallinity and P₂O₅And the content of the non-metallic additive are also shown in table 1. The hydroxyl on the surface of the modified alumina is measured by infrared spectrum after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) The PA5 was used to prepare the support Z5 and the hydrogenation catalyst C5 according to the method of example 1.

Comparative example 10

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared according to the method of example 5, except that no ribonic acid and silica were added to the three-necked flask, to obtain 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.

Comparative example 11

Pseudo-boehmite, a support and a hydrogenation catalyst were prepared according to the procedure of example 5, except that no silica was added to the three-necked flask, and after the same amount of ribonic acid was added, ammonia water was then added to adjust the pH to 8.5, followed by heating to 60 ℃, and then 500 g of molten aluminum isopropoxide was slowly dropped into the flask through a separatory funnel to obtain 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.

Comparative example 12

Pseudo-boehmite, a carrier and a hydrogenation catalyst were prepared according to the method of example 5, except that concentrated phosphoric acid and oxygen were not added to the three-necked flaskAnd (4) carrying out silicon melting to obtain the 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.

Example 6

Adding 1000 g of an isopropanol-water azeotrope (the water content is 15 wt%) into a 2-liter three-neck flask with a stirring and reflux condenser pipe, adding 7.0mL of 85% concentrated phosphoric acid, 20g of ammonium fluoride and 12g of ribonic acid, adding ammonia water to adjust the pH 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 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. The PA6 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA6 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅And the content of the non-metallic additive 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.

The PA6 was used to prepare the support Z6 and the hydrogenation catalyst C6 according to the method of example 1.

Comparative example 13

Pseudo-boehmite containing phosphorus was prepared according to the typical method in the research on Carrier Material for heavy oil hydrogenation catalyst, using 85% concentrated phosphoric acid 8.8mL with a concentration of 57 g.L^-13000mL of aluminum sulfate solution (D) and a concentration of 64 g.L^-1Precipitating 2500mL sodium metaaluminate solution, neutralizing pH to 8.0, reacting for a period of timeAging at 90 deg.C and pH 8.5 for 70min, filtering, pulping and washing the filter cake with deionized water for 2 times, and drying the filter cake at 120 deg.C for 24 hr to obtain 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.

The CPA13 was prepared according to the method of example 1 to give DZ13 and DC 13.

Comparative example 14

A phosphorus-modified pseudo-boehmite catalyst carrier material and a preparation method thereof are 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, and relative crystallinity is also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

The CPA14 was prepared according to the method of example 1 to give DZ14 and DC 14.

Example 7

Modified pseudoboehmite, modified alumina and a hydrogenation catalyst were prepared by following the procedure of example 1 except that 17g of silica sol was further added to the aluminum sulfate solution to obtain hydrated alumina PA 7. The PA8 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA7 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅And the content of the non-metallic additive 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.

Example 8

Modified pseudoboehmite, modified alumina and a hydrogenation catalyst were prepared by following the procedure of example 5 except that 15g of ammonium fluoride was added instead of silica in the three-necked flask, to obtain modified pseudoboehmite PA 8.

The characterization by XRD according to the method of example 1, PA8 has a pseudo-boehmite structure, and the H value of PA10 calculated by XRD characterization is shown in Table 1, and the relative crystallinity is also shown in Table 1. The hydroxyl on the surface of the 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.

TABLE 1

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

As can be seen from the results in Table 1, the modified pseudoboehmite prepared by the method provided by the invention has the characteristic that h is more than or equal to 1.7 and less than or equal to 4,preferably 2.2. ltoreq. h.ltoreq.3.5, and the h values of the various pseudoboehmite prepared by the processes of the prior art and the process of the comparative example are all less than 1.7. As can be seen from the results in Table 1, in the IR characteristic spectrum of the modified alumina obtained by roasting the modified pseudoboehmite prepared by the method of the invention at 600 ℃, the hydroxyl group has the characteristic (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9-3.5, preferably 2-3.3, 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

A poor-quality heavy oil (poor-quality residual oil having a sulfur content of 2.5% by weight, a nitrogen content of 0.52% by weight, a Ni content of 32. mu.g/g, a V content of 24. mu.g/g, and a carbon residue value of 9.7% by weight) was used as a raw material, and the catalyst was evaluated in a 100-ml small fixed-bed reactor.

The hydrogenation catalysts prepared in the above 100mL of examples 1 to 8 and comparative examples 1 to 14 were each crushed into particles having a diameter of 2 to 3 mm and then presulfided under the presulfiding conditions: the vulcanized oil adopts Qingdao regular 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 of 14.0MPa, hydrogen-oil volume ratio of 600, and constant temperature vulcanization at 360 ℃ for 3 hours. Then the reaction temperature is 380 ℃, the hydrogen partial pressure is 15 MPa, and the liquid hourly space velocity is 0.6 h^-1The catalyst loading was 100ml by sampling analysis after 100 hours of reaction at a hydrogen-oil volume ratio of 600 to evaluate the hydrogenation activity and stability of the catalyst, and the results are shown in table 2.

Wherein the calculation methods of the (Ni + V) removal rate, the desulfurization rate and the carbon residue removal 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.

Wherein, the content of nickel and vanadium in the oil sample is determined by an inductively coupled plasma emission spectrometer (ICP-AES) (the used instrument is a PE-5300 type plasma photometer of PE company in America, and the specific method is shown in petrochemical engineering analysis method RIPP 124-90);

measuring the sulfur content in the oil sample by using 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).

TABLE 2

It can be seen from table 2 that when the modified alumina prepared by calcining the modified pseudoboehmite provided by the invention is used as a hydrogenation catalyst carrier, the catalyst has better hydrogenation activity under the same conditions, and also has good stability.

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.

Claims

1. The modified pseudo-boehmite contains phosphorus elements and non-metal auxiliary elements, and h of the modified pseudo-boehmite satisfies 1.7-4, wherein h is D (031)/D (020), D (031) represents the grain size of a crystal face represented by a 031 peak in an XRD spectrogram of a pseudo-boehmite grain, D (020) represents the grain size of a crystal face represented by a 020 peak in the XRD spectrogram of the pseudo-boehmite grain, the 031 peak is a peak with 2 theta of 34-43 degrees in the XRD spectrogram, the 020 peak is a peak with 2 theta of 10-15 degrees in the XRD spectrogram, D is K lambda/(Bcos theta), K is a Scherrer constant, lambda is the diffraction wavelength of a target material, B is the half-width of the diffraction peak, and 2 theta is the position of the diffraction peak.

2. The modified pseudoboehmite according to claim 1, wherein h of the modified pseudoboehmite satisfies 1.9. ltoreq. h.ltoreq.4, preferably satisfies 2.2. ltoreq. h.ltoreq.3.5;

preferably, the non-metallic additive element comprises fluorine element and/or silicon element;

preferably, Al is based on the total dry basis of the modified pseudoboehmite₂O₃In an amount of from 79 to 98.9% by weight, preferably from 85 to 97.5% by weight; p₂O₅The content of (A) is 1-6 wt%, preferably 2-5 wt%, and the content of the non-metal auxiliary element is 0.1-15 wt%, preferably 0.5-10 wt%;

preferably, the modified pseudoboehmite has a relative crystallinity of 45 to 77%.

3. A preparation method of modified pseudo-boehmite comprises the following steps:

4. The production method according to claim 3, 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 nonmetal-containing auxiliary 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.

5. The production method according to claim 3 or 4, 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;

6. The production method according to claim 3 or 4, 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 and the nonmetal-containing auxiliary compound are used in such amounts that the modified pseudo-boehmite is prepared in such an amount that P is the amount of P based on the total dry weight of the modified pseudo-boehmite₂O₅The content of (A) is 1-6 wt%, preferably 2-5 wt%, and the content of the non-metal auxiliary element is 0.1-15 wt%, preferably 0.5-10 wt%;

preferably, the non-metal containing adjuvant compound 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;

7. The production method according to any one of claims 3 to 6, 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.

8. The production method according to any one of claims 3 to 7, 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.

9. A modified alumina obtained by roasting modified pseudoboehmite, characterized in that the modified pseudoboehmite is the modified pseudoboehmite according to claim 1 or 2 or the modified pseudoboehmite prepared by the method according to any one of claims 3-8.

10. The modified alumina contains phosphorus element and non-metal auxiliary element, and in the IR spectrogram of the modified alumina, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) 1.9 to 3.5, preferably 2 to 3.3; wherein, I₃₆₇₀Is 3670cm^-1Peak height, I₃₅₈₀Is 3580cm^-1Peak height, I₃₇₇₀Is 3770cm^-1Peak height, I₃₇₂₀Is 3720cm^-1Peak height.

11. The modified alumina according to claim 10, which is obtained by calcining modified pseudoboehmite according to claim 1 or 2 or prepared by the method according to any one of claims 3 to 8.

12. A hydrogenation catalyst comprising a carrier and an active metal component supported on the carrier, the carrier being the modified alumina according to any one of claims 9 to 11.

13. The hydrogenation catalyst of claim 12, wherein the active metal components comprise a group VIB metal component and a group VIII metal component;