阅读说明：本技术 改性含磷拟薄水铝石及其制备方法和改性含磷氧化铝及加氢催化剂 (Modified phosphorus-containing pseudo-boehmite, preparation method thereof, modified phosphorus-containing alumina and hydrogenation catalyst ) 是由 贾燕子 聂红 曾双亲 杨清河 刘学芬 王轶凡 邵志才 于 2020-04-28 设计创作，主要内容包括：本发明涉及拟薄水铝石制备领域,公开了改性含磷拟薄水铝石及其制备方法和改性含磷氧化铝及加氢催化剂,该改性含磷拟薄水铝石的h满足1.7≤h≤4,其中h＝D(031)/D(020),所述D(031)表示拟薄水铝石晶粒的XRD谱图中031峰所代表的晶面的晶粒尺寸,D(020)表示拟薄水铝石晶粒的XRD谱图中020峰所代表的晶面的晶粒尺寸,所述031峰是指XRD谱图中2θ为34-43°的峰,所述020峰是指XRD谱图中2θ为10-15°的峰,D＝Kλ/(Bcosθ),K为Scherrer常数,λ为靶型材料的衍射波长,B为衍射峰的半峰宽,2θ为衍射峰的位置；所述改性含磷拟薄水铝石中含有磷元素和金属助剂元素。本发明的改性含磷拟薄水铝石由于具有1.7≤h≤4的特征,因而该改性含磷拟薄水铝石经焙烧后的改性含磷氧化铝更加适合用作加氢催化剂载体,其具有更优异的加氢活性。(The invention relates to the field of pseudo-boehmite preparation, and discloses a modified phosphorus-containing pseudo-boehmite, a preparation method thereof, a modified phosphorus-containing alumina and a hydrogenation catalyst, wherein h of the modified phosphorus-containing 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 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 represents a peak with 2 theta of 34-43 degrees in the XRD spectrogram, the 020 peak represents 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 a diffraction wavelength of a target material, B is a half-peak width of a diffraction, and 2 theta is a position of the diffraction peak; the modified phosphorus-containing pseudo-boehmite contains a phosphorus element and a metal auxiliary agent element. The modified phosphorus-containing pseudo-boehmite of 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 phosphorus-containing alumina after the modified phosphorus-containing pseudo-boehmite is roasted is more suitable for being used as a hydrogenation catalyst carrier and has more excellent hydrogenation activity.)

1. A modified phosphorus-containing pseudo-boehmite, characterized in that h of the modified phosphorus-containing pseudo-boehmite satisfies 1.7 ≤ h ≤ 4, wherein h ═ D (031)/D (020), D (031) represents a crystal grain size of a crystal face represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents a crystal grain size of a crystal face represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, the 031 peak is a peak having a2 θ of 34-43 ° in the XRD spectrum, the 020 peak is a peak having a2 θ of 10-15 ° 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 the diffraction peak, and 2 θ is a position of the diffraction peak; the modified phosphorus-containing pseudo-boehmite contains a phosphorus element and a metal auxiliary agent element.

2. The modified pseudo-boehmite containing phosphorus according to claim 1, wherein h of the modified pseudo-boehmite containing phosphorus satisfies 1.9. ltoreq. h.ltoreq.4, preferably satisfies 2.2. ltoreq. h.ltoreq.3.5;

preferably, the modified phosphorus-containing pseudo-boehmite dry basisAmount based on Al₂O₃In an amount of 84-98.99 wt.%, preferably 87-97.95 wt.%; p₂O₅In an amount of 1 to 6 wt.%, preferably 2 to 5 wt.%, and the metal promoter element in terms of oxide is in an amount of 0.01 to 10 wt.%, preferably 0.05 to 8 wt.%;

preferably, the metal promoter element is selected from at least one of group IA, group IIA and group IVB elements;

more preferably, the metal auxiliary element is selected from at least one of lithium, sodium and potassium in IA group, beryllium, magnesium and calcium in IIA group and zirconium and titanium in IVB group;

preferably, the modified pseudo-boehmite containing phosphorus has a relative crystallinity of 45 to 77%.

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

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

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

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 compound containing metal auxiliary element 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.

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, a compound containing a metal promoter element, 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;

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.

6. The production process according to claim 3 or 4, wherein the phosphorus-containing compound and the metal-containing promoter element-containing compound are used in amounts such that the modified pseudo-boehmite containing phosphorus is produced in which P is the amount of P based on the total amount of the modified pseudo-boehmite containing phosphorus on a dry basis₂O₅In an amount of 1 to 6 wt.%, preferably 2 to 5 wt.%, and the metal promoter element in terms of oxide is in an amount of 0.01 to 10 wt.%, preferably 0.05 to 8 wt.%;

preferably, 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 metal promoter element-containing compound is selected from compounds containing at least one of group IA, group IIA, and group IVB elements;

preferably, the compound containing the metal auxiliary element is selected from compounds containing at least one of lithium, sodium, potassium of IA group, beryllium, magnesium and calcium of IIA group and zirconium and titanium of IVB group;

preferably, the compound containing the metal auxiliary element is selected from at least one of a lithium-containing compound, a sodium-containing compound and a potassium-containing compound, a beryllium-containing compound, a magnesium-containing compound, a calcium-containing compound and a titanium-containing compound;

preferably, the lithium-containing compound is selected from at least one of lithium sulfate, lithium chloride, lithium hydroxide, lithium nitrate and lithium acetate;

preferably, the sodium-containing compound is selected from at least one of sodium chloride, sodium hydroxide, sodium bicarbonate, sodium carbonate, and sodium nitrate;

preferably, the potassium-containing compound is selected from at least one of potassium chloride, potassium hydroxide, potassium oxide and potassium nitrate;

preferably, the beryllium-containing compound is selected from at least one of beryllium chloride, beryllium oxide, beryllium hydroxide, beryllium sulfate and beryllium fluoride;

preferably, the magnesium-containing compound is selected from at least one of magnesium chloride, magnesium hydroxide, magnesium oxide, magnesium carbonate and magnesium sulfate;

preferably, the calcium-containing compound is selected from at least one of calcium chloride, calcium sulfate, calcium carbonate, calcium oxide and calcium hydroxide;

preferably, the titanium-containing compound is selected from at least one of titanium oxide, titanium fluoride, titanium sulfate, and metatitanic acid.

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 phosphorus-containing alumina obtained by roasting modified phosphorus-containing pseudo-boehmite, characterized in that the modified phosphorus-containing pseudo-boehmite is the modified phosphorus-containing pseudo-boehmite according to claim 1 or 2 or the modified phosphorus-containing pseudo-boehmite prepared by the method according to any one of claims 3 to 8.

10. The modified phosphorus-containing alumina contains phosphorus element and metal additive element, and in the IR spectrogram of the modified phosphorus-containing 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 phosphorus-containing alumina according to claim 10, which is obtained by calcining modified phosphorus-containing pseudo-boehmite, wherein the modified phosphorus-containing pseudo-boehmite is the modified phosphorus-containing pseudo-boehmite according to claim 1 or 2 or the modified phosphorus-containing pseudo-boehmite 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 a modified phosphorus-containing alumina as claimed in any one of claims 9 to 11.

Technical Field

The invention relates to the field of preparation of pseudo-boehmite, in particular to modified phosphorus-containing pseudo-boehmite, a preparation method thereof, modified phosphorus-containing 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, excellent diffusion performance and scale holding capacity, and the pore structure of the catalyst carrier has important influence on 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 will be relative to the amount of grain generation and the growth rateThe preparation process of various pseudo-boehmite provides respective process conditions and controls the grain size and the crystallinity of the product so as to achieve the aim of controlling the physical properties of the product, such as pore volume, specific surface area and the like.

The introduction of phosphorus into alumina can change the pore structure, surface acidity and thermal stability of the carrier, thereby improving the activity of the hydrogenation catalyst.

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 modified phosphorus-containing pseudo-boehmite, a preparation method thereof, modified phosphorus-containing alumina and a hydrogenation catalyst. The catalyst obtained by adopting the carrier prepared from the modified phosphorus-containing 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 pseudo-boehmite, the compound containing the phosphorus compound and the metal additive element is added into the raw materials, the grain growth regulator is added in the process of precipitation reaction or hydrolysis reaction, the pH of the precipitation reaction or hydrolysis reaction is controlled to be 4-7, and then the regulation of the grain growth mode is enhanced by regulating the pH to be 7-10.5 for aging, so that the modified phosphorus-containing pseudo-boehmite 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 the catalyst taking the modified phosphorus-containing alumina obtained after the modified phosphorus-containing pseudo-boehmite is roasted as the 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 pseudo-boehmite containing phosphorus 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 activity 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 phosphorus, wherein h satisfies 1.7 ≦ h ≦ 4, wherein h ═ D (031)/D (020), wherein D (031) represents a crystal grain size of a crystal face represented by a 031 peak in an XRD spectrum of the pseudo-boehmite crystal grain, D (020) represents a crystal grain size of a crystal face represented by a 020 peak in an XRD spectrum of the pseudo-boehmite crystal grain, wherein the 031 peak represents a peak having a2 θ of 34 to 43 ° in the XRD spectrum, the 020 peak represents a peak having a2 θ of 10 to 15 ° in the XRD spectrum, D ═ K λ/(Bcos θ), K is a Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-width of the diffraction peak, and 2 θ is a position of the diffraction peak; the modified phosphorus-containing pseudo-boehmite contains a phosphorus element and a metal auxiliary agent element.

Preferably, h of the modified pseudo-boehmite containing phosphorus 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 phosphorus-containing pseudo-boehmite, which comprises the following steps:

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

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

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 compound containing metal auxiliary element 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 phosphorus-containing alumina obtained by calcining modified phosphorus-containing pseudo-boehmite, wherein the modified phosphorus-containing pseudo-boehmite is the modified phosphorus-containing pseudo-boehmite of the first aspect or the modified phosphorus-containing pseudo-boehmite prepared by the method of the second aspect.

The fourth aspect of the invention provides a modified phosphorus-containing alumina, which contains phosphorus element and metal additive element, wherein in the IR spectrogram of the modified phosphorus-containing 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 phosphorus-containing alumina of the third or fourth aspect.

Compared with the prior art, the modified phosphorus-containing 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 phosphorus-containing alumina obtained by roasting the modified phosphorus-containing pseudo-boehmite is more suitable for being used as a carrier of a heavy oil hydrogenation catalyst, and the obtained catalyst has more excellent hydrogenation activity. The preparation method of the modified phosphorus-containing 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 compound containing the metal auxiliary agent element, the grain growth regulator and the sectional control of the pH value in the preparation process. The modified phosphorus-containing alumina after roasting has specific surface hydroxyl distribution, and in the IR spectrogram of the modified phosphorus-containing 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.

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 phosphorus-containing pseudo-boehmite, wherein h of the modified phosphorus-containing pseudo-boehmite satisfies 1.7 ≤ h ≤ 4, wherein h ═ D (031)/D (020), D (031) represents the crystal grain size of the crystal face represented by the 031 peak in the XRD spectrogram of the pseudo-boehmite crystal grain, D (020) represents the crystal grain size of the crystal face represented by the 020 peak in the XRD spectrogram of the pseudo-boehmite grain, the 031 peak refers to the peak with 2 theta of 34-43 ° in the XRD spectrogram, the 020 peak refers to the peak with 2 theta of 10-15 ° 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; the modified phosphorus-containing pseudo-boehmite contains a phosphorus element and a metal auxiliary agent element.

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.

Preferably, h of the modified pseudo-boehmite containing phosphorus 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.

The modified phosphorus-containing alumina prepared by roasting the modified phosphorus-containing pseudo-boehmite satisfying the specification has specific hydroxyl distribution, and is more favorable for improving the hydrogenation activity and the reaction stability of the catalyst. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.

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

According to the present invention, it is preferred that Al is contained in the modified pseudo-boehmite on a dry basis in a total amount₂O₃In an amount of 84-98.99 wt.%, preferably 87-97.95 wt.%; p₂O₅In an amount of from 1 to 6% by weight, preferably from 2 to 5% by weight, and the metal promoter element in terms of oxide in an amount of from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, more preferably from 0.2 to 3% by weight.

The metal auxiliary agent element has a wide selection range of types, and can be at least one of group elements containing IA, IIA, IIIA, IVA, VA, VIIA, IIB, IIIB and IVB and rare earth metal elements. Preferably, the metal promoter element is selected from at least one of group IA, group IIA and group IVB elements.

More preferably, the metal promoter element is selected from at least one of group IA, group IIA, and group IVB elements; further preferably, the metal promoter element is at least one element selected from the group consisting of lithium, sodium, potassium of group IA, beryllium, magnesium, calcium of group IIA, zirconium and titanium of group IVB.

In the present invention, the crystal structure of the modified phosphorus-containing pseudoboehmite was measured by an X-ray diffractometer model D5005 from Siemens Germany with CuKa radiation of 44 kV and 40 mA, and the scanning speed was 2 DEG/min.

The modified phosphorus-containing pseudo-boehmite provided by the invention contains phosphorus element and metal additive element, and has a specific crystal structure, and the catalyst containing the carrier prepared from the modified phosphorus-containing pseudo-boehmite provided by the invention has excellent hydrogenation activity and reaction stability.

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

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

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

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 compound containing metal auxiliary element 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.

In the method provided by the invention, the precipitation reaction or the hydrolysis reaction is carried out under the conditions that the pH is 4-7 and the existence of a grain growth regulator, a phosphorus-containing compound and a compound containing metal auxiliary element, so that the precipitation of phosphorus-containing hydrated alumina can be met, the pH condition is kept lower, the too fast growth of pseudo-boehmite grains under high pH is avoided, and the joint regulation effect of phosphorus and the growth regulator on the growth of the pseudo-boehmite is enhanced. The generation and aging of the hydrated alumina are carried out in the coexistence of a phosphorus-containing compound, a compound containing a metal auxiliary element and a grain regulator, so that the prepared modified phosphorus-containing 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 grain growth regulator and acid or alkali to perform a precipitation reaction, or performing a hydrolysis reaction on an organic aluminum-containing compound, a phosphorus-containing compound, a grain growth regulator and water; controlling the pH of the precipitation reaction or the hydrolysis reaction to be 4-7.

According to a preferred embodiment of the present invention, the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound, a compound containing a metal promoter element, at a pH of 4 to 6.5. So that the precipitation reaction or hydrolysis reaction is carried out at the preferable pH value, and the desulfurization performance of the prepared carrier in the hydrogenation of heavy oil is improved.

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

In the present invention, the grain growth regulator is a substance capable of regulating the growth rate of crystal grains on different crystal planes, and preferably a substance capable of regulating the growth rate of crystal grains on a 020 crystal plane and a 031 crystal plane. For example, the 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 compound containing the metal auxiliary element is not particularly limited, and the phosphorus-containing compound (or the aqueous solution of the phosphorus-containing compound) and/or the compound containing the metal auxiliary element (or the aqueous solution of the compound containing the metal auxiliary element) may be added alone, or the phosphorus-containing compound (or the aqueous solution thereof) and/or the compound containing the metal auxiliary element (or the aqueous solution thereof) may be mixed with one or more of the raw materials in advance, and then the raw materials containing the phosphorus-containing compound and the compound containing the metal auxiliary element may be reacted, as long as the precipitation reaction or the hydrolysis reaction is carried out in the presence of the phosphorus-containing compound and the compound containing the metal auxiliary element. The preparation method provided by the invention can ensure the regulating effect of the phosphorus-containing compound on the grain growth.

In order to better exert the regulating effect of the phosphorus-containing compound on the grain growth, the phosphorus-containing compound and the compound containing the metal auxiliary element are preferably used in such amounts that the prepared pseudo-boehmite containing phosphorus is P based on the total dry basis of the pseudo-boehmite containing phosphorus₂O₅In an amount of from 1 to 6% by weight, preferably from 2 to 5% by weight, and the metal promoter element in terms of oxide in an amount of from 0.01 to 10% by weight, preferably from 0.05 to 8% by weight, more preferably from 0.2 to 3% by weight.

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.

The compound containing the metal auxiliary element has a wide selection range of types, and can be a compound containing at least one of IA, IIA, IIIA, IVA, VA, VIIA, IIB, IIIB and IVB group elements and rare earth metal elements; preferably, the metal promoter element-containing compound is selected from compounds containing at least one of group IA, group IIA and group IVB elements. More preferably, the compound containing the metal auxiliary element is selected from compounds containing at least one of lithium, sodium, potassium of IA group, beryllium, magnesium and calcium of IIA group and zirconium and titanium of IVB group.

Preferably, the compound containing the metal auxiliary element is at least one selected from a lithium-containing compound, a sodium-containing compound, a potassium-containing compound, a beryllium-containing compound, a magnesium-containing compound, a calcium-containing compound and a titanium-containing compound.

Preferably, the lithium-containing compound is selected from at least one of lithium sulfate, lithium chloride, lithium hydroxide, lithium nitrate and lithium acetate.

Preferably, the sodium-containing compound is selected from at least one of sodium chloride, sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium nitrate.

Preferably, the potassium-containing compound is at least one selected from the group consisting of potassium chloride, potassium hydroxide, potassium oxide and potassium nitrate.

Preferably, the beryllium-containing compound is selected from at least one of beryllium chloride, beryllium oxide, beryllium hydroxide, beryllium sulfate and beryllium fluoride.

Preferably, the magnesium-containing compound is selected from at least one of magnesium chloride, magnesium hydroxide, magnesium oxide, magnesium carbonate and magnesium sulfate.

Preferably, the calcium-containing compound is selected from at least one of calcium chloride, calcium sulfate, calcium carbonate, calcium oxide and calcium hydroxide.

Preferably, the titanium-containing compound is selected from at least one of titanium oxide, titanium fluoride, titanium sulfate, and metatitanic acid.

It should be noted that, in the research process of the present invention, it is found that the addition of the grain growth regulator, the phosphorus-containing compound, and the compound containing the metal additive element during the precipitation reaction or the hydrolysis reaction is more beneficial to regulate the growth speed of the grains on the 020 crystal plane and the 031 crystal plane, so that h satisfies 1.7. ltoreq. h.ltoreq.4, preferably satisfies 1.9. ltoreq. h.ltoreq.4, and more preferably satisfies 2.2. ltoreq. h.ltoreq.3.5. Adding a grain growth regulator and a compound containing a phosphorus compound and a metal additive element 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 and the compound containing the phosphorus compound and the metal additive element. Preferably, no additional grain growth regulator, phosphorus-containing compound and metal additive element-containing 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 introduced in the form of a solution, the concentration of the base solution is not particularly limited, and OH is preferred^-The concentration of (A) is 0.2-4 mol/l. The grain growth regulator and the phosphorus-containing compound are calculated when sodium metaaluminate and/or potassium metaaluminate are used as alkaliThe amount of the compound, the compound containing the metal promoter element, is also taken into account in the amount of the corresponding 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 of a phosphorus-containing compound, a compound containing a metal auxiliary element and a grain growth regulator and an alkali solution or an acid solution into a reaction container in a concurrent flow or intermittent manner for precipitation reaction to obtain phosphorus-containing hydrated alumina slurry; or, adding a phosphorus-containing compound, a compound containing a metal auxiliary element and a grain growth regulator into deionized water to perform hydrolysis reaction with aluminum alkoxide to obtain phosphorus-containing hydrated alumina slurry, and performing precipitation reaction or hydrolysis reaction under the condition that the pH is 4-7, preferably 4-6.5, by using the amount of an acid solution or an alkali solution;

(2) adding alkaline solution into the phosphorus-containing hydrated alumina slurry obtained in the step (1) 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 phosphorus-containing pseudo-boehmite provided by the invention.

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

In a preferred embodiment of the present invention, the modified phosphorus-containing alumina is obtained by optionally forming, drying and calcining modified phosphorus-containing pseudo-boehmite 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 phosphorus-containing alumina, which contains phosphorus element and metal additive element, wherein in the IR spectrogram of the modified phosphorus-containing 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 modified phosphorus-containing 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 reaction stability.

The IR spectrum was obtained by Nicolet corporation, USAMeasured by a Nicolet 870 type Fourier infrared spectrometer. 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 a fourth aspect of the present invention, there is provided a modified phosphorus-containing alumina obtained by calcining modified phosphorus-containing pseudo-boehmite, wherein the modified phosphorus-containing pseudo-boehmite is the modified phosphorus-containing pseudo-boehmite according to the first aspect or the modified phosphorus-containing pseudo-boehmite obtained by the method according to the second aspect.

According to the invention, preferably, the nitrogen adsorption method pore volume of the modified phosphorus-containing alumina is 0.7-1.6 ml/g, the BET nitrogen adsorption method specific surface area is 250-380 square meters/g, and the 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 phosphorus-containing alumina provided by the invention has larger pore volume and specific surface area.

The modified phosphorus-containing alumina provided by the invention can be used as a substrate of various adsorbents, catalyst carriers and catalysts.

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 phosphorus-containing alumina described in the third or fourth aspect.

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 composite 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 360-700 ℃, and preferably 400-600 ℃; 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 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. Further preferably, the content of the VIB group metal component is 5-45 wt% and the content of the VIII group metal component is 1-15 wt% calculated by oxides based on the total amount of the hydrogenation catalyst.

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.

According to a preferred embodiment of the present invention, the method for preparing the hydrogenation catalyst comprises: dipping the modified phosphorus-containing alumina in dipping solution containing active metal components, then drying at 80-200 ℃ for 1-8 hours, and then roasting at 360-700 ℃ 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 with CuKa radiation, 44 kV, 40 mA, and a scanning speed of 2 DEG/min. According to the Scherrer formula: d ═ K λ/(Bcos θ) (D is the crystal grain size, λ is the diffraction wavelength of the target material, B is the half-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 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).

Example 1

This example illustrates the modified phosphorus-containing pseudo-boehmite and modified phosphorus-containing alumina provided by the present invention, along with a hydrogenation catalyst.

(1) Preparation of hydrated alumina PA 1:

5000 mL of aluminum sulfate solution with the concentration of 60 g/l and containing ribitol 6.0 g, magnesium nitrate 4g and 85 wt% of concentrated phosphoric acid 8.0mL and ammonia water solution with the concentration of 6 wt% are added into a 2-liter reaction tank in parallel for precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water 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 hydrated alumina PA1 which is characterized by XRD, wherein PA1 has a pseudo-boehmite structure.

The h values calculated by XRD characterization for PA1 are listed in Table 1. Relative crystallinity of PA1 and P₂O₅The contents are also shown in Table 1.

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

(2) Preparing a modified phosphorus-containing alumina carrier Z1:

1000 g of hydrated alumina PA1 and 30 g of sesbania powder (produced by Henan Lankao sesbania glue works) are weighed and mixed uniformly, 950 ml of aqueous solution containing 25g of nitric acid is added, and a butterfly-shaped wet strip with the outer diameter of 1.4mm is extruded on a plunger type strip extruding machine. The wet butterfly-shaped bars were then dried at 120 ℃ for 4 hours and then calcined at 600 ℃ for 3 hours to give Z1.

(3) Preparation of hydrogenation catalyst C1:

100g of Z1 was taken and 108 ml of MoO in the solution₃247 g/l and 55g/l NiO of mixed aqueous solution of ammonium molybdate and nickel nitrate, soaking for 1 hour, drying at 110 ℃ for 4 hours, and calcining at 400 ℃ for 3 hours to obtain the hydrogenation catalyst C1.

Comparative example 1

Pseudo-boehmite, a carrier and a catalyst 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 using ribitol and magnesium nitrate, to obtain hydrated alumina CPA 1. Characterization was performed by XRD according to the method of example 1,CPA1 has pseudo-boehmite structure, and H value of CPA1 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Comparative example 2

Pseudo-boehmite, a carrier and a catalyst were prepared according to the method of example 1, except that the aluminum sulfate solution contained no magnesium nitrate and the flow rate of the aqueous ammonia solution was directly controlled so that the pH of the reaction system was 8.7, and after the completion of the precipitation reaction, it was not necessary to add aqueous ammonia to the slurry to adjust the pH, thereby obtaining hydrated alumina CPA 2. According to the method of example 1, CPA2 has pseudo-boehmite structure and H value of CPA2 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Comparative example 3

Pseudo-boehmite, a carrier and a catalyst were prepared according to the procedure of example 1, except that 6.0 g of ribitol was added to the aluminum sulfate solution without containing concentrated phosphoric acid and magnesium nitrate, to obtain hydrated alumina CPA 3. According to the method of example 1, CPA3 has pseudo-boehmite structure and H value of CPA3 calculated by XRD characterization is shown in Table 1, 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 illustrates the modified phosphorus-containing pseudo-boehmite and modified phosphorus-containing alumina provided by the present invention, along with a hydrogenation catalyst.

(1) Preparation of hydrated alumina PA 2:

4000 ml of the mixture were introduced into a2 l reaction vessel in parallelCarrying out precipitation reaction on a 45 g/L aluminum trichloride solution containing 22.1mL of 85 wt% concentrated phosphoric acid, 4g of magnesium nitrate and 4.52 g/L sorbitol and 1000 mL of a sodium metaaluminate solution containing 210 g/L alumina and having a caustic coefficient of 1.58, wherein the reaction temperature is 80 ℃, the flow rate of reactants is adjusted to ensure that the neutralization pH value is 4.0, and the reaction residence time is 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 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.

(2) PA2 was used to prepare a modified phosphorus-containing alumina support Z2 in accordance with example 1;

(3) preparation of hydrogenation catalyst C2:

100g of Z2 was taken and 110 ml of MoO was added₃227 g/l of CoO 55g/l of mixed aqueous solution of ammonium molybdate and cobalt nitrate are immersed for 1 hour, dried for 3 hours at 120 ℃ and roasted for 3 hours at 420 ℃ to obtain the hydrogenation catalyst C2.

Comparative example 4

Pseudo-boehmite, a support and a catalyst were prepared according to the procedure of example 2, except that sorbitol and magnesium nitrate 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 catalyst were prepared according to the method of example 2, except that the aluminum trichloride solution contained no magnesium nitrate, 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 precipitation reaction was completed, the pH was adjusted without adding ammonia water to the slurry to obtain 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 catalyst were prepared according to the procedure of example 2, except that concentrated phosphoric acid and magnesium nitrate 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

This example illustrates the modified phosphorus-containing pseudo-boehmite and modified phosphorus-containing alumina provided by the present invention, along with a hydrogenation catalyst.

(1) Preparation of hydrated alumina PA 3:

into a 2-liter reaction tank were added 3000mL of an aluminum sulfate solution having a concentration of 60 g alumina/liter and a gluconic acid content of 4.5 g/liter, 8 g of magnesium nitrate, 3.5mL of a concentrated phosphoric acid solution having a concentration of 85% by weight, and 1000 mL of an aluminum sulfate solution having a concentration of 200g alumina/liter and a caustic factor in parallel1.58 of sodium metaaluminate solution is subjected to precipitation reaction, the reaction temperature is 55 ℃, the flow rate of reactants is adjusted to ensure that the pH value of neutralization is 6.5, the reaction is kept for 15 minutes, then 100g/L of sodium carbonate solution is added into the obtained slurry, the pH value of the slurry is adjusted to 9.5, the temperature is raised to 75 ℃, the aging is carried out for 5 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20L of deionized water (the temperature is 85 ℃) is additionally added into a filter cake to wash the filter cake for about 30 minutes. The filter cake was dried at 120 ℃ for 24 hours to give hydrated alumina PA 3. The PA3 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA3 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) PA3 was used to prepare a modified phosphorus-containing alumina support Z3 in accordance with example 1;

(3) preparation of hydrogenation catalyst C3:

100g of Z3 was taken and 100ml of WO was added₃And soaking the mixed aqueous solution of ammonium metatungstate and nickel nitrate of 387 g/L and NiO 44 g/L for 1 hour, drying the mixed aqueous solution at the temperature of 110 ℃ for 4 hours, and roasting the mixed aqueous solution at the temperature of 400 ℃ for 3 hours to obtain the 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 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 7

Pseudo-boehmite, support and catalyst were prepared according to the procedure of example 4, except that the aluminum sulfate solution contained no aluminum sulfateGluconic acid and magnesium nitrate to give hydrated alumina CPA 7. According to the method of example 1, CPA7 has pseudo-boehmite structure and H value of CPA7 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Comparative example 8

Pseudo-boehmite, a carrier and a catalyst were prepared according to the procedure of example 4, except that the aluminum sulfate solution contained no magnesium nitrate 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, the pH was adjusted without adding a sodium carbonate solution to the slurry 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 catalyst were prepared according to the procedure of example 4, except that concentrated phosphoric acid and magnesium nitrate 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

This example illustrates the modified phosphorus-containing pseudo-boehmite and modified phosphorus-containing alumina provided by the present invention, along with a hydrogenation catalyst.

(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, 8 g of magnesium nitrate 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 the aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA 5. The PA5 has a pseudo-boehmite structure, as characterized by XRD according to the method of example 1, and the h value of PA5 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

(2) PA5 was used to prepare a modified phosphorus-containing alumina support Z5 in accordance with example 1;

(3) 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 catalyst were prepared according to the procedure of example 5, except that no ribonic acid and magnesium nitrate 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 carrier and a catalyst were prepared according to the method of example 5, except that magnesium nitrate was not added to the three-necked flask and added theretoAfter the same amount of ribonic acid was added, ammonia was then added to adjust the pH to 8.5, then heated to 60 ℃, and then 500 grams of molten aluminum isopropoxide was slowly added dropwise to the flask via a separatory funnel to give hydrated alumina 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 support and a catalyst were prepared according to the procedure of example 5, except that concentrated phosphoric acid and magnesium nitrate were not added to the three-necked flask, to obtain hydrated alumina CPA 12. According to the method of example 1, CPA12 has pseudo-boehmite structure and H value of CPA12 calculated by XRD characterization is shown in Table 1, and relative crystallinity is also shown in Table 1. Roasting at 600 deg.c for 4 hr, infrared spectrum analysis to determine the hydroxyl radical on the surface of alumina,

(I₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

Example 6

This example illustrates the modified phosphorus-containing pseudo-boehmite and modified phosphorus-containing alumina provided by the present invention, along with a hydrogenation catalyst.

(1) Preparation of hydrated alumina PA 6:

adding 1000 g of isopropanol-water azeotrope (the water content is 15 weight percent) into a 2L three-neck flask with a stirring and reflux condenser pipe, adding 7.0mL of 85 percent concentrated phosphoric acid, 4g of magnesium chloride 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 water-containing isopropanol while aging, filtering aged hydrated alumina, drying at 120 ℃ for 24 hours to obtain hydrated oxygen oxideAlumina 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 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 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^-1And carrying out precipitation reaction on 2500mL of sodium metaaluminate solution, wherein the neutralization pH is 8.0, the reaction time is 70min, then aging is carried out, the aging temperature is 90 ℃, the aging pH is 8.5, filtering is carried out after aging, a filter cake is beaten and washed for 2 times by deionized water, and the filter cake is dried for 24 hours at 120 ℃ to prepare the phosphorus-containing pseudo-boehmite CPA 13. According to the method of example 1, CPA13 has pseudo-boehmite structure and H value of CPA13 calculated by XRD characterization is shown in Table 1, relative crystallinity and P₂O₅The contents are also shown in Table 1. The hydroxyl on the surface of the phosphorus-containing alumina is measured by infrared spectroscopy after being roasted for 4 hours at 600 ℃, (I)₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀) The values of (A) are listed in Table 1.

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 in the neutralization reaction kettle 1 flows into a neutralization reaction kettle 2 through an overflow reaction pipe, and sodium carbonate with the concentration of 150g/L is added into the neutralization reaction kettle 2Controlling the pH of the solution to be 9.5 and controlling the reaction temperature 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 phosphorus-containing pseudo-boehmite, modified phosphorus-containing alumina and a hydrogenation catalyst were prepared by following the procedure of example 1 except that 2g of sodium acetate and 2g of magnesium chloride were added to the aluminum sulfate solution in place of magnesium nitrate 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 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.

Example 8

Modified phosphorus-containing pseudo-boehmite, modified phosphorus-containing alumina and a hydrogenation catalyst were prepared by following the procedure of example 1 except that 9 g of titanium chloride was added to the aluminum sulfate solution in place of magnesium nitrate to obtain modified phosphorus-containing pseudo-boehmite PA 8.

The PA8 has a pseudo-boehmite structure, characterized by XRD according to the method of example 1, and the h value of PA8 calculated by XRD characterization is shown in Table 1,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.

Example 9

Modified phosphorus-containing pseudo-boehmite, modified phosphorus-containing alumina and a hydrogenation catalyst were prepared by following the procedure of example 5, except that 2g of sodium sulfate and 4g of titanium chloride were added to the flask, instead of adding magnesium nitrate, to obtain modified phosphorus-containing pseudo-boehmite PA 9.

The characterization by XRD according to the method of example 1, PA9 has a pseudo-boehmite structure, and the H value of PA9 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 phosphorus-containing pseudoboehmite prepared by the method provided by the present invention has a characteristic of 1.7. ltoreq. h.ltoreq.4, preferably 2.2. ltoreq. h.ltoreq.3.5, while the various pseudoboehmite prepared by the prior art method and the method in comparative example have h values of less than 1.7. It can also be seen from the results in Table 1 that in the IR characterization spectra of the modified phosphorus-containing aluminum oxide obtained by calcining the modified phosphorus-containing pseudo-boehmite 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, using the prior art method and comparative exampleThe pseudo-boehmite prepared by the method in the (1) is roasted at 600 ℃ to obtain the hydroxyl characteristics (I) in the IR characterization spectrogram of the alumina₃₆₇₀+I₃₅₈₀)/(I₃₇₇₀+I₃₇₂₀)<1.8。

Test example 1

The hydrogenation catalysts prepared in the above 100mL examples 1 to 9 and comparative examples 1 to 14 were crushed into particles having a diameter of 2 to 3 mm and then presulfided under the presulfiding conditions: the vulcanized oil adopts Qingdao normal second-line diesel 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, an inferior heavy oil (kowitt slag having a nickel content of 65ppm, a vanadium content of 97ppm, a sulfur content of 3.5 wt%, a nitrogen content of 0.74 wt%, an asphaltene content of 5.2 wt%, and a carbon residue value of 13%) was used as a raw material, and the hydrogenation activity and stability of the catalyst were evaluated in a 100ml small fixed bed reactor at a reaction temperature of 380 ℃, a hydrogen partial pressure of 15 MPa, and a liquid hourly space velocity of 0.5 hr^-1The results of sampling analysis after 200 hours of reaction at a hydrogen-oil volume ratio of 600 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 phosphorus-containing alumina prepared by roasting the modified phosphorus-containing pseudo-boehmite provided by the invention is used as a catalyst carrier, the catalyst has better activity of demetallization, desulfurization and carbon residue removal under the same conditions, and the catalyst has good activity and 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.