CN113019427A - Preparation method of hydrotreating catalyst - Google Patents

Preparation method of hydrotreating catalyst Download PDF

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CN113019427A
CN113019427A CN201911354051.3A CN201911354051A CN113019427A CN 113019427 A CN113019427 A CN 113019427A CN 201911354051 A CN201911354051 A CN 201911354051A CN 113019427 A CN113019427 A CN 113019427A
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molecular sieve
crystallization
acid
alumina
catalyst
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CN113019427B (en
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唐兆吉
樊宏飞
杜艳泽
王继锋
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
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Abstract

The invention discloses a preparation method of a hydrotreating catalyst. The method comprises the following steps: (i) taking amorphous silica-alumina dry gel as a raw material, adopting a P123 triblock copolymer as a template agent to carry out first crystallization to synthesize an Al-SBA-15 molecular sieve, then adding ultrastable Y molecular sieve slurry, and carrying out second crystallization to obtain a Y/Al-SBA-15 composite molecular sieve; (ii) kneading and molding the Y/Al-SBA-15 composite molecular sieve prepared in the step (i) and alumina to obtain a carrier; (iii) and (3) impregnating the carrier obtained in the step (ii) with an impregnation liquid containing an active metal component and chitosan, and then drying and roasting to obtain the hydrotreating catalyst. The hydrotreating catalyst prepared by the method is suitable for the hydrodesulfurization and denitrification processes of heavy distillate oil, and can obviously improve the hydrodenitrogenation activity.

Description

Preparation method of hydrotreating catalyst
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst.
Background
The crude oil has an increasing degree of heaviness, and the crude oil contains nitrogen, sulfur, oxygen, metal and other impurities, and the impurities not only poison the catalyst in the subsequent treatment process, but also discharge a large amount of harmful gases such as sulfur oxides and nitrogen oxides, thereby endangering the health of human beings and protecting the environment. The catalyst with high activity and good stability is used, so that the process conditions are mild, the hydrogen consumption can be reduced, and the effects of saving energy and reducing consumption are achieved.
The hydrotreating catalyst is prepared through loading metal oxide containing VIII and VIB groups onto refractory porous inorganic carrier, soaking alumina, silica, titania, silicon carbide, boric oxide, zirconia and other carrier to prepare catalyst precursor, drying and other steps. The finished catalyst is presulfided before use, i.e., the oxidized catalyst is converted to a sulfided catalyst in the presence of hydrogen sulfide, sulfur-containing organic compounds, or elemental sulfur.
CN101590416A discloses a method for preparing a molybdenum-nickel hydrogenation catalyst, which comprises the steps of mixing, kneading and dipping to prepare the catalyst, firstly adding nitric acid solution into molybdenum oxide, titanium-containing compound, phosphorus-containing compound and alumina, mixing, kneading, extruding into strips, drying and roasting to obtain alumina forming matter containing titanium, phosphorus and molybdenum, dipping into nickel-containing phosphoric acid solution, drying and roasting to obtain the molybdenum-nickel hydrogenation catalyst.
CN1052501A discloses a hydrofining catalyst and a preparation method thereof. The catalyst is prepared by taking silicon oxide-aluminum oxide as a carrier, adopting three active metal components of W-Mo-Ni and a boron auxiliary agent, impregnating by a sectional impregnation method, drying and roasting.
CN1302848A discloses a hydrogenation catalyst and a preparation method thereof, the catalyst takes VIB group and VIII group metals as active components, adopts fluorine as an auxiliary agent, simultaneously carries one or more of silicon, boron, magnesium, titanium and phosphorus as the auxiliary agent, and is prepared by a coprecipitation method.
CN102039148A discloses a preparation method of a paraffin hydrofining catalyst. The method mainly comprises the following steps: adding 6-17% of silicon-containing compound and 2-20% of phosphorus-containing compound solution into pseudo-boehmite dry glue powder, rolling, extruding, drying and roasting to obtain the silicon-and-phosphorus-containing alumina carrier.
The hydrotreating catalyst prepared by the prior art has low denitrification activity, can influence the reaction performance of the catalyst in a subsequent cracking section reactor, further influences the quality of cracked products, and shortens the running period of the device.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst. The hydrotreating catalyst prepared by the method is used in a heavy oil hydrotreating process, and can obviously improve the hydrodenitrogenation activity.
The invention provides a preparation method of a hydrotreating catalyst, which comprises the following steps:
(i) taking amorphous silica-alumina dry gel as a raw material, adopting a P123 triblock copolymer as a template agent to carry out first crystallization to synthesize an Al-SBA-15 molecular sieve, then adding ultrastable Y molecular sieve slurry, and carrying out second crystallization to obtain a Y/Al-SBA-15 composite molecular sieve;
(ii) kneading and molding the Y/Al-SBA-15 composite molecular sieve prepared in the step (i) and alumina to obtain a carrier;
(iii) and (3) impregnating the carrier obtained in the step (ii) with an impregnation liquid containing an active metal component and chitosan, and then drying and roasting to obtain the hydrotreating catalyst.
Further, the amorphous silica-alumina dry gel has the following properties: the surface area is 400-650 m2Per g, preferably 450 to 600m2The pore volume is 0.52-1.8 mL/g, preferably 0.85-1.5 mL/g, and the pore distribution is as follows: the pore volume with the pore diameter of 4-15 nm accounts for 85% -95% of the total pore volume, and the pore volume with the pore diameter of more than 15nm accounts for the total pore volume5% or less.
Further, in the amorphous silica-alumina dry gel, the mass content of alumina is 2-85%. The mass content of the alumina can be adjusted within a wide range, and can be, for example, 5%, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, and the like.
Further, the properties of the ultrastable Y molecular sieve are as follows: SiO 22/Al2O3The molar ratio is 25-150, and the specific surface area is 550-1000 m2(iv)/g, the total pore volume is 0.30-0.60 mL/g.
Furthermore, the ultrastable Y molecular sieve slurry can be prepared by adding water into an ultrastable Y molecular sieve and pulping, and the mass content of the ultrastable Y molecular sieve in the slurry is 20-40%.
Further, the specific preparation method of the Y/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) mixing amorphous silica-alumina dry gel and water to form slurry;
(2) preparing an acidic solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, adding the ultrastable Y molecular sieve slurry, and performing second crystallization to prepare the Y/Al-SBA-15 composite molecular sieve.
According to the method, the amorphous silica-alumina in the step (1) is prepared by a carbonization method, and can be prepared by the following steps:
a. respectively preparing a sodium aluminate solution and a sodium silicate solution;
b. adding part or all of sodium silicate solution into sodium aluminate solution, and introducing CO2Controlling the reaction temperature of the gas to be 10-40 ℃, preferably 15-35 ℃, and controlling the pH value of the gel to be 8-11; wherein when CO is introduced2When the gas amount accounts for 40-100 percent of the total input amount, preferably 50-80 percent, adding the rest sodium silicate solution;
c. b, ventilating and stabilizing the mixture for 10-30 minutes under the temperature and pH value control of the step b;
d. c, filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. d, pulping the filter cake obtained in the step d, then carrying out hydro-thermal treatment, filtering and drying to obtain the amorphous silica-alumina dry gel; the hydrothermal treatment conditions were as follows: treating for 2-10 hours at 120-150 ℃ and under the water vapor pressure of 0.5-4.0 MPa.
Further, in the step a, the concentration of the sodium aluminate solution is 15-55 gAl2O3A further optional amount of 15 to 35gAl2O3L, the concentration of the sodium silicate solution is 50-200 gSiO2A further amount of 50 to 150g SiO2/L。
Further, in the step b, part or all of the sodium silicate solution is added, namely 5wt% -100 wt% of the total added sodium silicate solution. The CO is2The concentration of the gas is 30-60 v%. And c, ventilating and stirring in the gelling process in the step b.
Further, the specific process of step b is as follows: (1) adding all sodium silicate into sodium aluminate, and introducing CO2A gas; (2) adding part of sodium silicate into sodium aluminate, and introducing all CO2Gas, then adding the remaining sodium silicate solution to the mixture; (3) after adding part of sodium silicate to sodium aluminate, part of CO is introduced2Gas, then CO is introduced2The gas was added to the remaining sodium silicate solution.
Further, filtering the slurry obtained in the step d, washing the slurry with deionized water at the temperature of 50-95 ℃ until the slurry is nearly neutral,
and further, mixing the filter cake obtained in the step e according to a solid-liquid volume ratio of 8: 1-12: 1, adding water and pulping.
Further, the drying in the step e can be performed by a conventional method, and can be performed for 6-8 hours at 110-130 ℃.
Further, the mass ratio of the amorphous silica-alumina dry gel to water in the step (1) is 10: 90-30: 70, preferably 15: 85-25: 75.
further, the pH value of the acidic aqueous solution in the step (2) is 1-5, preferably 1.2-2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5-5.0%, preferably 0.8-2.8%.
Further, in step (2), the P123 triblock copolymer is added to a dilute acid (such as dilute hydrochloric acid) at a concentration of H+0.05 to 0.3mol/L, preferably 0.1 to 0.2mol/L, and more preferably 0.13 to 0.18 mol/L; in order to sufficiently dissolve the P123 triblock copolymer, the temperature system is controlled to 10 to 60 ℃, preferably 20 to 40 ℃, and more preferably 25 to 35 ℃.
Further, in the step (3), the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), and the amounts of the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are such that the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 0.5:1 to 5:1, preferably 1:1 to 5:1, and more preferably 1:1 to 3: 1.
Further, the conditions of the first crystallization in the step (3) are: the crystallization temperature is 80-120 ℃, and preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH value in the crystallization process is controlled to be 2.0-5.0, preferably 3.2-4.8.
Further, the conditions of the second crystallization in the step (3) are: the crystallization temperature is 80-130 ℃, and preferably 90-120 ℃; the crystallization time is 4-20 h, preferably 10-15 h; the pH value is controlled to be 2.0-5.0, preferably 4.2-5.0 in the crystallization process.
Further, after the crystallization step of step (3), the Y/Al-SBA-15 composite molecular sieve may be separated from the obtained mixture by any conventionally known means, such as filtration, washing, drying, etc. The filtration can adopt suction filtration. The washing can be performed by using deionized water as a washing solution. The drying can be carried out at 80-150 ℃, preferably 90-130 ℃, and the drying time is 2-12 hours, preferably 3-6 hours. The drying may be carried out at atmospheric pressure.
Further, the composite molecular sieve prepared by the above method may be calcined to remove the template agent and water and the like if necessary. The roasting can be carried out according to any mode conventionally known in the field, the roasting temperature is controlled to be 450-600 ℃, preferably 480-580 ℃, further preferably 500-560 ℃, and the roasting time is 2-10 hours, preferably 3-6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
Further, the amount of strong acid in the Y/Al-SBA-15 composite molecular sieve is 0.6-1.2 mL/g, preferably 0.7-1.0 mL/g; the ratio of the B acid to the L acid in the composite molecular sieve is less than 1.2, preferably less than 1.0, further preferably less than 0.6, and further preferably more than 0.1, and specifically can be 0.1, 0.2, 0.3, 0.4 or 0.5.
Further, the properties of the composite molecular sieve are as follows: the specific surface area is 550-1000 m2Preferably 680 to 800 m/g2The total pore volume is 0.4 to 1.0mL/g, preferably 0.5 to 0.8 mL/g.
Further, in the composite molecular sieve, the mass content of alumina is 2% to 85%, preferably 5% to 82%, and more preferably 7.5% to 79.5%. The content of alumina in the molecular sieve can be adjusted within a wide range, and can be, for example, 10.5%, 15.5%, 16.5%, 18.2%, 20.5%, 25.5%, 30.2%, 32.5%, 35.5%, 40.1%, 45.5%, 50.5%, 55.3%, 60.5%, 70.5%, 78.5%, and the like.
Further, the pore distribution of the composite molecular sieve comprises: the pore volume of the pores with the pore diameter of 4-15 nm accounts for 42-72%, preferably 45-65%, and more preferably 55-65% of the total pore volume.
Further, in the composite molecular sieve, the mass content of the Y molecular sieve is 10-90%, preferably 25-85%.
Further, the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
Furthermore, based on the weight of the hydrotreating catalyst carrier, the weight content of the Y/Al-SBA-15 composite molecular sieve is 2-18%, preferably 3-12%, and the weight content of alumina is 80-98%, preferably 88-97%.
Further, the molding in step (ii) can be performed by a conventional method in the art, such as extrusion molding. Conventional forming aids such as at least one of extrusion aids, peptizing acids, binders, and the like may be added during the forming process. The peptizing acid may be at least one of citric acid and nitric acid. The binder may be a small pore alumina. The extrusion aid can be sesbania powder and the like. After forming, drying and roasting processes are generally required. The drying and roasting can be carried out by adopting a conventional method, the drying condition can be 80-150 ℃, the drying time can be 2-12 h, the roasting condition can be 450-650 ℃, and the roasting time can be 2-10 h.
Further, in step (iii), the active metal component is a group VIII metal, preferably Co and/or Ni, and a group VIB metal, preferably W and/or Mo. Based on the weight of the catalyst, the content of the VIII family metal calculated by oxide is 1wt% -15 wt%, preferably 4wt% -10 wt%, the content of the VIB family metal calculated by oxide is 10wt% -30 wt%, preferably 15wt% -28 wt%, and the content of the hydrotreating catalyst carrier is 65wt% -80 wt%, preferably 65wt% -75 wt%.
Further, in step (iii), the molar ratio of chitosan to group VIB atoms in the impregnation fluid is 0.01: 1-10: 1, preferably 0.01: 1-5: 1.
further, in the step (iii), an organic acid is preferably added to the impregnation solution containing the active metal component and the chitosan, and the organic acid is preferably one or more of citric acid, tartaric acid, malic acid, lactic acid, sorbic acid, gluconic acid, succinic acid and benzoic acid. The molar ratio of the organic acid to the group VIB atoms is 0.01: 1-2: 1, preferably 0.01: 1-1: 1.
further, in the step (iii), the drying temperature is 60 ℃ to 220 ℃, preferably 90 ℃ to 180 ℃, and the drying time is 0.5h to 10h, preferably 1h to 5 h. The roasting condition is that the temperature is 350-500 ℃, preferably 380-480 ℃, and the roasting time is 0.5-10 h, preferably 1-5 h.
Further, the preparation method can also comprise conventional additives, such as at least one of P, B, Ti, Zr and the like, wherein the additives account for less than 10% of the weight of the hydrotreating catalyst and can be 0.1-8.0%.
The invention also provides the hydrotreating catalyst prepared by the method.
Further, the properties of the hydrotreating catalyst are as follows: the specific surface area is 120-280 m2Preferably 140 to 250 m/g2The pore volume is 0.20 to 0.60mL/g, preferably 0.2 to 0.5 mL/g.
The invention also provides an application of the hydrotreating catalyst.
Further, the application is to apply the hydrotreating catalyst to hydrodesulfurization and denitrification reactions of heavy distillate oil.
Further, the reaction conditions of the hydrogenation catalyst applied to the hydrodesulfurization and denitrification reactions of the heavy distillate oil are as follows: the total reaction pressure is 3.0MPa to 18.0MPa, and the liquid hourly volume airspeed is 0.2h-1～4.0h-1The volume ratio of hydrogen to oil is 200: 1-2000: 1, and the reaction temperature is 230-430 ℃.
Compared with the prior art, the preparation method of the hydrotreating catalyst has the following advantages:
(1) in the preparation method, the catalyst carrier contains the Y/Al-SBA-15 composite molecular sieve prepared from specific raw materials, and the Y/Al-SBA-15 composite molecular sieve is an ordered mesoporous-microporous composite molecular sieve which has high stability, adjustable acid quantity and reasonable pore distribution; in addition, the composite molecular sieve has the characteristics of ordered micropore and mesoporous structure, can achieve reasonable matching of a catalyst hydrogenation center and an acid center, well improves the acid content of medium-strong acid, and obviously improves the denitrification activity of the catalyst.
(2) The method for preparing the composite molecular sieve adopts the amorphous silica-alumina dry gel as the raw material, and the Al is synchronously and directly introduced into the framework in a Si-O-Al bond form and is uniformly distributed without additionally introducing external silicon source and aluminum source, so that the agglomeration of the Al on the surface of the molecular sieve is avoided, the pore channel is smooth, and the reaction is favorably carried out; hydrothermal crystallization is carried out in a weakly acidic environment, so that the phenomenon that the original properties of the ultra-stable Y molecular sieve are damaged due to dealumination of the ultra-stable Y molecular sieve under the condition of long-time exposure to an acidic solution is avoided. The preparation method of the invention is adopted to form the ordered and uniform Y/Al-SBA-15 composite molecular sieve, and simultaneously the original acid property and structure of the ultrastable Y molecular sieve are kept complete.
(3) In the preparation method, the active metal component impregnation liquid contains chitosan, and particularly under the condition of adding organic acid, on one hand, the acidity of the surface of the catalyst can be adjusted, on the other hand, an active phase in a mosaic state is easy to form on the surface of the catalyst, the content of octahedron molybdenum of a precursor of the active phase of the catalyst is increased, and the number of effective active sites is increased. In conclusion, the comprehensive performance of the catalyst is improved, and the catalyst is particularly beneficial to hydrogenolysis of C-N bonds and greatly improving the hydrodenitrogenation activity.
Detailed Description
In the present invention, the Al-SBA-15 molecular sieve means that aluminum atoms are introduced into the SBA-15 molecular sieve, the existence state of the aluminum atoms in the SBA-15 molecular sieve is not particularly limited, and a part of the aluminum atoms are generally distributed on the framework of the SBA-15 molecular sieve.
In the invention, the determination of the L acid or the B acid adopts an infrared spectroscopy, an instrument adopts an American Nicot Fourier infrared spectrometer-6700, and the determination method comprises the following steps: weighing 20mg of sample with granularity less than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg of sample in cup of instrument, connecting absorption cell and adsorption tube, vacuumizing until vacuum degree reaches 4 × 10-2And Pa, heating to 500 ℃, keeping for 1 hour to remove adsorbates on the surface of the sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃, balancing for 1 hour, and desorbing the physically adsorbed pyridine to obtain the acid content of infrared total acid, B acid and L acid, wherein the unit of the B acid and the L acid is mmol/L.
In the invention, NH is adopted as the medium strong acid3TPD method. The adopted instrument is an Auto-Chem II 2920 chemical adsorption instrument of Mike instruments. Ammonia gas is used as an adsorption and desorption medium, helium gas is used as carrier gas, and the acid amount of different desorption temperature zones is obtained by adopting temperature programming desorption and chromatographic analysis, wherein the acid amount of medium-strong acidThe ammonia desorption temperature corresponding to the acid amount is 250-400 ℃, and the acid amount unit is as follows: mL/g is the amount of ammonia adsorbed per gram of molecular sieve.
In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is processed, liquid N2Used as adsorbate, the adsorption temperature is-196 ℃, and analysis and test are carried out. Wherein the specific surface area is calculated by a BET method, and the pore volume and the pore distribution are calculated by a BJH method.
In the present invention, the dispersity is achieved by a Multilab2000X photoelectron spectrometer manufactured by Thermo corporation, USA. MgK alpha is used as an excitation source, the energy is 1253.6 eV, and the power is 200W. And C1s (284.6 eV) of a pollution carbon peak is taken as a calibration standard, and the influence of the charge effect is subtracted to determine the real binding energy of the sample.
In the invention, the relative desulfurization activity and the relative denitrification activity are calculated as follows:
the hydrodesulfurization activity of the catalyst was calculated on the 1.7 scale, and the hydrodenitrogenation activity was calculated on the 1 scale.
Hydrodesulfurization activity =
Figure DEST_PATH_IMAGE001
，
Hydrodenitrogenation activity =
Figure DEST_PATH_IMAGE002
，
Relative activity: the hydrodesulfurization activity and hydrodenitrogenation activity of catalyst a were used as references:
the relative desulfurization activity of catalyst B was: hydrodesulfurization activity of catalyst B ÷ hydrodesulfurization activity of catalyst A × 100%,
the relative denitrification activity of catalyst B was: the hydrodenitrogenation activity of catalyst B is multiplied by the hydrodenitrogenation activity of catalyst A by 100%,
the relative desulfurization and denitrification activity of catalyst A at this time was recorded as 100.
The effects and effects of the technical solutions of the present invention are further described below by way of examples and comparative examples, but the present invention should not be construed as being limited to these specific examples, and the following examples and comparative examples of the present invention are given as mass percentages unless otherwise specified. wt% is mass fraction.
Example 1
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A1 and slurry: sodium aluminate solution concentration 20gAl2O3Per L, sodium silicate solution concentration 100gSiO2Putting 0.75L of sodium aluminate solution into a gelling tank, adding 0.35L of sodium silicate solution, controlling the reaction temperature to be 20 ℃, and introducing 40 v% CO2Gas, introduction of CO2When the gas accounts for 50 percent of the total input amount, 0.15L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.5, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 65 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 10: 1 for pulping, the treatment is carried out for 2 hours at the temperature of 130 ℃ and the water vapor pressure of 3.5MPa, and after the drying is carried out for 6 hours at the temperature of 120 ℃, the amorphous silica-alumina product A1 is obtained by crushing and sieving. The properties of the amorphous silica-alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silica-alumina A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 18: 82;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.13mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.2, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 25 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.6 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.2:1, the crystallization temperature is 90 ℃, and the crystallization time is 20 hours; controlling the pH value to be 3.3 in the crystallization process;
(4) slurry containing 12g of USY molecular sieve (wherein the USY molecular sieve has the following properties of 785m of specific surface area2Per g, pore volume 0.53 mL. g-1，SiO2/Al2O3The USY molecular sieve slurry is prepared by pulping the USY molecular sieve and water at a molar ratio of 45) and pumping into the mixed system prepared in the step (3) by using a vacuum pump, drying for 3h at 100 ℃ after the crystallization time is 10h at a pH value of 4.6 and a temperature of 90 ℃, and roasting for 3h at 550 ℃ to obtain a finished product YAS-1. The properties are shown in Table 2.
(ii) Preparation of the support
Weighing alumina dry glue powder (the specific surface area is 308 m)225g of composite molecular sieve with the pore volume of 0.81 mL/g and the average pore diameter of 8.8nm, 85g of YAS-1 composite molecular sieve and 4g of sesbania powder, adding 120mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 12.6g and the amount of the citric acid is 4.5g), kneading, rolling, extruding into strips, drying at 120 ℃ for 3 hours, and roasting at 550 ℃ for 4 hours to obtain the final carrier containing the composite molecular sieve, wherein the number is Z1.
(iii) Preparation of the catalyst
Soaking Z1 in a soaking solution containing Mo, Ni, P, chitosan and citric acid in equal volume, wherein the molar ratio of the chitosan to Mo in the soaking solution is 0.05: 1, the molar ratio of the consumption of citric acid to Mo in the impregnation liquid is 0.01: 1, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-1. The catalyst composition and properties are shown in table 3.
The catalyst C-1 is subjected to a catalyst activity evaluation experiment, and specifically comprises the following steps: the catalyst was presulfided prior to evaluation, on a 200mL small scale hydrogenation unit. The properties of the raw oil used are shown in Table 5. The activity evaluation conditions were as follows: the total reaction pressure is 14.5MPa, and the liquid hourly volume airspeed is 1.1h-1Hydrogen-oil volume ratio 750: 1, the reaction temperature is 380 ℃. The results of the catalyst activity tests are shown in Table 6.
Example 2
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A2 and slurry: sodium aluminate solution concentration 20gAl2O3Per L, sodium silicate solution concentration 35gSiO2L, putting 0.3L of sodium aluminate solution into a gelling tank, then adding 0.2L of sodium silicate solution, controlling the reaction temperature to be 22 ℃, and introducing 35 v% CO2Gas, introduction of CO2When the gas accounts for 50% of the total input amount, 0.2L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.5, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 75 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 8:1 for pulping, the obtained product is treated for 2 hours at 120 ℃ under the water vapor pressure of 3.0MPa, the obtained product is dried for 8 hours at 120 ℃, crushed and sieved to obtain an amorphous silica-alumina product A2, and the properties of the amorphous silica-alumina dry gel powder A2 are shown in Table 1. Mixing the prepared amorphous silica-alumina A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 23: 77;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.15mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.4, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 28 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.3 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.2:1, the crystallization temperature is 92 ℃, and the crystallization time is 18 hours; controlling the pH value to be 3.4 in the crystallization process;
(4) slurry containing 56.98g of USY molecular sieve (wherein the USY molecular sieve has the following properties: specific surface area 823 m2Per g, pore volume 0.52 mL. g-1，SiO2/Al2O3The USY molecular sieve slurry is prepared by pulping the USY molecular sieve and water at a molar ratio of 47) and pumping into the mixed system prepared in the step (3) by using a vacuum pump, drying at 100 ℃ for 4h and roasting at 550 ℃ for 3h after the crystallization time is 11h at the pH value of 4.8 and the temperature of 95 ℃, so as to obtain a finished product YAS-2. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier is the same as that of example 1, except that YAS-1 is replaced by YAS-2, and the carrier containing the composite molecular sieve is prepared, and the code is Z2.
(iii) Preparation of the catalyst
Soaking Z2 in equal volume of soaking solution containing Mo, Ni, P, chitosan and tartaric acid, wherein the molar ratio of the chitosan dosage to Mo in the soaking solution is 0.05: 1, the molar ratio of the consumption of tartaric acid to Mo in the impregnation liquid is 0.02: 1, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-2. The catalyst composition and properties are shown in table 3.
Catalyst C-2 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
Example 3
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A3 and slurry: sodium aluminate solution concentration 21gAl2O3Per L, sodium silicate working solution concentration 65gSiO2L, putting 0.83L of sodium aluminate solution into a gel forming tank, then adding 0.5L of sodium silicate solution, controlling the reaction temperature to be 32 ℃, and introducing 52 v% CO2Stopping gas when the pH value reaches 9.8, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 9: 1 for pulping, treating for 3 hours at 130 ℃ under the water vapor pressure of 3.9MPa, drying for 8 hours at 130 ℃, crushing and sieving to obtain an amorphous silica-alumina product A3. The properties of the amorphous silica-alumina dry gel powder A3 are shown in Table 1. Mixing the prepared amorphous silica-alumina A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 19: 81;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.9 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.3:1, the crystallization temperature is 96 ℃, and the crystallization time is 12 hours; the pH value is controlled to be 3.6 in the crystallization process,
(4) slurry containing 50.9g of USY molecular sieve (wherein the USY molecular sieve has the following properties of specific surface area of 795m2Per g, pore volume 0.54 mL. g-1，SiO2/ Al2O3The molar ratio is 43: 1, pulping the USY molecular sieve with water) and pumping the USY molecular sieve and water into the mixed system prepared in the step (3) by using a vacuum pump, drying the USY molecular sieve at 100 ℃ for 4h and roasting the USY molecular sieve at 550 ℃ for 3h after the pH value is 4.9 and the temperature is 95 ℃ and the crystallization time is 10h, thus obtaining the finished product YAS-3. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier is the same as that of example 1, except that YAS-1 is replaced by YAS-3, and the carrier containing the composite molecular sieve is prepared, and the code is Z3.
(iii) Preparation of the catalyst
Soaking Z3 in a soaking solution containing Mo, Ni, P, chitosan and malic acid in equal volume, wherein the molar ratio of the chitosan dosage to Mo in the soaking solution is 0.05: 1, the molar ratio of the consumption of the malic acid to Mo in the impregnation liquid is 0.03: 1, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-3. The catalyst composition and properties are shown in table 3.
Catalyst C-3 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
Example 4
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
(1) Preparation of amorphous silica-alumina dry gel powder A4 and slurry: sodium aluminate solution concentration 25gAl2O3Per L, sodium silicate solution concentration 55gSiO2L, putting 0.5L of sodium aluminate solution into a gel forming tank, then adding 0.15L of sodium silicate solution, controlling the reaction temperature to be 35 ℃, and introducing 60v% CO2Stopping gas when pH value reaches 9.5, ventilating for 20 min, washing to neutral, pulping filter cake with water at solid-liquid volume ratio of 8:1, treating at 130 deg.C under 3.2MPa water vapor pressure for 2.5 hr, drying at 130 deg.C for 8 hr, and pulverizingSieving to obtain amorphous silica-alumina product A4. The properties of the amorphous silica-alumina dry gel powder A4 are shown in Table 1. Mixing the prepared amorphous silica-alumina A4 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 24: 76;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.5 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.8:1, the crystallization temperature is 96 ℃, and the crystallization time is 12 hours; controlling the pH value to be 3.6 in the crystallization process;
(4) slurry containing 79.25g of USY molecular sieve (wherein the USY molecular sieve has the following properties that the specific surface area is 798m2Per g, pore volume 0.51 mL. g-1，SiO2/Al2O3The USY molecular sieve slurry is prepared by pulping USY molecular sieve and water, and the USY molecular sieve slurry is prepared by beating the USY molecular sieve and water), pumping the USY molecular sieve slurry and the water into the mixed system prepared in the step (3) by using a vacuum pump, drying the USY molecular sieve slurry for 4 hours at the temperature of between 110 ℃ after the crystallization time is 12 hours at the pH value of 5.0, and roasting the USY molecular sieve slurry for 4 hours at the temperature of between 540 ℃ to obtain a finished product YAS-4. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier is the same as that of example 1, except that YAS-1 is replaced by YAS-4, and the carrier containing the composite molecular sieve is prepared, and the code is Z4.
(iii) Preparation of the catalyst
Soaking Z4 in a soaking solution containing Mo, Ni, P, chitosan and lactic acid in equal volume, wherein the molar ratio of the chitosan dosage to Mo in the soaking solution is 0.08: 1, the molar ratio of the using amount of the lactic acid to Mo in the impregnation liquid is 0.02: 1, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-4. The catalyst composition and properties are shown in table 3.
Catalyst C-4 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
Comparative example 1
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
Respectively weighing template agent triblock copolymer P123 and silicon source tetraethoxysilane, wherein the mass of the template agent P123 is 5.5g, and the mass of tetraethoxysilane is 10.2 g; adding a template agent and a silicon source into an HCl solution with the pH value of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20h at 120 ℃, washing with deionized water, and drying to obtain SBA-15. Pulping the obtained SBA-15 molecular sieve with a solid-to-liquid ratio of 1:10, adding the obtained SBA-15 molecular sieve into hydrochloric acid solution containing 23g of aluminum isopropoxide, heating to 100 ℃, stirring for 20 hours, and cooling to room temperature to obtain a mixed system F.
Pumping 12g of USY molecular sieve slurry (same as example 1) into a mixed system of the mixed solution F by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 12h at the pH value of 3.7 and the temperature of 100 ℃, and roasting at 540 ℃ for 4h to obtain a finished product YAS-5. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier is the same as that of example 1, except that YAS-1 is replaced by YAS-5, and the carrier containing the composite molecular sieve is prepared, and the code is Z5.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced by support Z5 to give the catalyst designated C-5. The catalyst composition and properties are shown in table 3.
Catalyst C-5 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
Comparative example 2
(i) Preparation of Y/Al-SBA-15 composite molecular sieve
Adding 5g of P123 into 2mol/L125mL hydrochloric acid solution, and stirring at 40 ℃ until the P123 is completely dissolved; adding 8.5g of tetraethoxysilane into hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the molar ratio of silicon to aluminum to be 35, continuing to stir for 20 hours, adding the solution into a 250mL reaction kettle, stirring for 48 hours at 100 ℃, cooling to room temperature, adjusting the pH value to 7.5 by using 4mol of ammonia water solution, continuously stirring, heating to 100 ℃, stirring for 72 hours, and cooling to 40 ℃ to obtain mixed solution A for later use.
Pumping slurry containing 12g of molecular sieve (same as example 1) into a mixed system of the mixed solution A by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 12h at the pH value of 3.5 and the temperature of 100 ℃, and roasting at 540 ℃ for 4h to obtain a finished product YAS-6. The properties are shown in Table 2.
(ii) Preparation of the support
The preparation method of the carrier is the same as that of example 1, except that YAS-1 is replaced by YAS-6, and the carrier containing the composite molecular sieve is prepared, and the code is Z6.
(iii) Preparation of the catalyst
The catalyst was prepared as in example 1 except that the support Z1 was replaced by support Z6 to give the catalyst designated C-6. The catalyst composition and properties are shown in table 3.
Catalyst C-6 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
Comparative example 3
The preparation of the support Z1 was identical to that of example 1.
Soaking Z1 in an equal volume of a soaking solution containing Mo, Ni, P and citric acid, wherein the molar ratio of the using amount of the citric acid to the Mo in the soaking solution is 0.01: 1, drying at 130 ℃ for 2h, and roasting at 430 ℃ for 3h to finally obtain the catalyst C-7. The catalyst composition and properties are shown in table 3.
Catalyst C-7 was subjected to a catalyst activity evaluation test in the same manner as in example 1. The properties of the raw oil used are shown in Table 5. The results of the catalyst activity tests are shown in Table 6.
TABLE 1 amorphous silica-alumina chemistry
Item A1 A2 A3 A4
Specific surface area, m2/g 485 511 503 518
Pore volume, mL/g 1.31 1.27 1.30 1.33
Hole distribution,%
4～15nm 91 86 85 88
＞15nm 2.5 3.8 4.7 4.2
TABLE 2 Properties of Y/Al-SBA-15 composite molecular sieves obtained in examples and comparative examples
Item YAS-1 YAS-2 YAS-3 YAS-4 YAS-5 YAS-6
Alumina content, wt% 23.56 31.53 35.17 61.3 17.49 20.56
Specific surface area, m2/g 769 756 782 763 716 718
Pore volume, mL/g 0.58 0.62 0.57 0.63 0.44 0.47
Relative degree of crystallinity after firing at 900% 98 97 98 98 87 86
Acid amount of medium strong acid, mL/g 0.72 0.76 0.82 0.85 0.63 0.67
B/L 0.228 0.245 0.233 0.251 1.20 1.26
Hole distribution,%
4～15nm 55.25 56.37 62.08 61.03 35.47 32.32
＞15nm 4.86 3.28 4.35 4.15 15.37 11.03
TABLE 3 physicochemical Properties of the catalyst
Catalyst numbering C-1 C-2 C-3 C-4 C-5 C-6
MoO3，wt% 22.9 23.2 23.2 23.0 22.8 22.9
NiO，wt% 4.05 3.85 3.90 3.85 3.90 3.85
P，wt% 1.23 1.21 1.21 1.20 1.19 1.20
Pore volume, mL/g 0.42 0.43 0.41 0.39 0.32 0.33
Specific surface area, m2/g 185 192 195 188 172 175
TABLE 4 characterization results of XPS analysis
Catalyst numbering C-1 C-2 C-3 C-4 C-5 C-6
Mo/Al 0.132 0.130 0.135 0.138 0.112 0.109
Ni//Al 0.043 0.045 0.041 0.042 0.030 0.028
As can be seen from the analysis results in Table 4, the dispersion degree of the active metal on the surface of the hydrotreating catalyst is well improved, which is beneficial to generating more active centers and improving the reaction activity of the catalyst.
TABLE 5 Properties of the feed oils
Raw oil
Density (20 ℃ C.), g/cm3 0.9082
Distillation range, deg.C 308～560
Nitrogen content, μ g-1 1420
TABLE 6 evaluation results of catalyst Activity
Catalyst and process for preparing same C-1 C-2 C-3 C-4 C-5 C-6 C-7
Relative denitrification activity,% 145 142 140 139 100 105 131
Relative desulfurization activity of% 130 128 131 129 100 103 122
As can be seen from Table 6, the hydrotreating catalyst prepared by the process of the present invention has significantly higher hydrodesulfurization and hydrodenitrogenation activities as compared to the catalysts of the comparative examples.

Claims (20)

1. A method of preparing a hydroprocessing catalyst, comprising:
(i) taking amorphous silica-alumina dry gel as a raw material, adopting a P123 triblock copolymer as a template agent to carry out first crystallization to synthesize an Al-SBA-15 molecular sieve, then adding ultrastable Y molecular sieve slurry, and carrying out second crystallization to obtain a Y/Al-SBA-15 composite molecular sieve;
(ii) kneading and molding the Y/Al-SBA-15 composite molecular sieve prepared in the step (i) and alumina to obtain a carrier;
(iii) and (3) impregnating the carrier obtained in the step (ii) with an impregnation liquid containing an active metal component and chitosan, and then drying and roasting to obtain the hydrotreating catalyst.
2. The method according to claim 1, wherein the amorphous silica-alumina dry gel has the following properties: the specific surface area is 400-650 m2Per g, preferably 450 to 600m2The pore volume is 0.52-1.8 mL/g, preferably 0.85-1.5 mL/g, and the pore distribution is as follows: the pore volume with the pore diameter of 4-15 nm accounts for 85% -95% of the total pore volume, and the pore volume with the pore diameter of more than 15nm accounts for less than 5% of the total pore volume.
3. The method according to claim 1, wherein the mass content of alumina in the amorphous silica-alumina dry gel is 2-85%.
4. The method of claim 1, wherein the ultrastable Y molecular sieve has the following properties: SiO 22/Al2O3The molar ratio is 25-150, and the specific surface area is 550-1000 m2(iv)/g, the total pore volume is 0.30-0.60 mL/g.
5. The method of any one of claims 1-4, wherein the method for preparing the Y/Al-SBA-15 composite molecular sieve comprises:
(1) mixing amorphous silica-alumina dry gel and water to form slurry;
(2) preparing an acidic solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, adding the ultrastable Y molecular sieve slurry, and performing second crystallization to prepare the Y/Al-SBA-15 composite molecular sieve.
6. The method according to claim 5, wherein the mass ratio of the amorphous silica-alumina dry gel to water is 10: 90-30: 70, preferably 15: 85-25: 75.
7. the method according to claim 5, wherein the pH of the acidic aqueous solution in the step (2) is 1 to 5, preferably 1.2 to 2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5 to 5.0%, preferably 0.8 to 2.8%.
8. The process of claim 5, wherein the P123 triblock copolymer is added to dilute acid in step (2), said dilute acid solution having a concentration of H+0.05 to 0.3mol/L, preferably 0.1 to 0.2 mol/L; the temperature system is controlled to be 10-60 ℃, and preferably 20-40 ℃.
9. The method according to claim 5, wherein in the step (3), the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are used in an amount such that the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 0.5: 1-5: 1, preferably 1: 1-5: 1.
10. The method as claimed in claim 5, wherein the conditions of the first crystallization in the step (3) are: the crystallization temperature is 80-120 ℃, and preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH value in the crystallization process is controlled to be 2.0-5.0, preferably 3.2-4.8.
11. The method as claimed in claim 5, wherein the conditions of the second crystallization in the step (3) are: the crystallization temperature is 80-130 ℃, and preferably 90-120 ℃; the crystallization time is 4-20 h, preferably 10-15 h; the pH value is controlled to be 2.0-5.0, preferably 4.2-5.0 in the crystallization process.
12. The method of claim 1, wherein the mass content of the Y/Al-SBA-15 composite molecular sieve is 10-90%, preferably 25-85%.
13. The process according to claim 1, wherein the properties of the alumina in step (ii) are as follows: the specific surface area is 150-450 m2Preferably 230 to 340 m/g2(ii)/g; the pore volume is 0.4-1.4 mL/g, preferably 0.8-1.2 mL/g, and the average pore diameter is 8-14 nm.
14. The process of claim 1, wherein the Y/Al-SBA-15 composite molecular sieve is present in an amount of from 2% to 18%, preferably from 3% to 12%, and the alumina is present in an amount of from 80% to 98%, preferably from 88% to 97%, by weight of the hydroprocessing catalyst support.
15. The process according to claim 1, wherein in step (iii), the active metal component is a group VIII metal, preferably Co and/or Ni, and a group VIB metal, preferably W and/or Mo.
16. A process according to claim 15, wherein the amount of group viii metal, calculated as oxide, is from 1wt% to 15wt%, preferably from 4wt% to 10wt%, the amount of group vib metal, calculated as oxide, is from 10wt% to 30wt%, preferably from 15wt% to 28wt%, and the amount of hydrotreating catalyst support is from 65wt% to 80wt%, preferably from 65wt% to 75wt%, based on the weight of the catalyst.
17. The method as claimed in claim 1, wherein in step (iii), the molar ratio of chitosan to group VIB atoms in the impregnation fluid is 0.01: 1-10: 1, preferably 0.01: 1-5: 1.
18. the method as claimed in claim 1 or 17, wherein in step (iii), the impregnation solution containing the active metal component and chitosan is added with an organic acid in a molar ratio of the organic acid to the group VIB atom of 0.01: 1-2: 1, preferably 0.01: 1-1: 1.
19. the method of claim 18, wherein the organic acid is one or more of citric acid, tartaric acid, malic acid, lactic acid, sorbic acid, gluconic acid, succinic acid, and benzoic acid.
20. The process according to claim 1, wherein in step (iii), the drying conditions are a drying temperature of 60 ℃ to 220 ℃, preferably 90 ℃ to 180 ℃, and a drying time of 0.5h to 10h, preferably 1h to 5 h; the roasting condition is that the temperature is 350-500 ℃, preferably 380-480 ℃, and the roasting time is 0.5-10 h, preferably 1-5 h.
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