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CN113019429A - Preparation method of hydrotreating catalyst - Google Patents

Preparation method of hydrotreating catalyst Download PDF

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Publication number
CN113019429A
CN113019429A CN201911355176.8A CN201911355176A CN113019429A CN 113019429 A CN113019429 A CN 113019429A CN 201911355176 A CN201911355176 A CN 201911355176A CN 113019429 A CN113019429 A CN 113019429A
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Prior art keywords
catalyst
alumina
molecular sieve
triblock copolymer
sba
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CN201911355176.8A
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CN113019429B (en
Inventor
唐兆吉
樊宏飞
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a hydrotreating catalyst. The method comprises the following steps: (i) preparing an Al-SBA-15 molecular sieve by using amorphous silica-alumina dry gel as a raw material and a P123 triblock copolymer as a template agent; (ii) kneading and molding the Al-SBA-15 mesoporous 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 a trihydroxymethyl compound, and then drying and roasting to obtain the hydrotreating catalyst. The hydrotreating catalyst is used in the heavy fraction oil hydrodenitrogenation reaction and shows high activity.

Description

Preparation method of hydrotreating catalyst
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a catalyst suitable for heavy distillate oil hydrotreating.
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 catalysts prepared in the prior art are roughly of two types, one is a calcined catalyst with a type I active center, and the other is a non-calcined catalyst with a type II active center. The catalyst with the characteristic of I-type active center has good stability but poor activity; the catalyst with the characteristic of II-type active centers has poor stability but high activity. At present, neither of these two types of catalysts is able to meet the technical requirements for processing heavy crude oils.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst. The catalyst prepared by the method has the high stability of the I-type active center catalyst and the high activity of the II-type active center catalyst, and shows higher activity when being used for the hydrodenitrogenation reaction of heavy distillate oil.
Preparation method of (I) hydrotreating catalyst
In a first aspect, the present invention provides a method for preparing a hydrotreating catalyst, comprising:
(i) preparing an Al-SBA-15 molecular sieve by using amorphous silica-alumina dry gel as a raw material and a P123 triblock copolymer as a template agent;
(ii) kneading and molding the Al-SBA-15 mesoporous 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 a trihydroxymethyl compound, and then drying and roasting to obtain the hydrotreating catalyst.
Further, the pore distribution of the Al-SBA-15 molecular sieve in the step (i) comprises: the pore volume occupied by pores with a pore diameter <4nm is less than 20%, preferably less than 15% of the total pore volume; in the Al-SBA-15 molecular sieve, the ratio of B acid to L acid is below 1.
Furthermore, the ratio of B acid to L acid in the Al-SBA-15 molecular sieve can be less than 0.8, less than 0.5 and less than 0.4. The ratio of the B acid to the L acid in the molecular sieve can be more than 0.1, and can also be more than 0.2.
Furthermore, in the Al-SBA-15 molecular sieve, the amount of the medium strong acid is 0.6-1.0 mL/g, preferably 0.7-0.9 mL/g.
Furthermore, in the Al-SBA-15 molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%, and more preferably 5-75%. The amount of alumina in the molecular sieve can be adjusted within wide limits and can be, for example, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, etc.
Further, the pore distribution of the Al-SBA-15 molecular sieve also comprises: the pore volume of the pores with the pore diameter of 4-15nm is 40-70%, preferably 45-65%, and more preferably 50-60% of the total pore volume.
Further, the properties of the Al-SBA-15 molecular sieve are as follows: the specific surface area is 550 to 850m2Preferably 650 to 750 m/g2The total pore volume is 0.7 to 1.3mL/g, preferably 0.9 to 1.2 mL/g.
Further, step (i) is a method for preparing the Al-SBA-15 molecular sieve, which 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) mixing the slurry prepared in the step (1) with the acidic solution containing the P123 triblock copolymer prepared in the step (2); and crystallizing to obtain the Al-SBA-15 molecular sieve.
Further, the mass content of the alumina in the amorphous silica-alumina dry gel is 2-85%, preferably 5-82%, and more preferably 5-75%. The mass content of the aluminum oxide can be adjusted within wide ranges, and can be, for example, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, and the like.
Further, the properties of the amorphous silica-alumina dry gel are as follows: 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 4-15nm 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.
Further, the amorphous silica-alumina dry gel 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 ℃ to control the reaction temperature to beThe pH value of the glue is 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 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 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 0.2 mol/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 crystallization temperature in the step (3) 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, after the crystallization step in step (3), the Al-SBA-15 molecular sieve may be separated from the obtained mixture by any conventionally known means, for example, by at least one of filtration, washing and drying. 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 molecular sieve prepared by the above method may be calcined to remove the template agent and moisture, etc., if necessary. The roasting can be carried out according to any mode conventionally known in the art, for example, the roasting temperature is generally 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 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, the weight content of the Al-SBA-15 mesoporous molecular sieve is 2-20%, preferably 3-12%, and the weight content of the alumina is 80-98%, preferably 88-97%, based on the weight of the hydrotreating catalyst carrier.
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%.
In step (iii), the trimethylol compound is one or more selected from trimethylolpropane, trimethylolethane, tris, trimethylolglycine, tris, and tris.
Further, in the step (iii), the molar ratio of the trimethylol compound in the impregnation liquid to the group VIB atom in the hydrotreating catalyst is 0.01: 1-10: 1, preferably 0.01: 1-5: 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 ℃, the preferential temperature is 380-430 ℃, and the roasting time is 0.5-10 h, the preferential time is 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%.
(II) hydrotreating catalyst and application thereof
The second aspect of the invention provides the hydrotreating catalyst prepared by the method.
Further, the properties of the hydrotreating catalyst are as follows: the specific surface area is 120-260 m2Preferably 140 to 230 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 that the hydrotreating catalyst is applied to the hydrodenitrogenation reaction of heavy distillate oil.
Further, the reaction conditions of the hydrotreating catalyst applied to the heavy distillate oil hydrodenitrogenation reaction 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 Al-SBA-15 molecular sieve prepared from the specific raw materials, the addition of the Al-SBA-15 molecular sieve improves the acid property of the catalyst, more suitable acid centers are generated, the acid amount of medium and strong acid on the surface of the catalyst is increased, the content of the strong acid is obviously reduced, the C-N bond breaking capacity is improved, and the denitrification capacity is obviously improved; in addition, after the Al-SBA-15 molecular sieve is added, the dispersion degree of the active component on the surface of the carrier is obviously increased, more active sites can be generated, and the effective utilization rate of the active component is improved.
(2) In the preparation method, the active metal component impregnation liquid contains a trihydroxymethyl organic auxiliary agent, the functional group of the trihydroxymethyl organic auxiliary agent can fully occupy the coordination unsaturated center on the surface of the carrier alumina, the organic auxiliary agent plays a role of isolating molecules, the strong interaction between the active component and the carrier is effectively prevented, the active component is easy to reduce in the vulcanization process, and the hydrogenation performance of the catalyst is obviously improved.
(3) The catalyst prepared by the preparation method has the characteristics of stability of the I-type active center catalyst and activity of the II-type active center catalyst, solves the problem of low activity of the I-type active center catalyst and the problem of poor stability of the II-type active center catalyst, has a deep denitrification function, and particularly has a very obvious effect on hydrotreating heavy distillate oil with high nitrogen content.
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 a carrier gas, and the acid quantities of different desorption temperature areas are obtained by adopting temperature programming desorption and chromatographic analysis, wherein the ammonia gas desorption temperature corresponding to the acid quantity of medium-strong acid is 250 to400 ℃, acid amount unit: 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.
According to the TEM characterization, a Japanese JEM-2100 type high-resolution transmission electron microscope is adopted, the accelerating voltage is 200 KV, the LaB6 filament is adopted, the point resolution is 0.23 nm, a small amount of catalyst is taken out during measurement, the catalyst is finely pressed in an agate mortar and then dispersed in an ethanol solution by ultrasonic waves, and then a small amount of suspension is taken and placed on a carbon-coated copper screen for sample preparation and analysis.
In the present invention, the XPS-characterized metal dispersion is measured by a Multilab2000X photoelectron spectrometer, U.S.A. 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.
The function and effect of the technical solution of the present invention are further illustrated by the following 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 not specifically illustrated, and the percentages are mass percentages.
Example 1
(i) Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A1 and slurry: sodium aluminate solution concentration 28gAl2O3Per L, sodium silicate solution concentration 90gSiO2Putting 0.75L of sodium aluminate solution into a gelling tank, adding 0.55L of sodium silicate solution, controlling the reaction temperature at 30 ℃, and introducing 40 v% CO2Gas, introduction of CO2When gas accounts for 55% of total input amount, adding 0.12L sodium silicate solution while introducing gas, controlling pH value of the gel to 9.7, then ventilating and stabilizing for 20 min, filtering the slurry, washing with 65 deg.C deionized water to neutral, adding water into filter cake according to solid-liquid volume ratio of 12: 1Pulping, treating at 120 deg.C under 3.5MPa water vapor pressure for 2 hr, drying at 120 deg.C for 6 hr, pulverizing, and sieving to obtain amorphous silica-alumina product A1. 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 19: 81;
(2) preparing an acidic 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 1.3, 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 1.2 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); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-1, the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 2.5:1, the crystallization temperature is 90 ℃, and the crystallization time is 20 hours; the pH value is controlled to be 3.3 in the crystallization process, the drying temperature is controlled to be 100 ℃, the drying time is 3 hours, the roasting temperature is controlled to be 550 ℃, the roasting time is 3 hours, and the properties of the A-S-1 molecular sieve are shown in Table 1.
(ii) Preparation of hydrotreating catalyst support
Weighing alumina dry glue powder (specific surface area is 321 m)2138g of A-S-1 molecular sieve, 7.3g of A-S-1 molecular sieve and 4g of sesbania powder, wherein the pore volume is 1.15mL/g, the average pore diameter is 12.3nm, 85mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 7.7g and the amount of the citric acid is 3.5g) is added, and the mixture is kneaded, rolled, extruded into strips and molded, dried at 120 ℃ for 3 hours and roasted at 550 ℃ for 3 hours to obtain the molecular sieve-containing alumina carrier with the number of Z1.
(iii) Preparation of hydrotreating catalyst
Soaking Z1 in an equal volume of a soaking solution containing Mo, Ni, P and trimethylolpropane, wherein the molar ratio of the trimethylolpropane to the Mo is 0.05: drying at 1,140 ℃ for 3h, and calcining at 430 ℃ for 2h to obtain the final catalyst C-1, wherein the composition and properties of the catalyst are shown in tables 2-4.
Catalyst C-1 activity evaluation experiments were conducted on a 100mL small scale hydrogenation unit, with the catalyst presulfided prior to evaluation. The evaluation conditions of the catalyst are that the total reaction pressure is 14.5MPa, and the liquid hourly volume space velocity is 1.1h-1Hydrogen-oil volume ratio 750: 1, the reaction temperature is 380 ℃. Properties of the raw oil for the activity evaluation test are shown in Table 5, and the results of the activity evaluation are shown in Table 6.
Example 2
(i) Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A2 and slurry: sodium aluminate solution concentration 25gAl2O3Per L, sodium silicate solution concentration 120gSiO2L, putting 0.5L of sodium aluminate solution into a gel forming tank, then adding 0.58L of sodium silicate solution, controlling the reaction temperature to be 35 ℃, and introducing 55 v% CO2Stopping gas when the pH value reaches 10.2, 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 10: 1 for pulping, treating for 2.5 hours at 130 ℃ under the water vapor pressure of 3.2MPa, drying for 8 hours at 120 ℃, crushing and sieving to obtain the amorphous silica-alumina product A2. 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 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 1.9, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the 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); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-2, the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 2.8:1, the crystallization temperature is 98 ℃, and the crystallization time is 20 hours; and in the crystallization process, the pH is controlled to be 3.3, the drying temperature is controlled to be 130 ℃, the drying time is 5 hours, the roasting temperature is controlled to be 550 ℃, and the roasting time is 5 hours. The A-S-2 molecular sieve properties are shown in Table 1.
(ii) Preparation of hydrotreating catalyst support
Weighing alumina dry glue powder (specific surface area is 318 m)295g of A-S-2 molecular sieve, 7.7g of Sesbania powder and 4g of sesbania powder, wherein the pore volume is 1.09 mL/g, the average pore diameter is 11.6nm, 105mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 8.1g, and the amount of the citric acid is 4g) is added, and the mixture is kneaded, rolled, extruded into strips and molded, dried at 110 ℃ for 3 hours and roasted at 550 ℃ for 3 hours to obtain the final alumina carrier containing the molecular sieve, the number of which is Z2.
(iii) Preparation of hydrotreating catalyst
Soaking Z2 in the same volume of soaking solution containing Mo, Ni, P and tris (hydroxymethyl) aminomethane, wherein the molar ratio of tris (hydroxymethyl) aminomethane to Mo is 0.05: drying at 1,140 ℃ for 3h, and calcining at 430 ℃ for 2h to obtain the final catalyst C-2, wherein the composition and properties of the catalyst are shown in tables 2-4.
The evaluation conditions of the activity of catalyst C-2 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Example 3
(i) Preparation of Al-SBA-15 molecular sieve
(1) Preparation of amorphous silica-alumina dry gel A3 and slurry: sodium aluminate solution concentration 18gAl2O3Per L, sodium silicate solution concentration 50gSiO2Putting 0.78L of sodium aluminate solution into a gelling tank, then adding 0.12L of sodium silicate solution, controlling the reaction temperature at 23 ℃, and introducing 45 v% CO2Controlling the pH value of the formed gel to be 8.8, ventilating and stabilizing for 20 minutes, filtering the slurry, washing with deionized water at 75 ℃ until the slurry is neutral, adding water into a filter cake according to the solid-liquid volume ratio of 11: 1 for pulping, treating for 2 hours at 120 ℃ under the water vapor pressure of 3.5MPa, drying for 6 hours at 120 ℃, crushing and sieving to obtain an amorphous silica-alumina product A3. 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 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 content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.8 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); crystallizing, filtering, drying and roasting to obtain an Al-SBA-15 molecular sieve, wherein the number is A-S-3, the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 2.5:1, the crystallization temperature is 95 ℃, and the crystallization time is 22 hours; and in the crystallization process, the pH is controlled to be 3.9, the drying temperature is controlled to be 120 ℃, the drying time is 5 hours, the roasting temperature is controlled to be 550 ℃, and the roasting time is 5 hours. The A-S-3 molecular sieve properties are shown in Table 1.
(ii) Preparation of hydrotreating catalyst support
Weighing alumina dry glue powder (the specific surface area is 315 m)2121g of Al-SBA-15 molecular sieve, 8.5g of the molecular sieve and 4g of sesbania powder, wherein the average pore diameter is 12.2nm, 115mL of aqueous solution containing nitric acid and citric acid (the amount of the nitric acid is 8.4g and the amount of the citric acid is 3.5g) is added, and the mixture is kneaded, rolled, extruded and formed into strips, dried at 120 ℃ for 4 hours and roasted at 550 ℃ for 4 hours to obtain the final molecular sieve-containing alumina carrier, wherein the number is Z3.
(iii) Preparation of hydrotreating catalyst
Soaking Z3 in equal volume of soaking solution containing Mo, Ni, P and trimethylolethane, wherein the molar ratio of the trimethylolethane to the Mo is 0.1: 1, drying at 140 ℃ for 3h, and roasting at 400 ℃ for 2h to finally obtain the catalyst C-3. The catalyst properties are shown in tables 2-4.
The evaluation conditions of the activity of catalyst C-3 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Example 4
The other conditions are the same as in example 1, except that in the step (3) of preparing the Al-SBA-15 molecular sieve, the pH value is controlled to be 4.8 in the crystallization process, an amorphous silica-alumina product A4 is obtained, the properties of the A-S-4 molecular sieve are finally obtained and shown in Table 1, an alumina carrier containing the molecular sieve is obtained, the number of the alumina carrier is Z4, and the number of the finally prepared catalyst is C-4.
The evaluation conditions of the activity of catalyst C-4 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Example 5
The same other conditions were used as in example 2 except that in step (2), the pH of the acidic aqueous solution containing the P123 triblock copolymer was 2.2, Z2 was impregnated in the catalyst preparation process in equal volumes with an impregnation solution containing Mo, Ni, P and trimethylol methane propanesulfonic acid in a molar ratio of 0.2 of trimethylol methane propanesulfonic acid to Mo: 1, drying at 140 ℃ for 3h, and roasting at 430 ℃ for 2h to finally obtain the catalyst C-5, wherein the properties of the catalyst are shown in tables 2-4.
The evaluation conditions of the activity of catalyst C-5 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Comparative example 1
Weighing macroporous alumina dry glue powder (specific surface area is 318 m)270g of small-pore alumina (specific surface area 275 m) with pore volume of 0.78mL/g and average pore diameter of 12.5nm265g of sesbania powder and 4g of sesbania powder, wherein the volume of pores is 0.45mL/g, the average pore diameter is 8.3nm, 120mL of aqueous solution containing nitric acid and citric acid (the amount of nitric acid is 6.7g and the amount of citric acid is 3.5g) is added, and the mixture is kneaded, rolled, extruded into strips and molded, dried at 120 ℃ for 4 hours and roasted at 550 ℃ for 4 hours to obtain the alumina carrier with the number of Z6.
Soaking Z6 in a soaking solution containing Mo, Ni and P in the same volume, drying the soaked sample at 140 ℃ for 3h, and roasting at 430 ℃ for 2h to obtain the finally obtained catalyst C-6, wherein the composition and properties of the catalyst are shown in Table 2.
The evaluation conditions of the activity of catalyst C-6 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the activity evaluation are shown in Table 6.
Comparative example 2
100g of alumina carrier Z6 is taken, and Z6 is immersed in an equal volume of immersion liquid containing Mo, Ni, P and trimethylolpropane, wherein the molar ratio of trimethylolpropane to Mo is 0.05: after drying at 1,140 ℃ for 3h, the final catalyst was designated as C-7 and the catalyst composition and properties are shown in Table 2.
The evaluation conditions of the activity of catalyst C-7 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Comparative example 3
6.2g of P123 was added to 600mL0.18mol/L hydrochloric acid solution, and after heating to 26 ℃ and stirring at a constant temperature for 6 hours, the solution was transparent after P123 was completely dissolved. Adding 5.2gY molecular sieve slurry, controlling pH at 3.3, stirring at constant temperature for reaction for 6 hr, and heating to 98 deg.C for hydrothermal crystallization for 24 hr. Then, the mixture is filtered, washed, dried at 120 ℃ for 6 hours and roasted at 550 ℃ for 6 hours to obtain Al-SBA-15 mesoporous molecular sieve, the serial number of which is A-S-8, and the properties of which are shown in Table 1.
The preparation of the support and catalyst was carried out as in example 1 except that A-S-1 was replaced with A-S-8 to obtain a support Z8 and a catalyst C-8.
The evaluation conditions of the activity of catalyst C-8 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Comparative example 4
Roasting and activating kaolin at 700 ℃ for 4h, weighing 12g of roasted kaolin, soaking for 4h by adopting 6mol/L hydrochloric acid, then carrying out suction filtration and washing by using deionized water until the kaolin is neutral, and drying; roasting the dried sample at 900 ℃ for 2 h; then the mixture is put into NaOH aqueous alkali of 5mol/L to react for 3h under high temperature and high pressure (the temperature is 160 ℃, the pressure is 0.5MPa), and after the reaction is finished, the pH value is adjusted to be 14.0. Then, the mesoporous material is dropwise added into a mixed solution of a surfactant and an acid (n (FSO-100)/n (P123) ═ 5.5), the concentration of hydrochloric acid is 7.5mol/L, the mixture is stirred and reacted for 24 hours at 40 ℃, the mixture is subjected to hydrothermal reaction for 48 hours at 160 ℃, and after filtration, washing and drying, the mesoporous material is roasted for 6 hours at 550 ℃ in a muffle furnace to obtain the mesoporous material A-S-9, wherein the properties of the mesoporous material are shown in Table 1.
The preparation of the support and catalyst was carried out as in example 1 except that A-S-1 was replaced with A-S-9 to obtain a support Z9 and a catalyst C-9.
The evaluation conditions of the activity of catalyst C-9 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Comparative example 5
Adding 4g 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 an ammonia water solution, continuously stirring, heating to 100 ℃, stirring for 72 hours, filtering, washing, drying overnight at 60 ℃, roasting for 6 hours at 550 ℃, and obtaining the mesoporous material A-S-10, wherein the properties are shown in Table 1.
The preparation methods of the carrier and the catalyst were the same as example 1 except that A-S-1 was replaced with A-S-10 to obtain a carrier Z10 and a catalyst C-10.
The evaluation conditions of the activity of catalyst C-10 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
Comparative example 6
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, filtering, washing, drying at 60 ℃ overnight, and roasting at 550 ℃ for 5 hours to obtain the mesoporous material A-S-11, wherein the properties are shown in Table 1.
The preparation of the support and catalyst was carried out as in example 1 except that A-S-1 was replaced with A-S-11 to obtain a support Z11 and a catalyst C-11.
The evaluation conditions of the activity of catalyst C-11 were the same as in example 1, the properties of the feedstock are shown in Table 5, and the results of the evaluation of the activity are shown in Table 6.
TABLE 1 Al-SBA-15 molecular Sieve Properties
Item A-S-1 A-S-2 A-S-3 A-S-4 A-S-5
Specific surface area, m2/g 736 734 742 738 735
Alumina content, wt% 25.83 15.22 70.05 25.83 15.22
Pore volume, mL/g 1.09 1.11 1.02 1.10 1.13
Acid amount of medium strong acid, mL/g 0.81 0.79 0.83 0.82 0.80
B/L 0.316 0.283 0.275 0.317 0.291
Hole distribution,%
＜4nm 11.23 12.76 12.63 14.05 13.05
4～15nm 55.62 56.65 54.02 57.56 58.89
＞15nm 33.15 30.59 33.35 28.39 28.06
TABLE 1
Item A-S-8 A-S-9 A-S-10 A-S-11
Specific surface area, m2/g 720 695 708 706
Alumina content, wt% 4 8 13 17.25
Pore volume, mL/g 0.85 0.78 1.05 1.04
Acid amount of medium strong acid, mL/g 0.53 0.41 0.43 0.45
B/L 1.21 1.24 1.32 1.25
Hole distribution,%
＜4nm 42.69 46.28 45.36 43.05
4～5nm 38.25 35.69 36.45 37.56
＞15nm 19.06 18.03 18.19 19.39
TABLE 2 physicochemical Properties of the catalyst
Item C-1 C-2 C-3 C-4 C-5
MoO3，wt% 23.1 23.0 23.3 23.5 23.2
NiO，wt% 3.48 3.45 3.42 3.51 3.53
P，wt% 1.21 1.19 1.22 1.23 1.25
Pore volume, mL/g 182 189 185 192 188
Specific surface area, m2/g 0.37 0.36 0.37 0.35 0.36
TABLE 2
Item C-6 C-7 C-8 C-9 C-10 C-11
MoO3，wt% 23.6 23.6 23.2 23.5 23.7 23.2
NiO，wt% 3.48 3.45 3.45 3.48 3.51 3.48
P，wt% 1.23 1.20 1.21 1.19 1.23 1.21
Specific surface area, m2/g 165 172 169 166 171 168
Pore volume, mL/g 0.33 0.32 0.32 0.30 0.29 0.31
TABLE 3 TEM analysis results
Item C-7 C-6 C-4
Average length/nm 5.41 5.29 5.38
Average number of layers 3.42 3.13 3.38
10000nm2Number of platelets contained on surface 76 72 89
From the analysis results in table 3, the catalyst prepared by the method of the present invention has the average length of platelets and the average number of layers of platelets between those of the class i active center catalyst and the class ii active center catalyst, and has the characteristics of both the class i active center catalyst and the class ii active center catalyst, i.e., the catalyst has the stability of the class i active center catalyst and the activity of the class ii active center catalyst.
TABLE 4 characterization results of XPS analysis
Item C-1 C-2 C-3 C-4 C-5
Mo/Al 0.16 0.17 0.16 0.15 0.16
Ni/Al 0.05 0.04 0.05 0.06 0.04
TABLE 4
Item C-6 C-7 C-8 C-9 C-10 C-11
Mo/Al 0.10 0.11 0.11 0.12 0.12 0.13
Ni/Al 0.03 0.03 0.04 0.03 0.04 0.03
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 prepared by the method of the present invention 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.cm-3 0.918
Nitrogen content, μ g-1 1480
Distillation range, deg.C 305~540
TABLE 6 evaluation results of catalyst Activity
Catalyst and process for preparing same C-1 C-2 C-3 C-4 C-5
Nitrogen content, μ g-1 7.2 7.2 6.8 6.5 5.3
TABLE 6 continuation
Catalyst and process for preparing same C-6 C-7 C-8 C-9 C-10 C-11
Nitrogen content, μ g-1 25 28 32 33 29 32
As can be seen from Table 6, the hydrotreating catalyst prepared by the process of the present invention has significantly higher denitrification activity as compared with the catalyst of the comparative example.
TABLE 7 Properties of amorphous silica-alumina
Amorphous silica-alumina numbering A1 A2 A3 A4
Specific surface area, m2/g 535 528 519 508
Pore volume, mL/g 1.26 1.21 1.20 1.19
Hole distribution,%
4～15nm 87 92 88 93
＞15nm 3 4 2 3

Claims (16)

1. A method of preparing a hydroprocessing catalyst, comprising:
(i) preparing an Al-SBA-15 molecular sieve by using amorphous silica-alumina dry gel as a raw material and a P123 triblock copolymer as a template agent;
(ii) kneading and molding the Al-SBA-15 mesoporous 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 a trihydroxymethyl compound, and then drying and roasting to obtain the hydrotreating catalyst.
2. The method according to claim 1, wherein in step (i), the properties of the amorphous silica-alumina dry gel are as follows: the specific surface area is 400-650 m2The pore volume is 0.52-1.8 mL/g, and the pore distribution is as follows: the pore volume with the pore diameter of 4-15nm 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 process of claim 1 or 2, wherein in step (i), the preparation method of the Al-SBA-15 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 (3) mixing the slurry prepared in the step (1) with the acidic solution containing the P123 triblock copolymer prepared in the step (2), and crystallizing to prepare the Al-SBA-15 molecular sieve.
4. The method according to claim 3, wherein the mass ratio of the amorphous silica-alumina dry gel to the water in the step (1) is 10: 90-30: 70, preferably 15: 85-25: 75.
5. the method according to claim 3, 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%.
6. The process of claim 3, 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; in the step (2), the temperature system is controlled to be 10-60 ℃, and preferably 20-40 ℃.
7. The method according to claim 3, wherein the slurry prepared in step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in step (2) in step (3), and the amounts of the slurry prepared in step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in step (2) are 0.5:1 to 5:1, preferably 1:1 to 5:1, by mass, of the P123 triblock copolymer and the amorphous silica-alumina in the mixed system.
8. The method according to claim 3, wherein the crystallization temperature in step (3) is 80 to 120 ℃, preferably 90 to 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.
9. According to claim 1The process according to (i), wherein in step (ii), the properties of the alumina 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.
10. The process of claim 1 or 9, wherein the Al-SBA-15 mesoporous molecular sieve is present in an amount of 2% to 20%, preferably 3% to 12%, and the alumina is present in an amount of 80% to 98%, preferably 88% to 97%, by weight of the hydroprocessing catalyst support.
11. 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.
12. The method according to claim 1, wherein in step (iii), the trimethylol compound is one or more selected from the group consisting of trimethylolpropane, trimethylolethane, tris (hydroxymethyl) aminomethane, tris (hydroxymethyl) glycine, tris (hydroxymethyl) melamine, and tris (hydroxymethyl) aminomethane sulfonic acid.
13. The method as claimed in claim 1 or 12, wherein in step (iii), the molar ratio of the trimethylol compound in the impregnating solution to the group VIB atom in the hydrotreating catalyst is 0.01: 1-10: 1, preferably 0.01: 1-5: 1.
14. A process according to claim 11, 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 60wt% to 80wt%, preferably from 65wt% to 75wt%, based on the weight of the catalyst.
15. The process according to claim 11, 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 ℃, the preferential temperature is 380-430 ℃, and the roasting time is 0.5-10 h, the preferential time is 1-5 h.
16. A hydroprocessing catalyst characterized by being prepared by the process according to any one of claims 1-15.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116060085A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 Aromatic hydrocarbon hydrogenation saturation catalyst and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462078A (en) * 2007-12-18 2009-06-24 中国石油化工股份有限公司 Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst
CN101590425A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 Catalyst used for hydrogenation of distilled oil fraction and preparation method thereof
CN103781727A (en) * 2011-09-09 2014-05-07 环球油品公司 Methods for forming zeolites from homogeneous amorphous silica alumina
CN104148082A (en) * 2013-05-16 2014-11-19 中国石油化工股份有限公司 Preparation method and applications of hydrofining catalyst
CN106698459A (en) * 2017-01-16 2017-05-24 中国石油大学(华东) Method for preparing nano zeolite molecular sieve by after-treatment of amorphous precursors
WO2018059871A1 (en) * 2016-09-28 2018-04-05 IFP Energies Nouvelles Hydrotreatment method using a catalyst based on a group viiib metal and a group vib metal prepared in a supercritical fluid medium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462078A (en) * 2007-12-18 2009-06-24 中国石油化工股份有限公司 Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst
CN101590425A (en) * 2008-05-29 2009-12-02 北京三聚环保新材料股份有限公司 Catalyst used for hydrogenation of distilled oil fraction and preparation method thereof
CN103781727A (en) * 2011-09-09 2014-05-07 环球油品公司 Methods for forming zeolites from homogeneous amorphous silica alumina
CN104148082A (en) * 2013-05-16 2014-11-19 中国石油化工股份有限公司 Preparation method and applications of hydrofining catalyst
WO2018059871A1 (en) * 2016-09-28 2018-04-05 IFP Energies Nouvelles Hydrotreatment method using a catalyst based on a group viiib metal and a group vib metal prepared in a supercritical fluid medium
CN106698459A (en) * 2017-01-16 2017-05-24 中国石油大学(华东) Method for preparing nano zeolite molecular sieve by after-treatment of amorphous precursors

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOSE ESCOBAR ET AL.: "Effect of ethyleneglycol addition on the properties of P-doped NiMo/Al2O3 HDS catalysts: Part I. Materials preparation and characterization", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116060085A (en) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 Aromatic hydrocarbon hydrogenation saturation catalyst and preparation method and application thereof

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