CN112717948A - Boron modified hydrofining catalyst and preparation method and application thereof - Google Patents

Boron modified hydrofining catalyst and preparation method and application thereof Download PDF

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Publication number
CN112717948A
CN112717948A CN201911031583.3A CN201911031583A CN112717948A CN 112717948 A CN112717948 A CN 112717948A CN 201911031583 A CN201911031583 A CN 201911031583A CN 112717948 A CN112717948 A CN 112717948A
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catalyst
carrier
drying
content
boron
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CN112717948B (en
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丁思佳
杨占林
王继锋
蒋淑娇
姜虹
王会刚
刘奕
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/394—
    • B01J35/60—
    • B01J35/615—
    • B01J35/633—
    • B01J35/635—
    • 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
    • C10G45/06—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 nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

Abstract

The invention discloses a boron modified hydrorefining catalyst and a preparation method and application thereof, wherein based on the weight of the final catalyst, the content of VIB group metal in terms of metal oxide is 5.0-33.0%, the content of VIII group metal in terms of metal oxide is 1.0-15.0%, and the mass fraction of boron is B2O3The content is 0.2-6.0%, and the hydrodenitrogenation and aromatic hydrocarbon saturation performances of the boron modified hydrofining catalyst are greatly improved.

Description

Boron modified hydrofining catalyst and preparation method and application thereof
Technical Field
The invention relates to a boron modified hydrofining catalyst and a preparation method and application thereof, in particular to a boron modified hydrofining catalyst with proper acid distribution and a preparation method and application thereof.
Technical Field
The gamma-alumina is a common carrier of hydrogenation catalysts, can well disperse active metals, and is characterized in that the surface of the gamma-alumina has more Lewis acids. The gamma-alumina prepared by the conventional method has wider acid strength distribution, and an over-strong L acid center has too strong interaction with active metal, so that the vulcanization of the active metal is not facilitated, or the gamma-alumina contacts with sulfur, nitrogen compounds or polycyclic aromatic hydrocarbon of reactants in the hydrogenation process, so that the carbon deposition speed in the reaction process is too high. The two points have great influence on the activity and the stability of the hydrogenation catalyst. Therefore, weakening the acidity of the strong L acid or converting the strong L acid into a B acid center beneficial to hydrodenitrogenation and isomerization reaction in the preparation process of the carrier has positive significance for improving the activity and stability of the hydrogenation catalyst. Boron is a common element for modifying an alumina carrier, and can convert an L acid center on the alumina carrier into a B acid center.
CN102861591A discloses a preparation method of a hydrorefining catalyst, which comprises mixing a boron-containing compound (boric acid, metaboric acid or boron trioxide) with a cellulose alcohol (methyl cellulose, hydroxyethyl methyl cellulose and their mixture), then making the mixture into a directly-mixed and formed carrier with alumina, and then preparing the hydrorefining catalyst by an impregnation method.
CN106140122A discloses a method for preparing a boron-containing hydrogenation demetallization catalyst, which comprises the steps of respectively dipping a physical pore-enlarging agent in a hydrogenation active component dipping solution and a boron-containing solution, then forming the physical pore-enlarging agent, pseudo-boehmite dry glue powder, a chemical pore-enlarging agent and the like to obtain a modified alumina carrier, and dipping active components to obtain the boron-containing hydrogenation demetallization catalyst.
CN106311263A discloses a high-load boron modified hydrofining catalyst and a preparation method thereof, the method comprises the steps of placing an alumina carrier in a hydrothermal treatment furnace, reacting for 0.5-9 h under the conditions of pressure of 0-0.5 Mpa and temperature of 350-700 ℃, and then introducing a prepared boric acid aqueous solution into the furnace to obtain the boron modified alumina carrier.
CN101314130A discloses a boron-containing hydrodesulfurization catalyst and a preparation method thereof, which prepares an alumina carrier having a δ or θ structure in advance. And then soaking the alumina carrier by using a boron-containing aqueous solution, and then treating to obtain the boron-containing alumina carrier with a delta or theta structure. Then the alumina carrier is used for loading active metal to prepare the hydrodesulfurization catalyst.
US2012-0037540 discloses a process for preparing a hydrorefining catalyst containing phosphorus and boron, which comprises kneading a high content of boron with an alumina carrier, impregnating the carrier with a phosphorus-containing active metal impregnation solution to obtain a hydrorefining catalyst containing phosphorus and boron.
The activity of the hydrogenation catalyst prepared from the boron-modified alumina needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a boron modified hydrofining catalyst and a preparation method and application thereof. The boron modified hydrofining catalyst prepared by the method has greatly improved hydrodenitrogenation and aromatic hydrocarbon saturation performances.
The boron modified hydrorefining catalyst has the content of VIB group metal in metal oxide of 5.0-33.0 wt%, preferably 10.0-28.0 wt%, further preferably 16.0-22.0 wt%, and the content of VIII group metal in metal oxide of 1.0-15.0 wt%, preferably 2.0-7.0 wt%, further preferably 3.0-5.0 wt%, and boron in the B weight fraction2O3The content is 0.2-6.0%, preferably 0.3-4.0%, more preferably 0.4-2.0%, the total acid content of the catalyst is 0.2-1.0 mmol/g, preferably 0.3-0.8 mmol/g, more preferably 0.4-0.6 mmol/g, NH3The weak acid proportion with desorption temperature less than 300 ℃ is 40-90%, preferably 60-75%, NH3The proportion of moderately strong acids at desorption temperatures of from 300 ℃ to 400 ℃ is from 5% to 40%, preferably from 15% to 30%.
In the catalyst, the specific surface area of the catalyst is 120-320 m2G, preferably 180-270 m2(ii)/g, more preferably 200-2A pore volume of 0.2 to 0.6 ml/g, preferably 0.30 to 0.55 ml/g, and more preferably 0.40 to 0.50 ml/g.
A preparation method of a boron modified hydrofining catalyst comprises the following steps:
(1) dipping an amino borane compound on an alumina carrier, drying, and then carrying out vacuum treatment or heat treatment or directly carrying out vacuum treatment or heat treatment without drying, and roasting after treatment to obtain a boron modified alumina carrier;
(2) and (2) introducing active metal into the carrier obtained after roasting in the step (1), and drying and roasting to obtain the final hydrotreating catalyst.
In step (1) of the above method, the alumina carrier may be commercially available or prepared according to the prior art.
In the method, the preparation method of the conventional alumina carrier comprises the steps of taking dry glue powder of aluminum hydroxide as a raw material, and preparing the alumina carrier after molding, drying and roasting. The aluminum hydroxide dry glue powder or the aluminum hydroxide dry glue powder containing the auxiliary agent can be a commercial product or prepared by any one of the prior art. Preferably, the specific surface of the aluminum hydroxide dry glue powder after activation (roasting at 500 ℃ for 6 hours) is 200-500 m2Per g, preferably 280-420 m2A pore volume of 0.5 to 1.3 ml/g, preferably 0.7 to 1.0 ml/g.
In the step (1), the amino borane compound is one or more of dimethylamino borane, trimethylamine borane, borane ethylenediamine complex, borane triethylamine complex and borane-N, N-dimethylaniline complex, preferably dimethylamino borane.
In the step (1), the impregnation is carried out in excess volume, and the solvent used for the aminoborane compound impregnation liquid is one or more of water, ethanol, propylene glycol and toluene. In the solution, the mass fraction of the aminoborane compound borane is 0.05-10%, preferably 2-5%.
In the step (1), the drying temperature is 60-120 ℃ and the drying time is 2-6 h. Low temperature drying in order to remove the solvent.
In the step (1), the vacuum treatment is performed by vacuum pumping, the vacuum degree is maintained at 0.5-5.0 torr, and the temperature is controlled at 100-.
Step (1) of the above process) Wherein the heat treatment temperature is 150 ℃ to 500 ℃, preferably 200 ℃ to 400 ℃, and the heat treatment is preferably carried out under the action of flowing gas purging. The flowing gas can be one or a mixture of nitrogen, argon or helium, and the gas space velocity is 0.2-1.5 h-1。
In the step (1), the calcination temperature is 200-400 ℃, preferably 250-350 ℃, and the calcination time is 0.5-4.0 h. The heating rate in the roasting process is 0.2-3.0 ℃, preferably 0.5-1.5 ℃ per min.
In step (2) of the above method, the active metal is a metal of group VIB and/or group VIII, the group VIB metal is preferably molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel.
In step (2) of the above method, the active metal is loaded on the carrier by an impregnation method, and the impregnation may be of equal volume, or excess, or stepwise, or co-impregnation, preferably equal volume. Impregnation methods are well known to the skilled person. The impregnation solution is prepared by using compounds of metals of groups VIB and VIII, contains two or more components of molybdenum, tungsten, nickel and cobalt, and the concentration of the solution can be adjusted by the addition of each compound, so as to prepare the catalyst with the specified content of active components, and the preparation method of the solution is well known to those skilled in the art.
In the step (2), the drying temperature is 80-300 ℃, preferably 120-180 ℃, and the drying time is 1.0-10.0 h, preferably 2.0-5.0 h; the roasting temperature is 350-700 ℃, preferably 450-600 ℃, and the roasting time is 1.0-6.0 h, preferably 2.0-4.0 h.
In the prior art, the modification of the carrier acidity by boron modification does not generally consider the acidity intensity, so that the L acid which has too strong interaction with metal is weakened, and meanwhile, a plurality of weak L acids which are beneficial to metal dispersion are covered. This application uses dimethylamino borane as boron modified carrier, the amino can interact with the L acid on alumina surface in its molecule, because dimethylamino borane itself's boiling point is lower, when drying under the nitrogen gas condition, can follow the desorption with carrier surface weak acid interact's molecule, and can continue to stay on the carrier surface with strong acid interact's molecule, and the carrier is after hydrogen peroxide oxidation again, boron element then loads the surface at acid center with stable oxidation state, through controlling dry temperature in nitrogen gas, can directional control boron element's load and the intensity at the acid center of cover.
Detailed Description
In one or more embodiments of the present invention, the alumina carrier is prepared by the following steps: adding peptizing agent and extrusion aid into the aluminum hydroxide dry glue powder, kneading, rolling, molding, drying, roasting, and drying and roasting to prepare the gamma-Al2O3And (3) a carrier. The peptizing agent is one or more of nitric acid, acetic acid and oxalic acid. The extrusion aid is one or more of citric acid, sesbania powder or starch.
In the method of the invention, the raw material of the active component is generally a compound of salt, oxide or acid type, for example, molybdenum is generally one or more from molybdenum oxide, ammonium molybdate and ammonium paramolybdate, tungsten is generally from ammonium metatungstate, nickel is one or more from ammonium nitrate, nickel carbonate and basic nickel carbonate, and cobalt is one or more from cobalt nitrate, cobalt carbonate and basic cobalt carbonate.
The following examples and comparative examples are given to further illustrate the action and effect of the method of the present invention, but the following examples are not intended to limit the method of the present invention.
Example 1
This example describes the preparation of a hydrogenation catalyst with higher boron content by impregnating the support with a high level aqueous solution of dimethylaminoborane and vacuum drying at low temperature.
Weighing 800.0 g of dry rubber powder, adding 12.0 g of citric acid and 14.0 g of sesbania powder, uniformly mixing, and adding 650.0 g of aqueous solution containing 2.0 mass percent of nitric acid. Rolling for 10.0 min, and extruding with 2.0 mm-diameter clover orifice plate. Drying at 120 ℃ for 2.0 h, and then roasting at 550 ℃ for 3.0 h. The calcined support was designated S-0.
Weighing 20.0 g of dimethylamino borane to prepare 300.0 ml of aqueous solution, marking as Q-1, weighing 200.0 g of S-0 carrier, soaking the S-0 carrier in the Q-1, drying for 4.0 h at 100 ℃, and then drying for 4.0 h at 150 ℃ under the condition that the vacuum degree is 1.0 torr. Roasting the carrier after vacuum drying at 280 ℃ for 2.0 h, and controlling the heating rate to be 1.0 ℃ per min to obtain the carrier which is marked as S-1.
Ammonium molybdate, nickel nitrate and ammonia water are used to prepare aqueous solution containing Mo (0.22 mol) and Ni (0.08 mol) and having a pH value of 10-11 per 100 ml, which is recorded as MQ-1. 85.0 ml of MQ-1 is weighed, 100.0 g S-0 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Mo-1.
An aqueous solution containing W (0.12 mol) and Ni (0.08 mol) was prepared from ammonium metatungstate and nickel nitrate (100 ml), and the aqueous solution was designated as WQ-1. 85.0 ml of WQ-1 is weighed, 100.0 g S-0 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Wo-1.
Example 2
This example describes the preparation of a hydrogenation catalyst with higher boron content by impregnating the support with an appropriate amount of ethanol solution of dimethylaminoborane and vacuum drying at low temperature. The alumina support S-0 was prepared as in example 1.
Weighing 20.0 g of dimethylamino borane to prepare 300.0 ml of ethanol solution, marking as Q-2, weighing 200.0 g of S-0 carrier, soaking S-0 in Q-2, drying for 4.0 h at 80 ℃, and then drying for 4.0 h at 200 ℃ under the condition that the vacuum degree is 1.0 torr. And roasting the vacuum-dried carrier at 280 ℃ for 2.0 h, and controlling the heating rate to be 1.0 ℃ per min to obtain the carrier which is marked as S-2.
The preparation of an aqueous solution MQ-1 containing ammonium molybdate, nickel nitrate and aqueous ammonia was the same as in example 1. 85.0 ml of MQ-1 is weighed, 100.0 g S-2 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Mo-2.
The preparation of the aqueous solution WQ-1 containing ammonium metatungstate and nickel nitrate was the same as in example 1. 85.0 ml of WQ-1 is weighed, 100.0 g S-2 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Wo-2.
Example 3
This example describes the preparation of a hydrogenation catalyst with moderate boron content by impregnating the support with a high level of dimethylaminoborane hydroalcoholic solution and drying at moderate temperature in nitrogen. The alumina support S-0 was prepared as in example 1.
Weighing 15.0 g of dimethylamino borane to prepare 180.0 ml of aqueous solution, marking as Q-3, weighing 200.0 g of S-0 carrier, soaking the S-0 carrier with the Q-3, drying for 4.0 h at 100 ℃, then carrying out heat treatment for 4.0 h at 250 ℃ in a nitrogen atmosphere, wherein the space velocity of nitrogen is 1.5 h-1. And roasting the heat-treated carrier for 2.0 h at the temperature of 280 ℃, and controlling the heating rate to be 1.0 ℃ per min. The resulting vector was designated S-3.
The preparation of an aqueous solution MQ-1 containing ammonium molybdate, nickel nitrate and aqueous ammonia was the same as in example 1. 85.0 ml of MQ-1 is weighed, 100.0 g S-3 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is recorded as Mo-3.
The preparation of the aqueous solution WQ-1 containing ammonium metatungstate and nickel nitrate was the same as in example 1. 85.0 ml of WQ-1 is weighed, 100.0 g S-3 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is recorded as Wo-3.
Example 4
This example describes the preparation of a hydrogenation catalyst with moderate boron content by impregnating the support with a suitable amount of ethanol solution of dimethylaminoborane and drying it at moderate temperature in nitrogen. The alumina support S-0 was prepared as in example 1.
Weighing 15.0 g of dimethylamino borane to prepare 180.0 ml of aqueous solution, marking as Q-3, weighing 200.0 g of S-0 carrier, soaking the S-0 carrier with the Q-3, drying for 4.0 h at 80 ℃, then carrying out heat treatment for 4.0 h at 300 ℃ in a nitrogen atmosphere, wherein the space velocity of nitrogen is 0.5 h-1. And roasting the carrier subjected to the nitrogen heat treatment for 2.0 hours at the temperature of 280 ℃, and controlling the heating rate to be 1.0 ℃ per minute. The resulting vector was designated S-4.
The preparation of an aqueous solution MQ-1 containing ammonium molybdate, nickel nitrate and aqueous ammonia was the same as in example 1. 85.0 ml of MQ-1 is weighed, 100.0 g S-4 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Mo-4.
The preparation of the aqueous solution WQ-1 containing ammonium metatungstate and nickel nitrate was the same as in example 1. 85.0 ml of WQ-1 is weighed, 100.0 g S-4 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Wo-4.
Example 5
This example describes the preparation of a hydrogenation catalyst having a lower boron content by impregnating the support with an appropriate amount of aqueous dimethylamine borane and drying the impregnated support at elevated temperature under argon. The alumina support S-0 was prepared as in example 1.
Weighing 15.0 g of dimethylamino borane to prepare 180.0 ml of aqueous solution, marking as Q-3, weighing 200.0 g of S-0 carrier, soaking the S-0 carrier with the Q-3, drying for 4.0 h at 100 ℃, then carrying out heat treatment for 4.0 h at 350 ℃ in argon atmosphere, wherein the airspeed of argon is 1.0 h-1. And roasting the carrier treated by the nitrogen for 2.0 h at the temperature of 280 ℃, and controlling the heating rate to be 1.0 ℃ per min. The resulting vector was designated S-5.
The preparation of an aqueous solution MQ-1 containing ammonium molybdate, nickel nitrate and aqueous ammonia was the same as in example 1. 85.0 ml of MQ-1 is weighed, 100.0 g S-5 carrier is soaked, dried for 4.0 h at 150 ℃, and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Mo-5.
The preparation of the aqueous solution WQ-1 containing ammonium metatungstate and nickel nitrate was the same as in example 1. 85.0 ml of WQ-1 is weighed, 100.0 g S-5 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Wo-5.
Example 6
This example describes the preparation of a lower boron hydrogenation catalyst by impregnating the support with a moderate solution of dimethylaminoborane in toluene and drying at high temperature under argon. The alumina support S-0 was prepared as in example 1.
Weighing 15.0 g of dimethylamino borane to prepare 180.0 ml of aqueous solution, marking as Q-3, weighing 200.0 g of S-0 carrier, soaking S-0 in Q-3, drying for 4.0 h at 80 ℃, then carrying out heat treatment for 4.0 h at 400 ℃ in argon atmosphere, wherein the airspeed of argon is 0.8h-1. And roasting the heat-treated carrier for 2.0 h at the temperature of 280 ℃, and controlling the heating rate to be 1.0 ℃ per min. The resulting vector was designated S-6.
The preparation of an aqueous solution MQ-1 containing ammonium molybdate, nickel nitrate and aqueous ammonia was the same as in example 1. 85.0 ml of MQ-1 is weighed, 100.0 g S-6 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Mo-6.
The preparation of the aqueous solution WQ-1 containing ammonium metatungstate and nickel nitrate was the same as in example 1. 85.0 ml of WQ-1 is weighed, 100.0 g S-6 carrier is soaked, dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as Wo-6.
Comparative example 1
This comparative example describes the preparation of a hydroprocessing catalyst containing no promoter. The alumina support S-0 was prepared as in example 1.
Soaking the MQ-1 solution in 87.0ml of S-0, drying at 150 ℃ for 4.0 h, and roasting at 500 ℃ for 2.0 h to obtain the catalyst Mo-7.
87.0ml of WQ-1 solution is taken to be dipped in S-0, and then dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as W-7.
Comparative example 2
This comparative example describes the preparation of a hydrogenation catalyst impregnated directly with an aqueous solution of boric acid. The alumina support S-0 was prepared as in example 1.
Weighing 3.0g of boric acid, preparing 180.0 ml of aqueous solution, marking as Q-6, weighing 200.0 g of S-0 carrier, soaking the S-0 carrier in the Q-6, drying at 140 ℃ for 4.0 h, and roasting at 500 ℃ for 2.0 h to obtain the carrier, marking as S-7.
And (3) soaking the S-7 in 87.0ml of MQ-1 solution, drying at 150 ℃ for 4.0 h, and roasting at 500 ℃ for 2.0 h to obtain the catalyst which is marked as Mo-8.
87.0ml of WQ-1 solution is taken to be dipped in S-7, and then dried for 4.0 h at 150 ℃ and roasted for 2.0 h at 500 ℃, and the obtained catalyst is marked as W-8.
The support properties of the examples and comparative examples are shown in table 1.
Figure DEST_PATH_IMAGE001
Table 1 main physicochemical properties of the prepared carrier
The properties of the Mo and Ni catalysts in the examples and comparative examples are shown in Table 2, and the properties of the Wo and Ni catalysts in the examples and comparative examples are shown in Table 3.
Figure 27415DEST_PATH_IMAGE002
Table 2 main physicochemical properties of Mo, Ni based catalyst prepared
Figure DEST_PATH_IMAGE003
Main physicochemical properties of W, Ni series catalyst prepared in table 3
The properties of the feedstocks VGO and CGO selected in the examples and comparative examples are shown in table 4.
TABLE 4 Properties of the feed oils
Figure 288632DEST_PATH_IMAGE004
The results of evaluating the activity of the Mo and Ni catalysts in the examples and comparative examples are shown in Table 5, and the results of evaluating the activity of the W, Ni catalysts are shown in Table 6.
TABLE 5 evaluation results of Mo and Ni-based catalyst activities
Figure DEST_PATH_IMAGE005
TABLE 6W, Ni evaluation results of catalyst activity
Figure 82144DEST_PATH_IMAGE006
According to the catalyst characterization result and the evaluation result, the invention can optimize the acidity of the carrier surface, adjust the dispersion state of the active metal and improve the desulfurization, denitrification and aromatic saturation performance of the hydrogenation catalyst by introducing the dimethylamino borane and carrying out vacuum or inert atmosphere drying treatment.
The boron-containing hydrogenation catalyst carrier dried under the low-temperature mild condition has the advantages that the L acid on the surface is more covered by boron, the whole carrier is weaker in acidity, the distribution of active metal is concentrated, the stacking of the active phase is higher, and the boron-containing hydrogenation catalyst carrier is suitable for treating oil products with higher aromatic hydrocarbon content such as coking wax oil. The boron-containing hydrogenation catalyst carrier dried under the high-temperature harsh condition has less coverage of L acid on the surface by boron element, limited coverage of the L acid on a strong L acid position, better dispersion of active metal and lower stacking of an active phase, and is suitable for treating oil products with less aromatic hydrocarbon content, such as vacuum gas oil and the like.

Claims (16)

1. A boron modified hydrorefining catalyst is characterized in that: based on the weight of the final catalyst, the content of VIB group metal calculated by metal oxide is 5.0-33.0%, the content of VIII group metal calculated by metal oxide is 1.0-15.0%, and the mass fraction of boron is B2O3The content is 0.2-6.0%, the total acid content of the catalyst is 0.2-1.0 mmol/g, and NH is added3The weak acid proportion with desorption temperature less than 300 ℃ is 40-90%, preferably 60-75%, NH3The proportion of acid with medium strength at the desorption temperature of 300-400 ℃ is 5-40%.
2. The catalyst of claim 1, wherein: based on the weight of the final catalyst, the content of the VIB group metal calculated by metal oxide is 10.0-28.0%, the content of the VIII group metal calculated by metal oxide is 2.0-7.0%, and the mass fraction of boron is B2O3The content is 0.3% -4.0%, the total acid content of the catalyst is 0.3-0.8 mmol/g, NH3The weak acid proportion with desorption temperature less than 300 ℃ is 40-90%, preferably 60-75%, NH3The proportion of acid with medium strength at the desorption temperature of 300-400 ℃ is 15-30%.
3. The catalyst of claim 1, wherein: the specific surface area of the catalyst is 120-320 m2The pore volume is 0.2-0.6 ml/g.
4. A preparation method of a boron modified hydrofining catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) dipping an amino borane compound on an alumina carrier, drying, and then carrying out vacuum treatment or heat treatment or directly carrying out vacuum treatment or heat treatment without drying, and roasting after treatment to obtain a boron modified alumina carrier;
(2) and (2) introducing active metal into the carrier obtained after roasting in the step (1), and drying and roasting to obtain the final hydrotreating catalyst.
5. The method of claim 4, wherein: in the step (1), the amino borane compound is one or more of dimethylamino borane, trimethylamine borane, borane ethylenediamine complex, borane triethylamine complex and borane-N, N-dimethylaniline complex.
6. The method of claim 4, wherein: in the step (1), the impregnation is carried out in a volume-excess manner, and the solvent adopted by the aminoborane compound impregnation liquid is one or more of water, ethanol, propylene glycol and toluene.
7. The method of claim 4, wherein: in the step (1), the mass fraction of the amino borane compound borane in the solution is 0.05-10%.
8. The method of claim 4, wherein: in the step (1), the drying temperature is 60-120 ℃ and the drying time is 2-6 h.
9. The method of claim 4, wherein: in the step (1), the vacuum treatment is performed by vacuum pumping, the vacuum degree is maintained at 0.5-5.0 torr, and the temperature is controlled at 100 ℃ and 400 ℃.
10. The method of claim 4, wherein: in the step (1), the heat treatment temperature is 150 ℃ and 500 ℃, and the heat treatment is carried out under the action of flowing gas purging.
11. According to claimThe method of 11, characterized by: the flowing gas is one or a mixture of nitrogen, argon or helium, and the gas space velocity is 0.2-1.5 h-1。
12. The method of claim 4, wherein: in the step (1), the roasting temperature is 200 ℃ and 400 ℃, and the roasting time is 0.5-4.0 h.
13. The method of claim 4, wherein: in the step (2), the active metal is a metal of group VIB and/or group VIII, the group VIB metal is molybdenum and/or tungsten, and the group VIII metal is preferably cobalt and/or nickel.
14. The method of claim 4, wherein: in the step (2), the active metal is loaded on the carrier by an impregnation method, and equal-volume impregnation or excess impregnation is adopted.
15. The method of claim 4, wherein: in the step (2), the drying temperature is 80-300 ℃, and the drying time is 1.0-10.0 h; the roasting temperature is 350-700 ℃, and the roasting time is 1.0-6.0 h.
16. Use of a catalyst according to any of claims 1 to 3 in hydroprocessing.
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