WO2018019203A1

WO2018019203A1 - Boron-modified hydrofining catalyst having high loading amount and preparation method therefor

Info

Publication number: WO2018019203A1
Application number: PCT/CN2017/094091
Authority: WO
Inventors: 许莉; 石友良; 张然; 冯春峰; 王杰华
Original assignee: 武汉凯迪工程技术研究总院有限公司
Priority date: 2016-07-29
Filing date: 2017-07-24
Publication date: 2018-02-01
Also published as: CN106311263B; CN106311263A

Abstract

A boron-modified hydrofining catalyst having a high loading amount and a preparation method therefor. The catalyst consists of an active metal component and a carrier. The active metal component is carried by the carrier. The active metal component consists of oxides containing group VIB and group VIII metals. The group VIB metal is Mo and/or W, and the group VIII metal is Ni and/or Co. The carrier is a boron-modified aluminium oxide carrier. The boron-modified hydrofining catalyst and B₂O₃ are uniformly distributed and concentrated on the surface of the aluminium oxide carrier, so as to prevent the active component from entering an aluminium oxide lattice, help to improve the dispersity and utilization of the metal component, and further improve the hydrogenation activity of the catalyst. In addition, a boracic hydrofining catalyst having a high loading amount can be obtained, and the catalyst has high denitrification activity.

Description

High-load boron modification hydrotreating catalyst and preparation method thereof

Technical field

The invention relates to a catalyst and a preparation method thereof, in particular to a high-load boron-modified hydrorefining catalyst and a preparation method thereof.

Background technique

A typical hydrofinishing catalyst typically consists of an alumina support and a hydrogenation active metal. The hydrogenation-active metal is a Group VIB and/or Group VIII metal, the commonly used Group VIB metal is Mo and/or W, and the Group VIII metal is Co and/or Ni. As a carrier material, alumina has a wide range of applications in the field of hydrogenation catalysis. However, due to the weak acidity of alumina, it is easy to interact with the active metal component to form inactive species, which affects the activity and stability of the catalyst. In order to improve the acidity of alumina and adjust its interaction with metal components, alumina is often modified by introducing additives such as Si, P, Ti, B, and F.

The effect of boron on the hydrotreating catalyst is mainly reflected in the improvement of denitrification activity and the improvement of metal dispersion, thereby improving the hydrogenation activity of the refined catalyst. The literature (Lewandowski M, Fuel, 2000, 79, 487) studied the effect of boron on the hydrodenitrogenation activity of hydrotreating catalysts. It was found that the hydrodenitrogenation activity of the catalyst gradually increased with the increase of boron loading. Increasing, the rate of deactivation of the catalyst is slowed down. The additive boron deepens the degree of hydrogenation reaction, because boron forms B ₂ O ₃ on the surface of alumina, promotes the vulcanization of the catalyst, reduces the carbon deposition in the hydrogenation process, and improves the dispersion of the active metal component. .

Boron as an auxiliary agent for alumina modification, the usual addition methods are divided into two types: one is to introduce boron during the formation of the carrier, including the coprecipitation method and the physical mixing method; the other is to pass the preform after the formation of the carrier. Impregnation is introduced. Boron is generally added to the support in the form of H ₃ BO ₃ , while the solubility of H ₃ BO ₃ is only 6 g/100 ml of water at room temperature, which limits the loading of boron to some extent.

The Chinese invention patent published as CN00122919.2 discloses a hydrodenitrogenation catalyst and a preparation method thereof. The catalyst uses alumina or silica-containing alumina as a carrier, Mo-Ni as an active component, and a boron auxiliary agent. By formulating a stable alkaline Mo-Ni-B solution and using a co-impregnation technique, the hydrodenitrogenation activity of the catalyst is improved. The catalyst is impregnated step by step, introducing ammonia water and polluting the environment.

Chinese Patent Publication No. CN00110018.1 discloses a hydrogenation catalyst and a preparation method thereof, The catalyst is a hydrogenation active component of Group VIB and Group VIII metals, supporting boron, silicon and other additives, and is prepared by coprecipitation. Some active metals may enter the bulk phase or be oxidized during coprecipitation and extrusion. Covered with aluminum particles, the utilization rate of the active metal is lowered, and the hydrogenation activity is low.

The Chinese invention patent publication CN101491767A discloses a preparation method of a hydrogenation catalyst, wherein the fluorine, silicon, phosphorus and the like in the catalyst carrier are passed through the gelation process of the dry rubber powder and the two stages of the carrier molding process. The addition can effectively improve the dispersion of the active metal on the surface, improve the utilization rate of the active metal, and further improve the performance of the catalyst. The boron content of the promoter in the catalyst is only about 1%.

In the above-disclosed patents, the modification of the hydrotreating catalyst by the auxiliary boron is involved. There are two problems in the prior art: first, the introduction of boron by conventional methods does not have a beneficial effect on the dispersion of the active metal component on the carrier; second, the loading of the auxiliary boron is low, and the catalyst is hydrolyzed. The activity of nitrogen is restricted.

Summary of the invention

The present invention provides a high-load boron-modified hydrotreating catalyst and a preparation method thereof in view of the deficiencies in the prior art. The method can not only better distribute the boron of the auxiliary agent on the surface of the alumina carrier, improve the dispersion degree of the active component, but also effectively increase the loading of boron in the catalyst and improve the hydrodenitrogenation activity of the catalyst. The hydrofinishing catalyst prepared by the present invention is particularly suitable for hydrotreating of high nitrogen feedstock oil.

In order to achieve the above object, the present invention provides a high-load boron-modified hydrotreating catalyst composed of an active metal component and a carrier, the active metal component being supported on a carrier, the active metal group It is composed of an oxide containing two metals of Group VIB and Group VIII, wherein the Group VIB metal is Mo and/or W, the Group VIII metal is Ni and/or Co, and the carrier is boron modified alumina. Carrier.

Further, in the catalyst, the content of the oxide containing the Group VIB metal is 8.9 to 30.1%, the content of the oxide containing the Group VIII metal is 1.9 to 10.1%, and boron in the boron-modified alumina carrier accounts for The mass fraction of the catalyst is from 1.0 to 11.5%.

Further, the content of the oxide containing the Group VIB metal is 15.0 to 26.0%, the metal of the Group VIII is preferably Ni, and the content of the oxide containing Ni is 2.2 to 6.5%, and the mass fraction of boron in the catalyst is 2.0 to 4.0%.

Further, in the catalyst, the catalyst has a specific surface area of 130 to 320 m ² /g and a total pore volume of 0.15 to 0.50 cm ³ /g.

Still further, the catalyst has a specific surface area of from 190 to 250 m ² /g and a total pore volume of from 0.33 to 0.40 cm ³ /g.

Still further, the method for preparing the boron-modified alumina carrier comprises the following steps:

1) Weighing the alumina precursor, the extrusion aid and the peptizer, mixing and rolling, extruding the strip to obtain an alumina extrudate, and then drying and roasting to obtain an alumina carrier;

2) preparing a boric acid solid into a boric acid aqueous solution having a mass fraction of 0.5 to 5.6%;

3) Weigh the alumina carrier obtained in step 1) in a hydrothermal treatment furnace, react at a pressure of 0-0.5 mpa and a temperature of 350-700 ° C for 0.5-9 h, and then pass the boric acid aqueous solution prepared in step 2). Into the furnace, a boron-modified alumina carrier is obtained.

Further, in the step 1), the alumina precursor is amorphous aluminum hydroxide, pseudo boehmite, boehmite, gibbsite, yttrium aluminum, and boehmite. Any one or several of them, or an aluminum oxide compound which can be converted into γ-Al ₂ O ₃ after calcination; the squeezing agent is citric acid and/or phthalocyanine powder, and the mass of the squeezing agent accounts for the mass of the alumina carrier 1.0 to 5.0%; the peptizer is an aqueous solution of an organic acid or an inorganic acid, the organic acid is formic acid and/or acetic acid, and the inorganic acid is any one or more of nitric acid, phosphoric acid, and hydrochloric acid; the acid content in the peptizing agent accounts for oxidation The mass of the aluminum carrier is 1.0 to 7.0%.

Further, the mass of the extrusion agent accounts for 2.0 to 3.5% of the mass of the alumina carrier; and the content of the acid in the gum solvent accounts for 1.8 to 4.0% of the mass of the alumina carrier.

Further, in the step 1), the drying temperature is 60 to 190 ° C, the drying time is 0.1 to 22 h, the baking temperature is 300 to 650 ° C, and the baking time is 3 to 6 h.

Further, in the step 1), the drying temperature is 90 to 130 ° C, the drying time is 1.5 to 8 hours, the baking temperature is 420 to 540 ° C, and the baking time is 3 to 6 hours.

Further, in the step 1), the alumina carrier is in the shape of a cylinder, a clover, a four-leaf clover or a gear, wherein the cylindrical strip-shaped alumina carrier has a particle diameter of 1.2 to 1.6 mm and a length of 5 to 10 mm; The two-leaf pitch of clover or four-leaf clover is 1.1 to 1.8 mm and the length is 5 to 10 mm.

Further, in the step 3), when the boric acid aqueous solution is introduced into the furnace, the mass space velocity of the boric acid aqueous solution is 0.1 to 5.5 h ^-1 .

Further, the mass space velocity of the aqueous boric acid solution is 1.2 to 4.0 h ^-1 .

The invention provides a preparation method of a high-load boron-modified hydrotreating catalyst, which comprises the following steps:

3) Weigh the alumina carrier obtained in step 1) in a hydrothermal treatment furnace, react at a pressure of 0-0.5 mpa and a temperature of 350-700 ° C for 0.5-9 h, and then pass the boric acid aqueous solution prepared in step 2). Into the furnace, obtaining a boron-modified alumina carrier;

4) weighing a metal salt containing two metals of Group VIB and Group VIII, and formulating the corresponding metal salt solution;

5) According to the difference of metal oxide loading, the boron-modified alumina carrier obtained in step 3) is weighed into the metal salt solution obtained in step 4) for impregnation; the impregnation method can select equal volume impregnation, excessive impregnation, and The two metal components may be co-impregnated or stepwise impregnated, preferably in an equal volume co-impregnation.

6) The carrier impregnated in the step 5) is dried and calcined to obtain a hydrotreating catalyst.

Preferably, in the step 4), the metal cobalt is selected from the group consisting of cobalt nitrate, cobalt chloride, cobalt carbonyl and cobalt carbonate; the metal molybdenum is selected from the group consisting of ammonium molybdate, molybdenum oxide and ammonium paramolybdate; the metal tungsten is selected from the group consisting of tungsten Ammonium acid and ammonium paratungstate; metal nickel is selected from the group consisting of nickel nitrate, basic nickel carbonate and nickel carbonate.

Preferably, in the step 6), the drying temperature is 70 to 200 ° C, preferably 95 to 125 ° C, the drying time is 1.0 to 24 h, preferably 3 to 6 h, and the calcination temperature is 250 to 600 ° C, preferably 400. The calcination time is ～510° C., and the calcination time is 1 to 15 h, preferably 3 to 5 h.

Preferably, in the step 6), the drying temperature is 95 to 125 ° C, the drying time is 3 to 6 hours, the baking temperature is 400 to 510 ° C, and the baking time is 3 to 5 hours.

The beneficial effects of the invention are:

1) The boron-modified hydrotreating catalyst prepared by the method of the invention has a uniform distribution of B ₂ O ₃ and is concentrated on the surface of the alumina carrier, which can prevent the active component from entering the alumina crystal lattice, and is favorable for increasing the dispersion degree of the metal component. , improving the utilization rate of the metal component, thereby increasing the hydrogenation activity of the catalyst;

2) The boron-modified hydrotreating catalyst prepared by the invention can obtain a high-loading boron-containing hydrotreating catalyst, and the catalyst has higher denitrification activity.

detailed description

In order to better explain the present invention, the main contents of the present invention will be further clarified below with reference to specific embodiments, but the content of the present invention is not limited to the following embodiments.

Preparation of raw materials:

Preparation method of Ni-W metal salt solution:

Taking nickel nitrate hexahydrate and ammonium metatungstate as raw materials, according to the target concentration of NiO and WO ₃ in the immersion liquid, an appropriate amount of metal salt is weighed in deionized water, stirred and dissolved to a dark green clarified solution, and used. The NiO content in the Ni-W metal salt solution is 10 to 15 g/100 ml, and the WO ₃ content is 40 to 44 g/100 ml.

Preparation method of Ni-Mo metal salt solution:

Using basic nickel carbonate, molybdenum trioxide and phosphoric acid as raw materials, according to the target concentration of NiO and MoO ₃ in the impregnation solution, an appropriate amount of metal salt and phosphoric acid solution are weighed and heated to reflux to obtain a clear dark green solution, which is ready for use. Among them, the NiO content in the Ni-Mo metal salt solution is 6 to 8 g/100 ml, and the MoO ₃ content is 38 to 42 g/100 ml.

According to the above preparation method, the metal salt and the oxide are selected according to actual conditions, such as:

The metal molybdenum is selected from the group consisting of ammonium molybdate, molybdenum oxide

The metal tungsten is selected from the group consisting of ammonium metatungstate and ammonium paratungstate;

The metallic nickel is selected from the group consisting of nickel nitrate, basic nickel carbonate and nickel carbonate.

The raw materials used in the following examples were purchased from the market.

Example 1

1) Weigh 150g of pseudo-boehmite, which is pseudo-hydrated boehmite (the dry basis of pseudo-boehmite is 80%, the specific surface is 380m ² /g, and the total pore volume is 0.86cm ³ / g), 5g of Tianjing powder, measuring 120ml of 4% dilute nitric acid aqueous solution, crushed into a squeezable cake in a wheel mill, extruded by a squeezer, the extrudate is 1.5mm in diameter a cylindrical shape; the extrudate is dried at 90 ° C for 16 h, and then calcined at 530 ° C for 6 h to obtain an alumina carrier Z1;

2) weighed 58g of boric acid solids, dissolved in 1000ml of deionized water at room temperature, stirred until completely dissolved, to obtain a boric acid aqueous solution A1 with a mass concentration of 5.5%;

3) Weigh 80g of Z1 in the hydrothermal oven, control the reaction pressure to 0.1mpa, the reaction temperature is 500 ° C, the reaction time is 3.5h, and the mass space velocity of the aqueous solution of boric acid A1 to the alumina carrier Z1 is 1.2h ^-1 . Obtaining a boron-modified alumina carrier BZ1;

4) The carrier BZ1 was impregnated with an equal volume of a metal salt solution containing Ni-Mo, dried at 100 ° C for 5 h, and calcined at 500 ° C for 3 h to obtain a catalyst C1.

Example 2

1) Weigh 200 g of amorphous aluminum hydroxide (70% dry base of amorphous aluminum hydroxide, specific surface area of 370 m ² /g, total pore volume of 0.89 cm ³ /g), 5 g of phthalocyanine powder, 120 ml of a 5% acetic acid aqueous solution was weighed, crushed into a squeezable cake in a wheel mill, and extruded by a squeezer, and the extrudate was a clover having a pitch of 1.6 mm; the extrudate was Drying at 100 ° C for 12 h, and then calcining at 510 ° C for 6 h, to obtain an alumina carrier Z2;

2) Weigh 60g of boric acid solid, dissolved in 1200ml of deionized water at room temperature, stirred until completely dissolved, to obtain a boric acid aqueous solution A2 with a mass concentration of 4.8%;

3) Weigh 80g of Z2 in a hydrothermal oven, control the reaction pressure to 0.2mpa, the reaction temperature is 550 ° C, the reaction time is 4.0h, and the mass space velocity of the aqueous solution of boric acid A2 to the alumina carrier Z2 is 1.5h ^-1 ; Obtaining a boron-modified alumina carrier BZ2;

4) The carrier BZ2 was impregnated with an equal volume of a metal salt solution containing Ni-Mo, dried at 110 ° C for 5 h, and calcined at 480 ° C for 4 h to obtain a catalyst C2.

Example 3

1) Weigh 200g of lycopene (75% dry base of beryllite, 350m ² /g of specific surface, 0.92cm ³ /g of total pore volume), 6g of phthalocyanine powder, and measure the concentration of 150ml It was a 4% aqueous acetic acid solution, crushed into a squeezable cake in a wheel mill, and extruded by a squeezer, and the extrudate was a clover with a pitch of 1.6 mm. The extrudate is dried at 110 ° C for 8 h, and then calcined at 530 ° C for 6 h to obtain an alumina carrier Z3;

2) Weigh 50g of boric acid solid, dissolved in 1500ml of deionized water at room temperature, stirred until completely dissolved, to obtain a boric acid aqueous solution A3 with a mass concentration of 3.2%;

3) Weigh 80g of Z3 in the hydrothermal treatment furnace, control the reaction pressure to be 0.15mpa, the reaction temperature is 600 °C, the reaction time is 6.0h, and the mass space velocity of the aqueous solution of boric acid A3 to the alumina carrier Z3 is 2.0h ^-1 . Obtaining a boron-modified alumina carrier BZ3;

4) The carrier BZ3 was impregnated with an equal volume of a metal salt solution containing Ni-Mo, dried at 110 ° C for 5 h, and calcined at 500 ° C for 4 h to obtain a catalyst C3.

Example 4

1) Weigh 200g of pseudo-boehmite (80% dry basis of pseudo-boehmite, specific surface area of 380m ² /g, total pore volume of 0.86cm ³ /g), 8g of Tianjing powder, 150 ml of a 4% aqueous solution of nitric acid was weighed, crushed into a squeezable cake in a wheel mill, and extruded by a squeezer. The extrudate was a cylindrical shape with a diameter of 1.6 mm, and the extrudate was at 110. It was dried at ° C for 8 h and then calcined at 530 ° C for 6 h to obtain an alumina carrier Z4.

2) Weigh 40g of boric acid solid, dissolve in 1500ml of deionized water at room temperature, stir until completely dissolved, A boric acid aqueous solution A4 having a mass concentration of 2.6%;

3) 80 g of Z4 was weighed in a hydrothermal oven, and the reaction pressure was controlled to 0.15 mPa, the reaction temperature was 600 ° C, and the reaction time was 5.0 h. The mass space velocity of the aqueous solution of boric acid A4 to the alumina carrier Z4 was 3.0 h ^-1 . Obtaining a boron-modified alumina carrier BZ4;

4) The carrier BZ4 was impregnated with an equal volume of a metal salt solution containing Ni-W, dried at 120 ° C for 5 h, and calcined at 520 ° C for 4 h to obtain a catalyst C4.

Comparative example 1

1) Weigh 150g of pseudo-boehmite (80% dry basis of pseudo-boehmite, specific surface 380m ² /g, total pore volume is 0.86cm ³ /g), 5g Tianjing powder, amount 120 ml of a dilute aqueous solution of dilute nitric acid having a mass concentration of 4% was taken, crushed into an extrudable cake in a wheel mill, and extruded by a squeezer, and the extrudate was a cylindrical shape having a diameter of 1.5 mm. The extrudate was dried at 90 ° C for 16 h and then calcined at 530 ° C for 6 h to obtain an alumina support Z5.

2) 55 g of boric acid solid was weighed, dissolved in 1000 ml of deionized water at room temperature, and stirred until completely dissolved to obtain a boric acid aqueous solution A5 having a mass concentration of 5.2%.

3) Weigh 80g of Z5 in the hydrothermal oven, control the reaction pressure to 0.1mpa, the reaction temperature is 500 °C, the reaction time is 2.0h, and the mass space velocity of the aqueous solution of boric acid A5 to the alumina carrier Z5 is 0.8h ^2-1 . A boron-modified alumina carrier BZ5 was obtained.

4) The carrier BZ5 was impregnated with an equal volume of a metal salt solution containing Ni-Mo, dried at 100 ° C for 5 h, and calcined at 500 ° C for 3 h to obtain a catalyst C5.

Comparative example 2

1) Weigh 200g of pseudo-boehmite (80% dry basis of pseudo-boehmite, specific surface 380m ² /g, total pore volume is 0.86cm ³ /g), and add 6g of tianjing powder. Then, 150 ml of a dilute nitric acid solution having a mass concentration of 4% dissolved in 9 g of boric acid was added, and the cake was rolled in a wet wheel mill and extruded into a extruder to form a cylindrical body having a diameter of 1.5 mm. . The extrudate was dried at 90 ° C for 16 h and then calcined at 530 ° C for 6 h to obtain an alumina support Z6.

2) 80 g of the carrier Z6 was impregnated with an equal volume of a metal salt solution containing Ni-Mo, dried at 100 ° C for 5 h, and calcined at 500 ° C for 3 h to obtain a catalyst C6.

The physicochemical properties of each catalyst are shown in Table 1. The metal dispersion is measured by photoelectron spectroscopy, and the larger the value of the dispersion, the better the metal dispersion. I is the area intensity of the photoelectron peak of an element, I _Ni /I _Al Al represents the dispersion of Ni element on alumina, I _Mo /I _Al represents the dispersion of Mo element on alumina, and I _W /I _Al represents W The dispersion of the elements on the alumina.

Table 1 Summary of catalyst physicochemical properties

The performance evaluation of the catalyst of the present invention was carried out in a 30 ml fixed bed reactor, and the catalyst was pre-vulcanized before the reaction. The performance evaluation conditions of the catalyst were a reaction pressure of 10.5 mPa, a hydrogen oil volume ratio of 1200, a raw material feed volume space velocity of 1.5 h ^-1 , and a reaction temperature of 385 °C. The properties of the feedstock oil are shown in Table 2, and the results of the activity evaluation of the catalyst are shown in Table 3.

It can be seen from Table 1 that the boron-containing hydrotreating catalyst is prepared by the method of the invention, the dispersion of the active component on the alumina carrier is good, the utilization ratio of the metal component is improved, and the hydrogenation of the catalyst can be remarkably improved. active. The data in Table 3 shows that the boron-containing hydrotreating catalysts C1 to C5 prepared by the method of the present invention have a B content of 2.0 to 4.0% in C1 to C4, have high hydrogenation activity, and aromatic hydrocarbons and sulfur nitrogen in the feedstock oil. The content is greatly reduced, and C4 exhibits excellent hydrogenation activity. The content of B in the catalyst C5 was only 0.98%, and the denitrification activity was slightly inferior. Kneading The prepared boron-containing hydrotreating catalyst C6 has the lowest hydrogenation activity and denitrification activity due to uneven distribution of boron in the carrier.

Table 2 raw oil properties

项目project	结果result
密度(20℃)，g/mlDensity (20 ° C), g / ml	0.93100.9310
馏程，℃Distillation range, °C
IBP/EBPIBP/EBP	312/547312/547
芳烃含量，m％Aromatic content, m%	18.2618.26
S，m％S, m%	1.201.20
N，m％N, m%	0.160.16

Table 3 product oil properties

Other parts not described in detail are prior art. While the above-described embodiments have been described in detail, the present invention is only a part of the embodiments of the present invention, but not all of the embodiments, and other embodiments may be obtained without inventiveness according to the embodiments. All belong to the scope of protection of the present invention.

Claims

A high-load boron-modified hydrotreating catalyst consisting of an active metal component and a carrier, the active metal component being supported on a carrier, characterized in that the active metal group is composed of a group VIB And an oxide composition of two metals of Group VIII, wherein the Group VIB metal is Mo and/or W, the Group VIII metal is Ni and/or Co, and the support is a boron modified alumina support.
The high-load boron-modified hydrotreating catalyst according to claim 1, wherein the catalyst contains a Group VIB metal having an oxide content of 8.9 to 30.1%, and an oxide content of the Group VIII metal. From 1.9 to 10.1%, boron in the boron-modified alumina carrier accounts for 1.0 to 11.5% by mass of the catalyst.
The high-load boron-modified hydrotreating catalyst according to claim 2, wherein the Group VIB-containing metal has an oxide content of 15.0 to 26.0%, and the Group VIII metal is Ni and contains Ni. The oxide content is 2.2 to 6.5%, and the boron content of the catalyst is 2.0 to 4.0%.
The high-load boron-modified hydrotreating catalyst according to claim 1 or 2 or 3, wherein the catalyst has a specific surface area of 130 to 320 m 2 /g and a total pore volume of 0.15 to 0.50. Cm 3 /g.
The high-load boron-modified hydrotreating catalyst according to claim 4, wherein:

The catalyst has a specific surface area of 190 to 250 m 2 /g and a total pore volume of 0.33 to 0.40 cm 3 /g.
The high-load boron-modified hydrotreating catalyst according to claim 1 or 2 or 3, wherein the boron-modified alumina carrier comprises the following steps:

1) Weighing the alumina precursor, the extrusion aid and the peptizer, mixing and rolling, extruding the strip to obtain an alumina extrudate, and then drying and roasting to obtain an alumina carrier;

2) preparing a boric acid solid into a boric acid aqueous solution having a mass fraction of 0.5 to 5.6%;

3) Weigh the alumina carrier obtained in step 1) in a hydrothermal treatment furnace, react at a pressure of 0-0.5 mpa and a temperature of 350-700 ° C for 0.5-9 h, and then pass the boric acid aqueous solution prepared in step 2). Into the furnace, a boron-modified alumina carrier is obtained.
The high-load boron-modified hydrotreating catalyst according to claim 6, wherein in the step 1), the alumina precursor is amorphous aluminum hydroxide, pseudo-boehmite, and thin water. Any one or more of aluminum stone, gibbsite, yttrium aluminum, and boehmite, or an aluminum oxide compound which can be converted into γ-Al 2 O 3 after calcination; the squeezing agent is citric acid And/or Tianjing powder, the mass of the extrusion agent is 1.0-5.0% of the mass of the alumina carrier; the peptizer is an aqueous solution of an organic acid or an inorganic acid, the organic acid is formic acid and/or acetic acid, and the inorganic acid is nitric acid, phosphoric acid, Any one or several of hydrochloric acid; the content of the acid in the peptizer is 1.0 to 7.0% of the mass of the alumina carrier.
The high-load boron-modified hydrotreating catalyst according to claim 7, wherein the mass of the extrusion agent accounts for 2.0 to 3.5% of the mass of the alumina carrier; and the acid content of the gum solvent accounts for the mass of the alumina carrier. 1.8 to 4.0%.
The high-load boron-modified hydrotreating catalyst according to claim 6, wherein in the step 1), the drying temperature is 60 to 190 ° C, the drying time is 0.1 to 22 h, and the calcination temperature is 300 to 650 ° C. The calcination time is 3 to 6 hours.
The high-load boron-modified hydrotreating catalyst according to claim 9, wherein in the step 1), the drying temperature is 90-130 ° C, the drying time is 1.5-8 h, and the calcination temperature is 420-540 ° C. The calcination time is 3 to 6 hours.
The high-load boron-modified hydrotreating catalyst according to claim 7 or 9, wherein in the step 1), the alumina carrier is in the shape of a cylinder, a clover, a four-leaf clover or a gear, wherein the cylindrical strip The alumina carrier has a particle size of 1.2 to 1.6 mm and a length of 5 to 10 mm; the two-leaf pitch of the clover or the four-leaf clover is 1.1 to 1.8 mm and the length is 5 to 10 mm.
The high-load boron-modified hydrotreating catalyst according to claim 7 or 9, wherein in the step 3), when the boric acid aqueous solution is introduced into the furnace, the mass space velocity of the boric acid aqueous solution is 0.1 to 5.5 h -1 .
The high-load boron-modified hydrotreating catalyst according to claim 7 or 9, wherein the mass ratio of the aqueous boric acid solution is from 1.2 to 4.0 h -1 .
A method for preparing a high-load boron-modified hydrotreating catalyst according to claim 1, comprising the steps of:

1) Weighing the alumina precursor, the extrusion aid and the peptizer, mixing and rolling, extruding the strip to obtain an alumina extrudate, and then drying and roasting to obtain an alumina carrier;

2) preparing a boric acid solid into a boric acid aqueous solution having a mass fraction of 0.5 to 5.6%;

3) Weigh the alumina carrier obtained in step 1) in a hydrothermal treatment furnace, react at a pressure of 0-0.5 mpa and a temperature of 350-700 ° C for 0.5-9 h, and then pass the boric acid aqueous solution prepared in step 2). Into the furnace, obtaining a boron-modified alumina carrier;

4) weighing a metal salt containing two metals of Group VIB and Group VIII, and formulating the corresponding metal salt solution;

5) Weigh the boron-modified alumina carrier immersed step obtained in step 3) according to the metal oxide loading. The metal salt solution obtained in step 4) is impregnated; the impregnation method may be selected by equal volume impregnation, excessive impregnation, or two metal components may be co-impregnated or stepwise impregnated, preferably by equal volume co-impregnation.

6) The carrier impregnated in the step 5) is dried and calcined to obtain a hydrotreating catalyst.
The method for preparing a high-load boron-modified hydrotreating catalyst according to claim 14, wherein in the step 4), the metal cobalt is selected from the group consisting of cobalt nitrate, cobalt chloride, cobalt carbonyl and cobalt carbonate; It is selected from the group consisting of ammonium molybdate, molybdenum oxide and ammonium paramolybdate; the metal tungsten is selected from the group consisting of ammonium metatungstate and ammonium paratungstate; the metal nickel is selected from the group consisting of nickel nitrate, basic nickel carbonate and nickel carbonate.
The method for preparing a high-load boron-modified hydrotreating catalyst according to claim 14, wherein in the step 6), the drying temperature is 70 to 200 ° C, preferably 95 to 125 ° C, and the drying time is 1.0. ～24h, preferably 3 to 6h, calcination temperature is 250 to 600 ° C, preferably 400 to 510 ° C, and calcination time is 1 to 15 h, preferably 3 to 5 h.
The method for preparing a high-load boron-modified hydrotreating catalyst according to claim 14, wherein in the step 6), the drying temperature is 95 to 125 ° C, the drying time is 3 to 6 hours, and the baking temperature is 400. ~ 510 ° C, the baking time is 3 ~ 5h.