阅读说明：本技术 加氢催化剂及其制备方法和应用 (Hydrogenation catalyst, preparation method and application thereof ) 是由 姜艳 祁兴维 李顺新 李梁善 张勇 于 2019-10-15 设计创作，主要内容包括：本发明涉及加氢脱氮、脱硫领域,公开了一种加氢催化剂及其制备方法和应用。本发明的加氢催化剂的制备方法包括以下步骤,1)将纳米二氧化锆分散液与氧化铝载体进行第一接触,并将第一接触后的载体进行第一焙烧,得到改性氧化铝载体；2)将步骤1)得到的改性氧化铝载体与含有羟乙基乙二胺的活性组分溶液进行第二接触,并将第二接触后的载体进行第二焙烧。本发明制得的加氢催化剂其活性组分分散度与硫化度得到很好的匹配,产生的活性位多,提高了催化剂的本征活性,而且制备方法简单,生产成本低。(The invention relates to the field of hydrodenitrogenation and desulfurization, and discloses a hydrogenation catalyst, and a preparation method and application thereof. The preparation method of the hydrogenation catalyst comprises the following steps of 1) carrying out first contact on a nano zirconium dioxide dispersion liquid and an alumina carrier, and carrying out first roasting on the carrier after the first contact to obtain a modified alumina carrier; 2) carrying out second contact on the modified alumina carrier obtained in the step 1) and an active component solution containing hydroxyethyl ethylenediamine, and carrying out second roasting on the carrier after the second contact. The hydrogenation catalyst prepared by the invention has the advantages that the dispersion degree of the active components is well matched with the vulcanization degree, the generated active sites are more, the intrinsic activity of the catalyst is improved, the preparation method is simple, and the production cost is low.)

1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps,

1) carrying out first contact on the nano zirconium dioxide dispersion liquid and an alumina carrier, and carrying out first roasting on the carrier after the first contact to obtain a modified alumina carrier;

2) carrying out second contact on the modified alumina carrier obtained in the step 1) and an active component solution containing hydroxyethyl ethylenediamine, and carrying out second roasting on the carrier after the second contact.

2. The method according to claim 1, wherein the nano zirconium dioxide dispersion has a nano zirconium dioxide content of 2 to 50 wt.%;

preferably, the nano zirconium dioxide dispersion liquid also contains polyethylene glycol, and the content of the polyethylene glycol is 0.2-8 wt%;

preferably, the nano zirconium dioxide dispersion liquid contains nano zirconium dioxide, polyethylene glycol and water;

further preferably, the content of the nano zirconium dioxide is 1 to 50 weight percent, the content of the polyethylene glycol is 0.1 to 8 weight percent, and the balance is water;

preferably, the nano zirconium dioxide powder is added into an aqueous solution containing polyethylene glycol to be mixed under the action of ultrasonic waves, so as to obtain the nano zirconium dioxide dispersion liquid.

3. The method of claim 1, wherein the temperature of the first contacting is 10-40 ℃;

preferably, the nano zirconia dispersion is used in an amount of 1 to 10g in terms of nano zirconia with respect to 100g of the alumina carrier.

4. A process according to any one of claims 1 to 3, wherein the first contacted support is dried prior to the first calcination;

preferably, the conditions of the first firing include: the roasting temperature is 450-580 ℃, and the roasting time is 1-24 h.

5. The method as claimed in any one of claims 1 to 3, wherein the hydroxyethylethylenediamine is present in an amount of 1 to 3% by weight of the modified alumina support in the solution of active ingredient containing hydroxyethylethylenediamine.

6. The method of any one of claims 1-3, wherein the active components comprise a group VIII metal and a group VIB metal;

preferably, the group VIII metal is Co and/or Ni, and the group VIB metal is W and/or Mo;

preferably, the compound providing the active component is used in an amount such that the content of group VIII metal, calculated as oxide, is from 1 to 18% by weight and the content of group VIB metal, calculated as oxide, is from 10 to 30% by weight, based on the weight of the hydrogenation catalyst.

7. The method of any one of claims 1-3, wherein the temperature of the second contacting is 10-40 ℃;

preferably, before the second roasting, the second contacted carrier is dried;

preferably, the conditions of the second firing include: the roasting temperature is 300-600 ℃, and the roasting time is 1-24 h.

8. The method of any one of claims 1-3, wherein the first contacting and the second contacting are performed by impregnation, which is saturated impregnation, supersaturated impregnation, or vacuum impregnation.

9. A hydrogenation catalyst prepared by the process of any one of claims 1 to 8.

10. Use of the hydrogenation catalyst of claim 9 for hydrodenitrogenation and desulfurization.

Technical Field

The invention relates to the field of hydrodenitrogenation and desulfurization, and particularly relates to a hydrogenation catalyst, and a preparation method and application thereof.

Background

With the increasing deterioration degree and the increasing pace of clean fuel upgrading, the processing capacity of the hydrogenation device is continuously improved, and the corresponding hydrogenation processing technology is rapidly developed. At present, refinery enterprises are confronted with the fact that the content of impurities such as nitrogen, sulfur, oxygen, metal and the like in crude oil is increased continuously, and the impurities not only poison a catalyst in the subsequent treatment process, but also discharge a large amount of toxic and harmful gases such as sulfur, nitrogen oxides and the like, so that the health of human beings and the protection of the environment are endangered. The catalyst with high activity, low cost and good stability can ease the refining process conditions, reduce the hydrogen consumption and achieve the effects of saving energy and reducing consumption.

Most of hydrotreating catalysts are supported, metal oxides containing VIII family and VIB family in the periodic table are supported in refractory inorganic porous materials, and generally, alumina, silica, titanium dioxide, silicon carbide, boron oxide, zirconia and composite carriers formed by combining the alumina, the silica, the titanium dioxide, the silicon carbide, the boron oxide and the zirconia are adopted. Preparing a catalyst precursor through an isometric impregnation process or a supersaturation impregnation process, and preparing a finished catalyst through drying and roasting processes.

The purpose of hydrogenation pretreatment is to remove impurities such as nitrogen, sulfur, oxygen and the like in the raw oil, so that the quality and the quantity of the middle distillate oil are increased. For example, hydrocracking and hydro-reforming reactions require a pretreatment of the feedstock oil to remove impurities from the feedstock oil and to prevent catalyst poisoning. Therefore, the hydrotreating process is one of the indispensable and very important steps in the refinery process. It is known in the art that the acid property (acid strength and acid type) of the catalyst is one of the main factors influencing the activity of the catalyst, and the preparation of the catalyst with proper acidity can improve the reaction activity and prolong the operation period of the device, thereby achieving the purpose of reducing the operation cost of a refinery. The development of a catalyst with high activity, high stability, low cost, no pollution in the preparation process and more effective active sites is a bottleneck to be broken through in the field.

In the field, a great deal of work is done on the aspect of improving the activity of the hydrogenation catalyst, and a lot of documents report and obtain great results, thereby laying the foundation for the future research and development. For example: US 5338717 describes a process for the preparation of a hydrogenation catalyst which is impregnated with a heteropolyacid-containing metal impregnation solution, the support being a refractory porous oxide material and the finished catalyst not requiring a calcination process. However, the method has a disadvantage that drying under vacuum condition before vulcanization is difficult to be carried out industrially.

US6281333A discloses a method for preparing a hydroprocessing catalyst. The carrier loads active metal impregnation liquid containing organic volatile components, and the catalyst is obtained without roasting. In the preparation process of the catalyst, the organic auxiliary agent is added into the impregnation liquid, so that the viscosity of the impregnation liquid is increased, the dispersion of the active metal on the surface of the carrier is not facilitated, the impregnated catalyst particles are easy to stick together and have a blocking phenomenon, and the metal precipitation phenomenon exists on the surface of the dried catalyst, so that the high dispersion of the active component on the surface of the carrier is influenced, and the activity of the catalyst is not influenced.

CN101940929A discloses a preparation method of a hydrotreating catalyst, which adopts the impregnation liquid prepared by the conventional method to prepare the catalyst. The immersion liquid has strong acidity, the specific surface area and the pore volume of the catalyst are seriously damaged, and after the catalyst is roasted at high temperature, active components are easy to aggregate on the surface of a carrier, so that the reaction activity is influenced.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a hydrogenation catalyst, a preparation method and application thereof. The hydrogenation catalyst prepared by the invention has the advantages that the dispersion degree of the active components is well matched with the vulcanization degree, the generated active sites are more, the intrinsic activity of the catalyst is improved, the preparation method is simple, and the production cost is low.

According to a first aspect of the present invention, there is provided a process for the preparation of a hydrogenation catalyst, the process comprising the steps of,

1) carrying out first contact on the nano zirconium dioxide dispersion liquid and an alumina carrier, and carrying out first roasting on the carrier after the first contact to obtain a modified alumina carrier;

2) carrying out second contact on the modified alumina carrier obtained in the step 1) and an active component solution containing hydroxyethyl ethylenediamine, and carrying out second roasting on the carrier after the second contact.

Preferably, the nano zirconium dioxide dispersion has a nano zirconium dioxide content of 2 to 50 wt%.

Preferably, the nano zirconium dioxide dispersion liquid also contains polyethylene glycol, and the content of the polyethylene glycol is 0.2-8 wt%.

Preferably, the nano zirconium dioxide dispersion liquid contains nano zirconium dioxide, polyethylene glycol and water;

further preferably, the content of the nano zirconium dioxide is 1 to 50 weight percent, the content of the polyethylene glycol is 0.1 to 8 weight percent, and the balance is water.

Preferably, the nano zirconium dioxide powder is added into an aqueous solution containing polyethylene glycol to be mixed under the action of ultrasonic waves, so as to obtain the nano zirconium dioxide dispersion liquid.

Preferably, the temperature of the first contact is 10-40 ℃.

Preferably, the nano zirconia dispersion is used in an amount of 1 to 10g in terms of nano zirconia with respect to 100g of the alumina carrier.

Preferably, the first contacted support is dried prior to the first calcination.

Preferably, the conditions of the first firing include: the roasting temperature is 450-580 ℃, and the roasting time is 1-24 h.

Preferably, in the active component solution containing the hydroxyethyl ethylene diamine, the amount of the hydroxyethyl ethylene diamine is 1-3 wt% of the modified alumina carrier.

Preferably, the active components include a group VIII metal and a group VIB metal.

Preferably, the group VIII metal is Co and/or Ni and the group VIB metal is W and/or Mo.

Preferably, the compound providing the active component is used in an amount such that the content of group VIII metal, calculated as oxide, is from 1 to 18% by weight and the content of group VIB metal, calculated as oxide, is from 10 to 30% by weight, based on the weight of the hydrogenation catalyst.

Preferably, the temperature of the second contacting is 10-40 ℃.

Preferably, the second contacted support is dried prior to said second calcination.

Preferably, the conditions of the second firing include: the roasting temperature is 300-600 ℃, and the roasting time is 1-24 h.

Preferably, the first contact and the second contact are carried out by means of impregnation, and the impregnation is saturated impregnation, supersaturated impregnation or vacuum impregnation.

According to a second aspect of the present invention, there is provided a hydrogenation catalyst prepared by the preparation method of the present invention.

According to a third aspect of the present invention, there is provided the use of the hydrogenation catalyst of the present invention in hydrodenitrogenation, desulfurization.

According to the invention, the alumina carrier is soaked in the nano zirconium dioxide dispersion liquid and then is roasted to form Al-O-Zr bonds, zirconium can be uniformly dispersed on the surface of the alumina, the acid property of the modified alumina carrier is better improved, the increasing range of the content of the medium strong acid and the content of the B acid is larger, the increase of the content of the medium strong acid is beneficial to improving the intrinsic activity of the catalyst, and the increase of the content of the B acid is beneficial to the breakage of the C-N bonds in the reaction process; in addition, hydroxyethyl ethylenediamine and nickel are added into the active component solution to form a stable complex, so that nickel vulcanization is delayed, and the molybdenum vulcanization degree is increased; in addition, the hydroxyethyl ethylenediamine is added into the active component solution, so that the pH value of the active component solution is increased, the corrosion effect of the active component solution on the carrier can be weakened, the specific surface area of the obtained hydrogenation catalyst is increased, the number of generated active sites is increased, and the comprehensive performance of the hydrogenation catalyst is better improved.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a process for the preparation of a hydrogenation catalyst, the process comprising the steps of,

1) carrying out first contact on the nano zirconium dioxide dispersion liquid and an alumina carrier, and carrying out first roasting on the carrier after the first contact to obtain a modified alumina carrier;

2) carrying out second contact on the modified alumina carrier obtained in the step 1) and an active component solution containing hydroxyethyl ethylenediamine, and carrying out second roasting on the carrier after the second contact.

According to the present invention, the nano zirconia content in the nano zirconia dispersion is preferably 1 to 50% by weight, preferably 2 to 50% by weight, more preferably 8 to 30% by weight, and still more preferably 8 to 20% by weight.

According to the present invention, it is preferable that the nano zirconium dioxide dispersion further contains polyethylene glycol. The content of the polyethylene glycol may be, for example, 0.1 to 8% by weight, preferably 0.2 to 8% by weight, more preferably 0.8 to 5% by weight, and still more preferably 0.5 to 2% by weight.

According to the present invention, preferably, the nano zirconium dioxide dispersion liquid contains nano zirconium dioxide, polyethylene glycol and water; further preferably, the nano zirconium dioxide dispersion liquid consists of nano zirconium dioxide, polyethylene glycol and water, wherein the content of the nano zirconium dioxide is 1-50 wt%, the content of the polyethylene glycol is 0.2-8 wt%, and the balance is water.

According to the invention, the particle size of the nano zirconium dioxide is in a nano level, preferably, the particle size of the nano zirconium dioxide is 10-100nm, and more preferably 10-50 nm.

According to the present invention, the nano zirconium dioxide dispersion may be prepared by various methods used in the art for preparing nano zirconium dioxide dispersions, and in a preferred embodiment of the present invention, the nano zirconium dioxide dispersion is obtained by adding the nano zirconium dioxide powder to an aqueous solution containing polyethylene glycol under the action of ultrasonic waves for mixing.

The power of the ultrasonic wave may be 2 to 80Hz, preferably 15 to 50 Hz. And (3) uniformly dispersing the nano zirconium dioxide within the ultrasonic time.

According to the invention, the nano zirconium dioxide dispersion liquid is prepared under the action of ultrasonic waves, so that the activity of the obtained hydrogenation catalyst can be further remarkably improved.

According to the present invention, the alumina carrier is not particularly limited, and may be an alumina carrier generally used in the art. The alumina carrier can be prepared by the conventional method in the field, for example, the alumina dry glue powder can be kneaded, rolled, formed, dried and roasted to prepare the carrier. Adding extrusion aid, binder, peptizer and other conventional forming aids in the kneading process. The drying conditions include: the drying temperature is 40-350 ℃, preferably 100-150 ℃, and the drying time is 0.5-24h, preferably 4-10 h. The roasting conditions comprise: the roasting temperature is 350-650 ℃, preferably 450-580 ℃, and the roasting time is 0.5-24h, preferably 8-15h, and more preferably 6-10 h. The drying and roasting atmosphere is air atmosphere, and the shape of the carrier can be five-tooth sphere or strip (clover or clover special-shaped strip) and the like. The shape of the carrier can be selected according to specific needs, and is preferably strip-shaped, and the size of the carrier can be selected to be different according to requirements.

According to the invention, the first contact is preferably carried out by means of impregnation, which is saturated impregnation, supersaturated impregnation or vacuum impregnation, preferably saturated impregnation.

Preferably, the first contact temperature is 10-40 ℃ and the contact time is typically 1-15 hours.

According to the present invention, the amount of the nano zirconia dispersion in terms of nano zirconia is preferably 1 to 10g, preferably 1.5 to 8g, more preferably 2 to 5g, relative to 100g of the alumina carrier.

According to the present invention, when polyethylene glycol is further contained in the nano zirconium dioxide dispersion, the amount of the polyethylene glycol is 0.1 to 1g, more preferably 0.1 to 0.5g, and still more preferably 0.15 to 0.3g, based on 100g of the alumina carrier.

According to the present invention, it is preferable that the support after the first contact is dried before the first firing is performed. The drying conditions are not particularly limited, and drying may be carried out, for example, at 40 to 200 ℃ and preferably 70 to 150 ℃ for 1 to 10 hours.

According to the present invention, preferably, the conditions of the first firing include: the roasting temperature is 450-580 ℃, and the roasting time is 1-24 h; more preferably, the conditions of the first firing include: the roasting temperature is 500-560 ℃, and the roasting time is 3-10 h.

According to the invention, after the modified alumina carrier is obtained, the obtained modified alumina carrier is subjected to second contact with an active component solution containing hydroxyethyl ethylenediamine, and the carrier after the second contact is subjected to second roasting.

According to the invention, preferably, in the active component solution containing the hydroxyethyl ethylenediamine, the amount of the hydroxyethyl ethylenediamine is 1 to 3 wt%, more preferably 1 to 2 wt% of the modified alumina carrier.

According to the invention, the hydrogenation catalyst takes the modified alumina as a carrier and metals in a VIII family and a VIB family as active metal components, namely, the active components comprise metals in the VIII family and metals in the VIB family. Preferably, the group VIII metal is Co and/or Ni and the group VIB metal is W and/or Mo. In addition, according to the use requirement of the hydrogenation catalyst, a proper auxiliary agent can be added, and the auxiliary agent comprises one or more of fluorine, phosphorus, boron, zinc, zirconium and the like.

In the active component solution containing hydroxyethyl ethylenediamine, a compound of active metal is provided, tungsten is mainly selected from one or two of ammonium metatungstate and ammonium tetrathiotungstate, molybdenum is mainly selected from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate and ammonium paramolybdate, nickel is mainly selected from one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride and nickel acetate, and cobalt is mainly selected from one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate and cobalt chlorate.

In the present invention, it is preferred that the compound providing the active component is used in an amount such that the content of the group VIII metal calculated as an oxide is 1 to 18% by weight and the content of the group VIB metal calculated as an oxide is 10 to 30% by weight based on the weight of the hydrogenation catalyst; more preferably, the compound providing the active component is used in an amount such that the content of group VIII metal on oxide basis is from 4 to 12% by weight and the content of group VIB metal on oxide basis is from 18 to 25% by weight, based on the weight of the hydrogenation catalyst.

According to the invention, the second contact is preferably carried out by means of impregnation, which is saturated impregnation, supersaturated impregnation or vacuum impregnation, preferably saturated impregnation.

Preferably, the temperature of the second contact is 10 to 40 ℃ and the contact time is generally 1 to 15 hours.

According to the present invention, it is preferable that the second contacted support is dried before the second calcination. The drying conditions are not particularly limited, and drying may be carried out, for example, at 40 to 200 ℃ and preferably 70 to 150 ℃ for 1 to 10 hours.

According to the present invention, preferably, the conditions of the second firing include: the roasting temperature is 300-600 ℃, and the roasting time is 1-24 h; more preferably, the conditions of the second firing include: the roasting temperature is 380-450 ℃, and the roasting time is 1-10 h.

According to a second aspect of the present invention, there is provided a hydrogenation catalyst prepared by the preparation method of the present invention.

According to a third aspect of the present invention, there is provided the use of the hydrogenation catalyst of the present invention in hydrodenitrogenation, desulfurization.

The hydrogenation catalyst is particularly suitable for hydrodenitrogenation and desulfurization of heavy distillate oil.

The conditions for using the hydrogenation catalyst of the present invention are not particularly limited, and may be various conditions generally used in the art for hydrogenation catalysts, and may include, for example: the reaction temperature is 300-380 ℃, preferably 330-375 ℃, the reaction pressure is 4-12MPa, preferably 5-10MPa, the hydrogen-oil ratio is 600: 1-1200: 1, preferably 750: 1-1000: 1.

the present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples. In the present invention,% is a weight unless otherwise specified.

Preparation example 1

Preparing a catalyst precursor by adopting pseudo-boehmite dry rubber powder, weighing 300g of alumina dry rubber powder, adding 4g of sesbania powder, uniformly mixing, and adding an acid solution, wherein the acid solution contains 11.26g of nitric acid, the concentration of the nitric acid is 2 wt%, 4g of citric acid and the balance of deionized water. Rolling for 15-25 minutes, extruding strips by using a clover orifice plate with the diameter of 1.5mm, drying for 10 hours at 120 ℃, and roasting for 5 hours at 550 ℃ to obtain a catalyst carrier, namely Z, wherein the properties of the catalyst carrier are as follows: the pore volume is 0.80ml/g, the specific surface area is 350m²/g。

Example 1

Preparing a mixed solution of nano zirconium dioxide and polyethylene glycol, wherein the mass content of the nano zirconium dioxide in the mixed solution is 8%, the mass content of the polyethylene glycol is 0.6%, the power of ultrasonic waves is 30Hz, and the particle size of the nano titanium dioxide is 15 nm; the solution was numbered A.

Weighing 100g of carrier Z, weighing 30g of solution A, diluting to 88ml, impregnating the carrier Z, drying the impregnated sample at 120 ℃ for 3h, and roasting at 550 ℃ for 5h to obtain the modified alumina GZ-1.

Weighing 100g of modified carrier GZ-1, and soaking Mo, Ni and P in soaking solution containing hydroxyethyl ethylenediamine, wherein the soaking solution is MoO₃The content of (A) is 88.5g/100ml, the NiO content is 15g/100ml, the P content is 2.3g/100ml, the weight of the hydroxyethyl ethylenediamine is 1.2 percent of the weight of the modified carrier, and the immersed sample is aged for 8 hours at room temperatureThen, the catalyst C-1 is obtained by drying at 120 ℃ for 3 hours and calcining at 430 ℃ for 3 hours. The physicochemical properties of the catalyst are shown in Table 1.

Example 2

(1) Preparing a mixed solution of nano zirconium dioxide and polyethylene glycol, wherein the mass content of the nano zirconium dioxide in the mixed solution is 10%, the mass content of the polyethylene glycol is 0.8%, the power of ultrasonic waves is 32Hz, and the particle size of the nano titanium dioxide is 25 nm; the solution was numbered B.

Weighing 100g of carrier Z, weighing 24g of solution B, diluting to 88ml, impregnating the carrier Z, drying the impregnated sample at 120 ℃ for 3h, and roasting at 550 ℃ for 5h to obtain the modified alumina GZ-2.

Weighing 100g of modified carrier GZ-2, and soaking Mo, Ni and P in soaking solution containing hydroxyethyl ethylenediamine, wherein the soaking solution is MoO₃The content of (b) was 86.5g/100ml, the NiO content was 14.5g/100ml, the P content was 2.5g/100ml, and hydroxyethylethylenediamine was 1.6% by weight of the modified support, and the impregnated sample was aged at room temperature for 10 hours, dried at 120 ℃ for 5 hours, and calcined at 430 ℃ for 5 hours to obtain catalyst C-2. The physicochemical properties of the catalyst are shown in Table 1.

Example 3

(1) Preparing a mixed solution of nano zirconium dioxide and polyethylene glycol, wherein the mass content of the nano zirconium dioxide in the mixed solution is 12%, the mass content of the polyethylene glycol is 1.2%, the power of ultrasonic waves is 40Hz, and the particle size of the nano titanium dioxide is 25 nm; the solution was numbered C.

Weighing 100g of carrier Z, weighing solution C15g, diluting to 88ml, impregnating, drying the impregnated sample at 120 ℃ for 3h, and roasting at 550 ℃ for 5h to obtain modified alumina GZ-3.

Weighing 100g of modified carrier GZ-3, and soaking Mo, Ni and P in soaking solution containing hydroxyethyl ethylenediamine, wherein the soaking solution is MoO₃The content of (b) is 85.5g/100ml, the NiO content is 15.2g/100ml, the P content is 2.2g/100ml, the weight of the hydroxyethyl ethylenediamine is 1.8% of the weight of the modified carrier, the impregnated sample is aged at room temperature for 10 hours, dried at 120 ℃ for 5 hours, and calcined at 430 ℃ for 5 hours, and the catalyst C-3 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

Example 4

(1) Preparing a mixed solution of nano zirconium dioxide and polyethylene glycol, wherein the mass content of the nano zirconium dioxide in the mixed solution is 16%, the mass content of the polyethylene glycol is 1.2%, the power of ultrasonic waves is 40Hz, and the particle size of the nano titanium dioxide is 35 nm; the solution was numbered D.

Weighing 100g of carrier Z, weighing solution D25g, diluting to 88ml, impregnating, drying the impregnated sample at 120 ℃ for 4h, and roasting at 550 ℃ for 6 h to obtain modified alumina GZ-4.

Weighing 100g of modified carrier GZ-4, and soaking Mo, Ni and P in soaking solution containing hydroxyethyl ethylenediamine, wherein the soaking solution is MoO₃The content of (b) is 83.5g/100ml, the NiO content is 14.2g/100ml, the P content is 2.2g/100ml, the weight of the hydroxyethyl ethylenediamine is 2.0% of the weight of the modified carrier, the impregnated sample is aged at room temperature for 10 hours, dried at 120 ℃ for 5 hours, and calcined at 430 ℃ for 5 hours, and the catalyst C-4 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

Example 5

(1) Preparing a mixed solution of nano zirconium dioxide and polyethylene glycol, wherein the mass content of the nano zirconium dioxide in the mixed solution is 18%, the mass content of the polyethylene glycol is 1.4%, the power of ultrasonic waves is 42Hz, and the particle size of the nano titanium dioxide is 40 nm; the solution was numbered E.

Weighing 100g of carrier Z, weighing solution E20g, diluting to 88ml, impregnating, drying the impregnated sample at 120 ℃ for 4h, and roasting at 550 ℃ for 6 h to obtain modified alumina GZ-5.

Weighing 100g of modified carrier GZ-5, and soaking Mo, Ni and P in soaking solution containing hydroxyethyl ethylenediamine, wherein the soaking solution is MoO₃The content of (b) is 83.5g/100ml, the NiO content is 14.2g/100ml, the P content is 2.2g/100ml, the weight of the hydroxyethyl ethylenediamine is 2.0% of the weight of the modified carrier, the impregnated sample is aged at room temperature for 10 hours, dried at 120 ℃ for 5 hours, and calcined at 430 ℃ for 5 hours, and the catalyst C-5 is obtained. The physicochemical properties of the catalyst are shown in Table 1.

Example 6

A mixed solution of nano zirconium dioxide and polyethylene glycol was prepared by following the procedure of example 1 except that mixing was performed by stirring to obtain a solution F.

Weighing 100g of carrier Z, weighing 30g of solution F, diluting to 88ml, impregnating the carrier Z, drying the impregnated sample at 120 ℃ for 3h, and roasting at 550 ℃ for 5h to obtain the modified alumina GZ-6.

Soaking the modified alumina GZ-6 in soaking liquid containing Mo, Ni and P, wherein the soaking liquid is MoO₃The content of (b) was 89.5g/100ml, the NiO content was 13.5g/100ml, and the P content was 2.2g/100 ml. The impregnated sample was aged at room temperature for 10 hours, dried at 120 ℃ for 3 hours in an air atmosphere, and then calcined at 480 ℃ for 3 hours to obtain catalyst C-6. The physicochemical properties of the catalyst are shown in Table 1.

Comparative example 1

Weighing a proper amount of carrier Z, and carrying out equal-volume impregnation on the carrier Z by using impregnation liquid containing Mo, Ni and P, wherein the impregnation liquid consists of MoO₃The catalyst C-7 was obtained by impregnating the catalyst (B) with the content of (C) of 88.5g/100ml, the content of NiO of 14.6g/100ml and the content of P of 2.3g/100ml, aging the resultant for 10 hours at room temperature, drying the resultant in an air atmosphere at 115 ℃ for 3 hours, and calcining the resultant at 480 ℃ for 5 hours. The physicochemical properties of the catalyst are shown in Table 1.

Comparative example 2

Weighing proper amount of carrier Z, and soaking in soaking solution containing MO, Ni and hydroxyethyl ethylenediamine, wherein the soaking solution consists of MoO₃The content of (b) is 88.5g/100ml, the NiO content is 15g/100ml, the amount of the hydroxyethyl ethylenediamine is 2.5 percent of the weight of the carrier, the catalyst C-8 is obtained after aging for 10 hours at room temperature by an equal volume impregnation method and drying for 3 hours at 120 ℃ in an air atmosphere. The physicochemical properties of the catalyst are shown in Table 1.

TABLE 1

Catalyst and process for preparing same	C-1	C-2	C-3	C-4	C-5	C-6	C-7	C-8
									Medium strong acid content%	32.34	31.98	32.56	32.09	32.61	25.52	21.36	23.35
B acid mmol/L	0.076	0.081	0.086	0.079	0.082	0.048	0.042	0.045

Test example 1

For the hydrogenation catalysts obtained in examples 1 to 6 and comparative examples 1 to 2, activity evaluation tests were carried out in a 50ml small hydrogenation reactor, and the used starting material was catalytic diesel oil, the properties of which are shown in Table 2. The catalyst is pre-sulfurized before use, the sulfurized oil is straight-run kerosene, 5 wt% of DMDS (dimethyl disulfide) is added, and after pre-sulfurization, raw oil is directly introduced for test reaction. The presulfiding and testing conditions are shown in Table 3, the initial activity evaluation results of the catalyst are shown in Table 4, and the 1200h activity evaluation results of the catalyst are shown in Table 5.

TABLE 2

Raw oil name	Catalytic diesel fuel
		Sulfur content, wt.%	1028
Nitrogen content,. mu.g/g	855

TABLE 3

	Conditions of prevulcanization	Test conditions
			Pressure, MPa	5.5	5.5
Temperature, C	320	340
			LHSV，h-1	1.0	1.0
Volume ratio of hydrogen to oil	1000：1	1000：1

TABLE 4

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7	C-8
									Relative denitrification activity,%	151	148	144	153	153	126	100	123
Relative desulfurization activity of%	146	150	143	148	151	123	100	125

Note: c-7 is a reference catalyst

The results of evaluating the initial activity of the C-1 to C-8 catalysts are shown in Table 4. As can be seen from the data in Table 4, the activity of the catalyst prepared by the process of the present invention is significantly higher than that of the catalyst prepared by the comparative example.

TABLE 5

Catalyst numbering	C-1	C-2	C-3	C-4	C-5	C-6	C-7	C-8
									Relative denitrification activity,%	148	143	141	153	151	131	100	121
Relative desulfurization activity of%	142	142	140	142	146	138	100	125

Note: c-7 is a reference catalyst

The 1200h activity evaluation results of the C-1-C-8 catalysts are shown in Table 5, and the data in Table 5 show that the catalysts prepared by the method have good stability and are beneficial to long-period operation.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.