CN111957318A - Hydrotreating catalyst and preparation method and application thereof - Google Patents

Abstract

The invention discloses a hydrotreating catalyst, which comprises a metal active component and a carrier for loading the metal active component, wherein the metal active component comprises WO₃NiO and MoO₃The structure of the carrier comprises MgO and a metal oxide matrix containing the pore channels, wherein the MgO is uniformly dispersed in the metal oxide matrix containing the pore channels, and at least most part of the MgO is uniformly dispersed on the surface of the pore channels of the metal oxide matrix containing the pore channels. The hydrotreating catalyst has high desulfurizing, denitrifying and hydrogenating saturation performance, and is suitable for hydrotreating process of various kinds of distillate oil, especially for hydrorefining process with desulfurizing, hydrogenating denitrifying and hydrogenating saturation. The invention also discloses a preparation method and application of the hydrotreating catalyst.

Description

A kind of hydrotreating catalyst and its preparation method and application

technical field

The present invention relates to the technical field of catalysis. More specifically, it relates to a hydrotreating catalyst and its preparation method and application.

Background technique

With the intensification of the severe deterioration of crude oil in the world and the continuous upgrading of oil quality standards, in the face of the gradual popularization of the production of national VI standard oil products, while maintaining the processing and production of ultra-low sulfur gasoline and diesel (<10ppm), oil refining enterprises, It is also necessary to further reduce the content of unsaturated hydrocarbons such as olefins, aromatic hydrocarbons and benzene in oil products. For the refining industry, the improvement of hydrogenation catalyst activity is undoubtedly the most economical way to ensure that multiple product indicators meet environmental protection indicators.

From the perspective of the reaction mechanism of the hydrogenation process, the higher the sulfurization degree of the catalyst, the more active phases in the multilayer stack, the more Type II active phases, and the more active centers in the corners of the active phase, the more It is beneficial to hydrodesulfurization, hydrodenitrogenation and hydrosaturation reactions. Commercially available hydrogenation catalysts are generally in an oxidized state prior to loading into the reactor and require sulfided to obtain a truly catalytically active sulfided state prior to use. The active metal Mo/W in traditional oxidation state catalysts is prone to strong interaction with alumina support (SMSI), which will hinder the formation of Type II active phase with high lamellae. If this SMSI can be effectively controlled, there are It is beneficial to improve the desulfurization, denitrification and hydrogenation saturation performance of the catalyst as a whole.

CN101092573A The reactor is charged with hydrogenation protection agent, hydrotreating catalyst I, hydrotreating catalyst II and optional hydrotreating catalyst III for contact. This scheme gives full play to the advantages of their respective catalysts in different desulfurization stages, and can obtain low-sulfur diesel fuel that meets Euro III and IV standards. Due to the demand for higher quality diesel, the activity of the catalyst needs to be further improved.

CN101591566A provides a catalyst gradation scheme. The reactor is divided into four reaction zones, and hydrogenation protection agent, hydrotreating catalyst I containing active metal Co-Mo, hydrotreating catalyst I and hydrotreating catalyst II are sequentially loaded A mixture of , a hydrofinishing catalyst II containing the active metal nickel-tungsten. The system improves the overall catalyst activity through the synergistic effect between the individual catalysts. However, this system cannot produce diesel with lower sulfur content at lower reaction temperatures.

The above-mentioned packing method is relatively complicated in the actual use process, which is not conducive to the regeneration of the catalyst. With the tightening of environmental protection standards and the decline of diesel feedstock quality, more ingenious catalyst preparation methods are required to obtain highly active hydrogenation catalysts.

CN108236965A patent discloses a modified hydrodesulfurization catalyst, which adopts a molecular sieve/alumina composite carrier impregnated with metal Mg and mechanically mixed with citric acid. Mg ²⁺ replaces the tetrahedral Al ³⁺ in the alumina spinel structure, which promotes the distribution of active components on the surface of the support, and promotes the sulfidation of Mo species. The addition of Mg is beneficial to reduce SMSI and make the catalyst exhibit higher performance. the reactivity.

However, the researchers of the present invention found in the research that in the above-mentioned existing research methods, Mg can actually play a limited role, so that the effect on improving the catalytic performance of the catalyst is also limited.

SUMMARY OF THE INVENTION

One object of the present invention is to provide a hydrotreating catalyst, which has high desulfurization, denitrification, and hydrosaturation performance at the same time, is suitable for various distillate hydrotreating processes, and is especially suitable for desulfurization, denitrification, and hydrogenation. Hydrorefining process for the purpose of hydrodenitrogenation and hydrosaturation.

The second object of the present invention is to provide a method for preparing a hydrotreating catalyst.

The third object of the present invention is to provide the application of a new hydrotreating catalyst.

For reaching above-mentioned first purpose, the present invention adopts following technical scheme:

A hydrotreating catalyst, comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component comprises WO ₃ , NiO and MoO ₃ , and the structure of the carrier comprises MgO and a A metal oxide matrix with channels, the MgO is uniformly dispersed in the metal oxide matrix containing channels, and at least most of the MgO is uniformly dispersed on the surface of the channels of the metal oxide matrix containing channels.

Optionally, based on the total weight of the catalyst, the catalyst comprises: 5-40 wt% of WO ₃ , 5-30 wt % of MoO ₃ , 0.1-15 wt % of NiO, and 0.1-5 wt % of MgO.

Optionally, based on the total weight of the catalyst, the catalyst comprises: 10-25 wt% of WO ₃ , 5-20 wt % of MoO ₃ , 1-10 wt % of NiO, and 0.5-3 wt % of MgO.

Optionally, the metal oxide matrix containing pores is selected from one or more of alumina and alumina-silica; preferably, the alumina is γ-Al ₂ O ₃ .

Optionally, the hydrotreating catalyst further comprises organic matter impregnated in the metal active component and/or the carrier.

Optionally, the organic matter is oxygen-containing organic matter or nitrogen-containing organic matter.

Optionally, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids.

Optionally, the nitrogen-containing organic substance is an organic amine.

Optionally, in the hydrotreating catalyst, the molar ratio of organic matter to Ni is 0.1-8, more preferably 0.2-3.

In order to achieve above-mentioned second purpose, the present invention adopts following technical scheme:

The preparation method of hydrotreating catalyst, comprises the steps:

The carrier is uniformly mixed with a solution of Ni-containing compound, Mo-containing compound and W-containing compound to obtain mixture A, which is dried or calcined to obtain the hydrotreating catalyst.

Optionally, the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate, and ethyl ammonium metatungstate.

Optionally, the Ni-containing compound is a water-soluble Ni salt, preferably one or more of Ni nitrate, acetate, carbonate, and basic carbonate.

Optionally, the Mo-containing compound is selected from one or more of molybdenum trioxide, ammonium paramolybdate and sodium molybdate.

Optionally, the mixing method is co-impregnation or step-by-step impregnation.

Optionally, the drying or roasting temperature is 100-600°C, and the time is 3-24 hours.

Optionally, the preparation of the carrier comprises the steps:

Mixing the powder of the metal oxide matrix containing pores with the Mg solution and the organic solvent uniformly, and then carrying out the secondary drying of the obtained mixture and calcining in a non-oxidizing atmosphere to obtain a product B;

The product B is then mixed with a binder, shaped, dried and calcined to obtain the carrier.

Optionally, the Mg solution is selected from one or more of aqueous solutions of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, and magnesium chloride.

Optionally, the organic solvent is selected from one or more of water-soluble lower alcohols, lower carbonic acids, lower amines and sugars.

Optionally, the water-soluble low-carbon alcohol is selected from ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol, diethylene glycol, butylene glycol, and sugar alcohol.

Optionally, the low carbonic acid is selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid, and sugar acid.

Optionally, the low-carbon amine is selected from sugar amines; the sugar is selected from sucrose, triose, pentose, hexose, and glycoside.

Optionally, the binder is an alumina precursor.

Optionally, the alumina precursor is selected from one or more of pseudo-boehmite, boehmite, boehmite, gibbsite, amorphous alumina, and pyrexite.

Optionally, the non-oxidizing atmosphere is an inert atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere.

Optionally, the roasting temperature of the roasting in a non-oxidizing atmosphere is 150-350° C., and the roasting time is 2-8 hours.

Optionally, the mass ratio of the organic solvent to the pore-containing metal oxide matrix is 10-50 wt%.

Optionally, the content of carbon in the product B is 1-20 wt %, and the content of Mg is 0.5-20 wt %.

Optionally, the mass ratio of the product B to the binder is 10-90 wt %.

Optionally, the calcination conditions for the product B and the binder mixture after molding and drying are: calcination temperature of 400-800° C. and calcination time of 2-10 hours.

Optionally, the powder of the metal oxide matrix containing pores and the Mg solution and the organic solvent are uniformly mixed by mixing the Mg-containing solution and the organic solvent with the powder of the metal oxide matrix containing pores at the same time, or The Mg solution is mixed with the metal oxide matrix powder containing pores, and the resultant is dried and then mixed with an organic solvent.

Optionally, the preparation method further includes the step of adding organic matter to the mixture A.

In order to achieve the above-mentioned third object, the present invention also provides the application of the above-mentioned hydrotreating catalyst in the hydro-refining process of distillate or crude oil secondary processed products.

The beneficial effects of the present invention are as follows:

According to an object of the present invention, the hydrotreating catalyst provided in the present invention adopts the oxide of Ni-Mo-W as the metal active component, combined with at least most of the metal oxide matrix containing pores uniformly dispersed in the carrier. The MgO on the surface of the pores effectively adjusts the desulfurization, denitrification, and hydrogenation saturation performance of the catalyst. According to another object of the present invention, in the preparation method of the hydrotreating catalyst provided by the present invention, the organic solvent protects the Mg well, overcomes the shortcoming that the Mg cannot be fully and uniformly distributed due to the capillary condensation phenomenon, thereby making the Mg more More and more uniform dispersion is exposed on the pore surface of the matrix, which is conducive to the interaction between Mg and the carrier and active metal components, and is conducive to the formation of a more reasonable pore structure, which is more conducive to the generation of sulfided active phases. It is beneficial to improve the low temperature activity of the catalyst. In addition, the organic solvent also has a protective effect on the pores of the matrix, which can protect the pore structure during the preparation of the carrier, avoid the blockage of pores with smaller pore sizes, and ultimately improve the overall performance of the catalyst. According to another object of the present invention, the hydrotreating catalyst provided by the present invention can be well used in the hydrorefining reaction of catalytic distillate or secondary processed products, and is especially suitable for the hydrodesulfurization and hydrodesulfurization of middle distillate oil. Nitrogen, hydrogenation saturation process.

Detailed ways

In order to illustrate the present invention more clearly, the present invention will be further described below with reference to the preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

In one aspect, an embodiment of the present invention provides a hydrotreating catalyst comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component comprises WO ₃ , NiO and MoO ₃ , the structure of the carrier includes MgO and a metal oxide matrix containing channels, the MgO is uniformly dispersed in the metal oxide matrix containing channels, and at least most of the MgO is uniformly dispersed in the metal oxide matrix containing channels pore surface.

During the research process, the inventors of the present invention found that in the current hydrotreating catalysts containing Mg, the main reason why Mg cannot be sufficiently used to improve the catalytic activity of the hydrotreating catalysts is that most of the Mg elements are generally used in the carrier forming process at present. It is added into the carrier or introduced by dipping after the carrier is formed. In the former, since Mg is fully mixed with pseudo-boehmite, the primary particles of pseudo-boehmite are transformed into secondary particles after the calcination process. Adjusting the acidity and alkalinity of the carrier is limited, and the Mg that interacts with the active metal is limited, which reduces the utilization rate of Mg. The latter, due to the process of impregnation and drying, during the drying process, with the evaporation of the solvent, the Mg solution in the pores of the shaped carrier is inevitably separated into many discontinuous segments, resulting in uneven distribution of Mg elements and reducing Mg elements to adjust the carrier. acid effect. In the hydrotreating catalyst of the present invention, the anti-coking performance of the obtained catalyst can be well improved by dispersing most of the MgO evenly on the surface of the pores of the metal oxide matrix containing pores. In the catalyst structure, it is uniformly dispersed on the surface of the pores of the substrate The MgO combined with the metal active components including W, Mo and Ni effectively enhanced the catalytic performance of the catalyst.

It can be understood that, in this embodiment, "at least most of" includes two concepts of "mostly" and "all". Among them, "mostly" is the content of more than 50 wt%.

In a preferred example, based on the total weight of the catalyst, the catalyst contains: _5-40wt % of WO3, 5-30wt% of MoO3, _0.1-15wt % of NiO, and 0.1-5wt% of MgO.

In another preferred example, based on the total weight of the catalyst, the catalyst contains: 10-25 wt% of WO ₃ , 5-20 wt % of MoO ₃ , 1-10 wt % of NiO, and 0.5-3 wt % of MgO.

In a preferred example, the pore-containing metal oxide matrix is selected from one or more of alumina and alumina-silica. Further, an exemplary metal oxide matrix containing pores is γ-Al ₂ O ₃ , and the obtained hydrotreating catalyst has better catalytic effect at this time.

In some examples, the metal active component and/or carrier can also be impregnated with organics. Through the complex impregnation technology, the active metal vulcanization is promoted, and the active metal main agent and the auxiliary agent are simultaneously vulcanized, so that the organic matter of the catalyst will be decomposed during the vulcanization process and the reaction process, which is conducive to the formation of highly active active phase and further enhances the catalyst activity. . Exemplary organic substances are oxygen-containing organic substances or nitrogen-containing organic substances; the oxygen-containing organic substances are selected from one or more of organic alcohols and organic acids; the nitrogen-containing organic substances are organic amines. In addition, in the hydrotreating catalyst, the molar ratio of organic matter to Ni is preferably 0.1-8, more preferably 0.2-3.

It can be understood that, when the hydrotreating catalyst is used, those skilled in the art can perform pre-sulfiding according to conventional methods.

In another aspect, according to another embodiment of the present invention, there is provided a method for preparing a hydrotreating catalyst, the method comprising the steps of:

The carrier is uniformly mixed with a solution of Ni-containing compound, Mo-containing compound and W-containing compound to obtain mixture A, which is dried or calcined to obtain the hydrotreating catalyst.

In some preferred examples, the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate, and ethyl ammonium metatungstate; the Ni-containing compound is a water-soluble salt of Ni, It is preferably one or more of Ni nitrate, acetate, carbonate and basic carbonate; the Mo-containing compound is selected from one of molybdenum trioxide, ammonium paramolybdate and sodium molybdate species or several.

In yet another preferred example, the mixing manner is co-impregnation or step-by-step impregnation. There is no requirement for the impregnation sequence of each component, as long as impregnation can be achieved.

In yet another preferred example, the drying or calcining temperature is 100-600° C. and the time is 3-24 hours. Further, the drying or calcining temperature may be further 100-500°C, and the time may be 3-18 hours.

In yet another preferred example, the preparation of the carrier comprises the following steps:

Mixing the powder of the metal oxide matrix containing pores with the Mg solution and the organic solvent uniformly, and then carrying out the secondary drying of the obtained mixture and calcining in a non-oxidizing atmosphere to obtain a product B;

The product B is then mixed with a binder, shaped, dried and calcined to obtain the carrier.

The organic solvent is introduced in the preparation process of the carrier, and the organic solvent and Mg are fully mixed evenly. The organic solvent protects the Mg well, so that the Mg is more and more uniformly dispersed on the surface of the pores of the matrix, which is beneficial to the Mg and the carrier. As well as the interaction between the active metal components, the SMSI was effectively adjusted, and the formation and dispersion of the highly active Type II active phase was promoted, thereby improving the low-temperature catalytic performance of the catalyst.

In the preparation process of the above-mentioned carrier, the Mg solution and the organic solvent may be mixed with the powder of the metal oxide matrix containing pores at the same time, or may be mixed separately. When the two are mixed separately, it is preferable to mix the powder of the metal oxide matrix containing pores with the Mg solution uniformly, and dry to obtain the Mg-containing powder; and then add an organic solvent to the Mg-containing powder. Wherein, the mode of mixing the powder of the metal oxide matrix containing pores with the Mg solution is preferably dipping or beating; the mode of adding an organic solvent to the Mg-containing powder is preferably dipping, more preferably equal volume dipping or supersaturated dipping; The drying conditions are preferably as follows: the drying temperature is 110-150° C., and the drying time is 3-12 hours. Further, when the Mg solution and the organic solvent are mixed with the powder of the metal oxide matrix containing pores at the same time, the addition amount of Mg and the organic solvent is greater than the addition amount of the two when they are mixed separately.

In a preferred example, the Mg solution includes, but is not limited to, one or more selected from aqueous solutions of magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, and magnesium chloride.

In a preferred example, the organic solvent includes, but is not limited to, one or more selected from water-soluble lower alcohols, lower carbonic acids, lower amines and sugars.

In a preferred example, the water-soluble low-carbon alcohol includes, but is not limited to, selected from ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol (number average molecular weight is 500-1000), diethyl alcohol Diol, butanediol, sugar alcohol; the low carbonic acid includes but is not limited to selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid, sugar acid; the low carbon amine is selected from sugar amine; the sugar includes But not limited to be selected from sucrose, triose, pentose, hexose, glycoside.

In a preferred example, the binder is an alumina precursor. Exemplary alumina precursors include, but are not limited to, one or more selected from pseudo-boehmite, boehmite, boehmite, gibbsite, amorphous alumina, and boehmite. .

In the above preparation method, the non-oxidizing atmosphere is preferably an inert atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere. In a preferred example, after calcination in a non-oxidative atmosphere, the obtained product B has a carbon content of 1-20 wt %, preferably 2-10 wt %, and a Mg content of 0.5-20 wt %.

Further, the roasting temperature of the roasting in the non-oxidizing atmosphere is 150-350° C., and the roasting time is 2-8 hours.

Further, the mass ratio of the product B to the binder is 10-90 wt%; the conditions for baking the mixture of the product B and the binder after molding and drying are as follows: the baking temperature is 400-800° C., and the baking time is 2-10 hours.

In yet another preferred example, the preparation method further includes the step of adding organic matter to the mixture A. The organic matter is impregnated in the metal active component and/or the carrier. The organic matter is preferably an oxygen-containing organic matter or a nitrogen-containing organic matter. For example, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids; the nitrogen-containing organic compound is an organic amine; in the hydrotreating catalyst, the molar ratio of the organic compound to Ni is preferably 0.1-8 , more preferably 0.2-3.

According to the preparation method of the catalyst provided in this embodiment, the carrier can be made into various easy-to-handle moldings, such as microspheres, spheres, tablets or bars, etc., depending on different purposes or requirements. The molding method can be carried out according to conventional methods, such as extrusion, spheronization, tableting and other methods. The extrusion molding method is preferred, and the shape of the catalyst is preferably a strip clover or a four-leaf clover.

In yet another aspect, one embodiment of the present invention provides the use of the hydrotreating catalyst as provided in the above embodiment in the hydrorefining process of distillate or crude oil secondary processed products.

The above-mentioned crude oil secondary processing products refer to the products of crude oil advanced processing technology other than distillation, such as catalytic cracking oil, coking oil, thermal cracking oil and the like. Among them, the deep processing technology includes but is not limited to: thermal cracking, catalytic cracking, delayed coking, catalytic reforming, hydrocracking and the like.

The hydrotreating catalyst provided in the above embodiment can be used in the hydrotreating process of distillate oil or reforming pretreatment feedstock, and is especially suitable for the hydrotreating process of oil products with high olefin content. The operating conditions can be adjusted within the following ranges according to the properties of the raw oil and the quality of the oil: reaction temperature 200-550℃, volume space velocity 0.5-20h ^-1 , hydrogen partial pressure 0.5-15MPa, hydrogen/oil ratio 50 -900:1.

Below, in conjunction with some specific embodiments to describe:

In the following examples and comparative examples, the content of each element in the catalyst was analyzed by X-ray fluorescence spectrometer of ZSX Primus IV model from Rigaku, and the carbon content on the powder was analyzed by Vario EL Cube element analyzer from Element Company in Germany.

Example 1

The present embodiment is a carrier for preparing a catalyst, comprising the following steps:

(1) After fully mixing 200 g of γ-Al ₂ O ₃ powder with 2100 mL of 54 g of magnesium nitrate hexahydrate solution, it was dried at 120° C. for 3 h to obtain Mg-containing γ-Al ₂ O ₃ powder. 200g of Mg-containing γ-Al ₂ O ₃ powder was saturated and immersed in a 192 mL aqueous solution containing 30 g of glycerol, dried at 120° C., and roasted in a nitrogen atmosphere at 215° C. for 3 hours (the content of element C in the powder was: 5.3 wt%).

(2) Mix 200 g of the above powder with 100 g of pseudo-boehmite in a mass ratio of 2:1. Then in the mixed powder, add 9g of saffron powder, mix evenly, weigh 8.4mL of nitric acid and water to make 204mL of solution, add this solution to the mixed powder under stirring, knead and extrude to make clover with a diameter of 1.6mm Then, the wet strip was dried at 120 °C for 3 h, and then calcined at 600 °C to obtain a Mg-containing γ-Al ₂ O ₃ carrier, denoted as S1, and the characterization by three-dimensional transmission electron microscopy showed that in the carrier, MgO It is uniformly dispersed in γ-Al ₂ O ₃ , and most of the MgO is uniformly dispersed on the channel surface of the γ-Al ₂ O ₃ .

Example 2

The present embodiment is a carrier for preparing a catalyst, comprising the following steps:

(1) Take 200 g of γ-Al ₂ O ₃ powder, mix and beat with 460 mL of magnesium-containing solution containing 64.7 g of magnesium nitrate hexahydrate, and dry at 130 °C for 3 h to obtain Mg-containing γ-Al ₂ O ₃ powder . The above-mentioned 200 g of Mg-containing γ-Al ₂ O ₃ powder was saturated and immersed in a 134 mL aqueous solution containing 30 g of glycerol, dried at 120 ° C, and calcined in a nitrogen atmosphere at 215 ° C for 2.5 hours (carbon content in the powder). 5.3 wt%).

(2) Mix 200 g of the above powder with 66.7 g of pseudo-boehmite in a mass ratio of 3:1. Then in the mixed powder, add 8 g of saffron powder, mix well, weigh 8.2 mL of nitric acid and water to make 187 mL of solution, add this solution to the mixed powder under stirring, knead and extrude to make clover with a diameter of 1.6 mm The wet strips were then dried at 120 °C for 3 h, and then calcined at 600 °C to obtain a Mg-containing γ-Al ₂ O ₃ carrier, denoted as S2, and its structure was similar to S1.

Example 3

The present embodiment is a carrier for preparing a catalyst, comprising the following steps:

(1) Take 200 g of γ-Al ₂ O ₃ powder and mix thoroughly with 212 mL of a solution containing 34.5 g of magnesium nitrate hexahydrate and 29 g of glucose, then dry at 120°C for 3 hours, and calcinate under argon at 260°C for 3 hours to obtain a solution containing Mg and C γ-Al ₂ O ₃ powder (the carbon content in the powder is 5.2 wt%).

(2) Mix 200 g of the above powder with 66.7 g of pseudo-boehmite in a mass ratio of 3:1. Then in the mixed powder, add 8 g of saffron powder, mix well, weigh 8.8 mL of nitric acid and water to make 141 mL of solution, add this solution to the mixed powder with stirring, knead and extrude to make clover with a diameter of 1.6 mm The wet strips were then dried at 120 °C for 3 h, and then calcined at 630 °C to obtain a Mg-containing γ-Al ₂ O ₃ carrier, denoted as S3, and its structure was similar to that of S1.

Example 4

This embodiment is to prepare Ni-Mo-W/γ-Al ₂ O ₃ (S1) catalyst, including the following steps:

26.44g of ammonium metatungstate, 13.9g of ammonium paramolybdate, 18.7g of nickel nitrate and a small amount of ammonia water were used to prepare a solution of 82mL, and 100g of S1 carrier was impregnated with this solution. After drying at 450°C for 3 hours, the catalyst C1 was obtained.

Example 5

This embodiment is to prepare Ni-Mo-W/γ-Al ₂ O ₃ (S2) catalyst, including the following steps:

6g of MoO ₃ was added to 35mL of aqueous solution containing a small amount of phosphoric acid, heated and boiled to dissolve, and after cooling to room temperature, 11.7g of ammonium metatungstate and 9.73g of nickel nitrate were added, and after a little heating and stirring to dissolve, the volume was adjusted to 40mL. Impregnate 50 g of S2 carrier with the same volume of this solution, let it stand for 2 hours, then dry it at 120°C for 3 hours and calcinate at 450°C for 3 hours to obtain catalyst C2.

Example 6

This embodiment is to prepare Ni-Mo-W/γ-Al ₂ O ₃ (S2) catalyst, including the following steps:

Dissolve 16.34 g of ammonium paramolybdate in 70 mL of aqueous solution containing a small amount of ammonia water, then add 16.1 g of ammonium metatungstate and 14.51 g of nickel acetate, stir to fully dissolve, and set the volume to 80 mL. The above 100g S2 carrier was impregnated with this solution in an equal volume, and after standing for 2 hours, it was dried at 130° C. for 3 hours and calcined at 480° C. for 3 hours to obtain catalyst C3.

Example 7

This embodiment is to prepare Ni-Mo-W/γ-Al ₂ O ₃ (S3) catalyst, including the following steps:

8g of MoO ₃ was added to 30 mL of low-concentration phosphoric acid water solution, heated to boiling, and cooled to room temperature after dissolving. 18.79g of ammonium metatungstate and 27.5g of basic nickel carbonate were prepared into a 45mL aqueous solution under heating and stirring, the above two solutions were fully mixed, immersed in 100g S3 carrier, and after standing for 2h, at 130 After drying at ℃ for 3h and calcining at 480℃ for 3h, catalyst C4 was obtained.

Example 8

This embodiment is to prepare complex Ni-Mo-W/γ-Al ₂ O ₃ (S2) catalyst, including the following steps:

Impregnate 100 g of S2 carrier with an equal volume of 80 mL of an aqueous solution containing 9 g of ammonium metatungstate, calcined at 420°C for 3 hours and cooled to room temperature, take 12.7 g of ammonium metatungstate, 13.25 g of ammonium paramolybdate, 16.8 g of nickel Glycerol was prepared into a solution of 74 mL, and the solution was immersed in an equal volume for 3 hours again, and then dried at 120 °C for 3 hours and 160 °C for 4 hours to obtain catalyst C5.

Comparative Example 1

This comparative example is to prepare Ni-Mo-W/γ-Al ₂ O ₃ (without adding Mg and C elements in the preparation process) catalyst, including the following steps:

(1) Weigh 170g of γ-Al ₂ O ₃ powder and 50g of pseudo-boehmite powder, add 6.5g of succulent powder, mix well, measure 6.2mL of concentrated nitric acid to prepare 182.5mL of nitric acid solution, and stir It was added to the above mixed powder, and then kneaded and extruded to make a clover-shaped wet bar with a diameter of 1.6 mm. Subsequently, the wet bar was dried at 140 ° C for 3 hours, and then γ-Al obtained by roasting at 600 ° C. ₂ O ₃ carrier.

(2) 16.2 g of ammonium metatungstate, 16.5 g of ammonium paramolybdate, and 14.6 g of nickel nitrate were used to prepare a solution of 84 mL, and the solution was immersed in an equal volume of step (1) to obtain 100 g of γ-Al ₂ O _3. The carrier was then dried at 130°C for 3h and calcined at 450°C for 3h to obtain catalyst D1.

Comparative Example 2

This comparative example is to prepare Ni-Mo-W/Mg/γ-Al ₂ O ₃ catalyst, including the following steps:

(1) Weigh 180g of γ-Al ₂ O ₃ powder and 70g of pseudo-boehmite powder, add 6.2g of succulent powder, mix well, measure 8.3mL of concentrated nitric acid and 22.1g of magnesium nitrate to prepare a 198mL solution , added to the above mixed powder under stirring, and then kneaded and extruded to make a clover-shaped wet bar containing Mg with a diameter of 1.6 mm. The Mg-containing γ-Al ₂ O ₃ support was obtained by calcination.

(2) 16.2 g of ammonium metatungstate, 16.5 g of ammonium paramolybdate, and 14.6 g of nickel nitrate were used to prepare a solution of 84 mL, and the solution was immersed in an equal volume of step (1) to obtain 100 g of γ-Al ₂ O _3. The carrier was then dried at 130°C for 3h and calcined at 450°C for 3h to obtain catalyst D2.

The catalyst properties of the above Examples 4-8 and Comparative Examples 1-2 are shown in Table 1 below.

Table 1 Properties of catalysts

Test example

In this test example, straight-run diesel fuel mixed with 30% catalytic diesel oil was used to evaluate the activity of catalysts C1-C5, and the activities of catalysts C1-C5 were compared with those of comparative examples D1-D2. The properties of the raw oil are shown in Table 2.

Table 2 Properties of raw material oil

Raw oil properties Numerical value Density (20℃), g/cm³ 0.8867 S, μg/g 3246.8 N, μg/g 443.5

The activity evaluation of the catalyst was carried out in a 200 mL fixed bed reactor using a hydrogen one-pass procedure. Before the catalyst evaluation, the pre-sulfiding treatment was carried out first. The sulfurized oil was hydrorefined gasoline containing 2.5%. The sulfurization conditions were as follows: the sulfurization pressure was 6.4MPa, the hydrogen/oil ratio was 500v/v, the volume space velocity was 1.5h ^-1 , and the device gas After the tightness is qualified, it is vulcanized at 360℃ for 12h. After the vulcanization, the vulcanized oil was switched to the raw oil, and the activity evaluation was started after 24 hours of stabilization under the reaction conditions. The reaction conditions were as follows: the reaction pressure was 6.0 MPa, the liquid hourly space velocity (LHSV) was 2.5h ^-1 , the reaction temperature was 310°C, and the hydrogen/oil ratio was 300v/v. The activity of each catalyst is the data obtained by analysis after running stably under the reaction conditions for 150 h, as shown in Table 3.

Table 3 Catalyst activity evaluation test results

Test case number catalyst number Sulfur content, μg/g Nitrogen content, μg/g Example 4 C1 15.34 17.25 Example 5 C2 7.47 8.2 Example 6 C3 20.68 18.54 Example 7 C4 32.47 26.42 Example 8 C5 4.62 6.31 Comparative Example 1 D1 112.83 98.57 Comparative Example 2 D2 88.46 76.42

[Note] The reaction conditions are: reaction pressure 6.0MPa, liquid hourly space velocity (LHSV) 2.5h ^-1 , reaction temperature 320°C, and hydrogen/oil ratio 300v/v.

The results in Table 3 show that, under the conditions of low pressure, lower reaction temperature and lower hydrogen-to-oil ratio, the catalyst prepared by the method provided by the present invention is effective for the desulfurization of 30% catalytic diesel blended diesel, The N performance is significantly better than that of the comparative conventional catalyst, which fully proves that the above-mentioned inventive method can effectively prepare a high-performance distillate hydrotreating catalyst.

Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the embodiments of the present invention. Changes or changes in other different forms cannot be exhausted here, and all obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (10)

1. A hydrotreating catalyst characterized by comprising a metal active component and a carrier supporting the metal active component, wherein the metal active component contains WO₃NiO and MoO₃The structure of the carrier comprises MgO and a metal oxide matrix containing channels, and the MgO is uniformly dispersed in the metal oxide matrix containing the channels and at leastMost of the MgO is uniformly dispersed on the pore surfaces of the metal oxide matrix containing pores.

2. The hydrotreating catalyst according to claim 1, characterized in that the catalyst comprises, based on the total weight of the catalyst: WO₃ 5-40wt％，MoO₃5-30 wt%, NiO 0.1-15 wt%, MgO 0.1-5 wt%; preferably, the catalyst comprises, based on the total weight of the catalyst: WO₃ 10-25wt％，MoO₃ 5-20wt％，NiO 1-10wt％，MgO 0.5-3wt％。

3. The hydrotreating catalyst according to claim 1 or 2, characterized in that the metal oxide matrix containing channels is selected from one or more of alumina, alumina-silica; preferably, the alumina is γ -Al₂O₃。

4. The hydrotreating catalyst according to claim 1, characterized in that the hydrotreating catalyst further comprises an organic matter impregnated in the metal active component and/or the carrier; preferably, the organic matter is oxygen-containing organic matter or nitrogen-containing organic matter; preferably, the oxygen-containing organic matter is selected from one or more of organic alcohol and organic acid; the nitrogenous organic matter is organic amine; preferably, the molar ratio of organic to Ni in the hydrotreating catalyst is in the range of 0.1 to 8, more preferably 0.2 to 3.

5. The process for preparing a hydroprocessing catalyst according to any one of claims 1-4, comprising the steps of:

and uniformly mixing the carrier with a Ni-containing compound, a Mo-containing compound and a W-containing compound solution to obtain a mixture A, and drying or roasting to obtain the hydrotreating catalyst.

6. The preparation method according to claim 5, wherein the W-containing compound is selected from one or more of ammonium tungstate, ammonium metatungstate, ammonium paratungstate and ammonium ethyl metatungstate;

the Ni-containing compound is water-soluble salt of Ni, preferably one or more of nitrate, acetate, carbonate and alkali carbonate of Ni;

the Mo-containing compound is selected from one or more of molybdenum trioxide, ammonium paramolybdate and sodium molybdate;

preferably, the mixing is carried out by co-impregnation or stepwise impregnation;

preferably, the drying or baking temperature is 100-600 ℃ and the time is 3-24 hours.

7. The production method according to claim 5 or 6, wherein the production of the carrier comprises the steps of:

uniformly mixing the powder of the metal oxide matrix containing the pore channels with Mg solution and organic solvent, and then carrying out secondary drying and roasting on the obtained mixture in a non-oxidizing atmosphere to obtain a product B;

and mixing the product B with a binder, molding, drying and roasting to obtain the carrier.

8. The preparation method according to claim 7, wherein the Mg solution is one or more selected from magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate and magnesium chloride;

the organic solvent is selected from one or more of water-soluble low-carbon alcohol, low-carbon acid, low-carbon amine and sugar;

preferably, the water-soluble lower alcohol is selected from ethylene glycol, glycerol, butanol, isopropanol, polyethylene glycol, diethylene glycol, butanediol, sugar alcohol; the low-carbon acid is selected from citric acid, lactic acid, malic acid, tartaric acid, succinic acid and sugar acid; the lower amine is selected from sugar amine; the sugar is selected from sucrose, triose, pentose, hexose, glycoside;

preferably, the binder is an alumina precursor;

more preferably, the alumina precursor is selected from one or more of pseudo boehmite, gibbsite, amorphous alumina and surge boehmite;

preferably, the non-oxidizing atmosphere is an inert atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere;

preferably, the roasting temperature of roasting in the non-oxidizing atmosphere is 150-350 ℃, and the roasting time is 2-8 hours;

preferably, the mass ratio of the organic solvent to the metal oxide matrix containing the porous channel is 10 to 50 wt%;

preferably, the carbon content of the product B is 1-20 wt%, and the Mg content is 0.5-20 wt%;

preferably, the mass ratio of the product B to the binder is 10 to 90 wt%; the roasting conditions after the product B and the binder mixture are molded and dried are as follows: the roasting temperature is 400-;

preferably, the method for uniformly mixing the powder of the metal oxide matrix with the pore channel, the Mg solution and the organic solvent is to mix the Mg solution and the organic solvent with the powder of the metal oxide matrix with the pore channel at the same time, or mix the Mg solution with the powder of the metal oxide matrix with the pore channel, dry the obtained product and mix the dried product with the organic solvent.

9. The method according to claim 5, further comprising the step of adding an organic substance to the mixture A.

10. Use of a hydrotreating catalyst as claimed in any one of claims 1 to 4 in a hydrofinishing process of a distillate or crude oil secondary processing product.