CN110152723A - A kind of hydrotreating catalyst and its preparation method and application - Google Patents

Abstract

The present invention provides a kind of Hydrobon catalysts and its preparation method and application, wherein by the gross weight of catalyst for 100wt% in terms of, which includes the carrier of 50wt%-95wt% and the active metal component of 5wt%-50wt%；The carrier includes Sn (II) AlPO₄- 5 molecular sieves and γ-Al₂O₃；The active metal component includes the oxide and/or sulfide of one or more of Co, Mo, Ni and W.Hydrobon catalyst provided by the invention, which uses, includes Sn (II) AlPO₄- 5 molecular sieves and γ-Al₂O₃Carrier so that catalyst has suitable surface acidity, and there is biggish specific surface area, be capable of providing more activated centre；Effectively increase hydrodesulfurization, the denitrification reaction activity of catalyst.

Description

A kind of hydrotreating catalyst and its preparation method and application

technical field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a hydrorefining catalyst and a preparation method and application thereof.

Background technique

Crude oil and distillates derived from crude oil contain impurities such as sulfur, nitrogen, oxygen and metals. The existence of these impurities not only affects the stability of oil products, but also emits SO _X , NO _X and other harmful gases to pollute the environment during use. During the secondary processing of oil, the presence of impurities such as sulfur, nitrogen, oxygen and metals can poison the catalyst. Therefore, the removal of the above impurities is an important process in oil processing. Distillate hydrotreating refers to the process of contacting raw oil and hydrogen with catalyst under certain temperature and pressure to remove impurities and to saturate aromatics.

With the successive introduction of increasingly stringent environmental regulations, people have put forward more and more stringent requirements for the quality of oil products, so the production of low-pollution clean fuels has attracted much attention. Hydrotreating is one of the important ways to produce clean fuels. Through hydrotreating, at least part of impurities such as sulfur, nitrogen, and oxygen in oil products can be converted into hydrogen sulfide, ammonia, and water to be removed; Olefins are partially hydrogenated and saturated, thereby improving oil quality.

The improved catalyst activity can make the hydrodesulfurization process conditions more moderate, or achieve better quality products or prolong the service life of the catalyst under the same process conditions. Therefore, the development of high-activity hydrotreating catalysts is a constantly pursued goal in this field.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned problems, an object of the present invention is to provide a hydrotreating catalyst.

Another object of the present invention is to provide a method for preparing the above-mentioned hydrotreating catalyst.

Another object of the present invention is to provide the application of the above hydrotreating catalyst in the hydrotreating reaction of gasoline and diesel.

Another object of the present invention is to provide a carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ .

Another object of the present invention is to provide a Sn(II)AlPO ₄ -5 molecular sieve.

In order to achieve the above object, the present invention provides a hydrofinishing catalyst, wherein, based on the total weight of the catalyst as 100wt%, the catalyst comprises 35wt%-95wt% of a carrier and 5wt%-50wt% of an active metal component ;

The carrier includes Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ ;

The active metal components include oxides and/or sulfides of one or more of Co, Mo, Ni and W.

In the above hydrorefining catalyst, a composite carrier is used, which at least includes two components, Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ . The applicant has found that the introduction of Sn(II)AlPO ₄ -5 molecular sieve has the effect of significantly improving the surface acidity of the carrier, and can improve the interaction between the carrier and the metal active component.

In the above hydrorefining catalyst, for the dosage of Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , those skilled in the art can determine the appropriate ratio according to the specific application environment. In a preferred embodiment, based on the total weight of the carrier as 100wt%, the content of Sn(II)AlPO ₄ -5 molecular sieve is 5wt%-60wt%; preferably 15wt%-45wt%. In this case, it is particularly effective for the hydrorefining of gasoline and diesel.

In the above-mentioned hydrorefining catalysts, the mixing method of Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ has no special requirements, and can be a simple mixing of the finished products of the two; the carrier can also be prepared by the following special methods: The carrier is prepared by mixing Sn(II)AlPO ₄ -5 molecular sieve with the precursor for preparing γ-Al ₂ O ₃ , and then forming and calcining. The carrier prepared by the above-mentioned special method has a more uniform acid distribution, which is also conducive to the uniform loading of the subsequent active metal components in the carrier, and therefore has a higher catalytic activity. Moreover, the carrier prepared in this way also has a significant increase in mechanical strength. Therefore, its comprehensive performance is obviously better than that of the carrier prepared by mixing the finished product. The precursor for preparing γ-Al ₂ O ₃ can be a conventional material in the field, and in a preferred embodiment, pseudo-boehmite is selected.

In the above-mentioned hydrotreating catalyst, when the carrier is prepared by the above-mentioned special method, the calcination conditions mainly consider the formation of γ-Al ₂ O ₃ . In a preferred embodiment, the calcination temperature is 450-650°C calcination. In addition, the molding can be carried out in a conventional manner in the art, such as kneading molding. After molding, it can be dried for a period of time (eg, at 90-120° C.), and then calcined.

In the above hydrotreating catalyst, all alumina in the carrier is not required to be γ-Al ₂ O ₃ , and other forms of alumina are also allowed. Of course, the carrier may also contain adjuvants such as dispersing aids, binders and other adjuvants conventional in the art to improve their corresponding properties. In the present invention, the molding shape of the carrier is not particularly limited, and can be adjusted according to specific needs.

In the above hydrorefining catalyst, the Sn(II)AlPO ₄ -5 molecular sieve is an AlPO ₄ -5 molecular sieve modified with divalent Sn, that is, Sn(II) is introduced into the AlPO ₄ -5 molecular sieve framework. In general, in a conventional method for preparing AlPO ₄ -5 molecular sieve, a divalent tin source is added to the raw material to prepare a gel, and then co-crystallized to obtain Sn(II)AlPO ₄ -5 molecular sieve. The content of SnO in the Sn(II)AlPO ₄ -5 molecular sieve can be in a conventional ratio. In a preferred embodiment, in the Sn(II)AlPO ₄ -5 molecular sieve, in terms of SnO, the content is 0.1wt%-4.0wt%; preferably 0.2wt%-2.0wt%. Test experiments show that the catalyst made of the molecular sieve with this ratio has better hydrogenation catalytic performance.

In the above hydrorefining catalyst, the active metal supported on the carrier can be one or a combination of Co, Mo, Ni and W. After calcination, these active metals generally exist in the form of oxides. Therefore, the active metal components can be oxides of the corresponding metals. In addition, the catalyst is sometimes subjected to pre-sulfide treatment before use, and part of the oxides will be converted into sulfides. Therefore, the active metal components can also be sulfides of the corresponding metals, or contain both oxides and sulfides. In a preferred embodiment, the active metal components are oxides and/or sulfides of Co and Mo (Co/Mo bimetallic catalysts), oxides and/or sulfides of Ni and W (Ni/W bimetallic catalysts). ), Co and Mo and W oxides and/or sulfides (Co/Mo/W trimetallic catalysts). Of course, the combination manner of the active metal components is not limited to the above three, and it can certainly be other conventional manners in the field. In another preferred embodiment, the active metal components are selected from oxides of the corresponding active metals. Taking the above three forms of catalysts as an example, the active metal components are a combination of CoO and MoO ₃ ; a combination of NiO and MoO ₃ ; a combination of CoO, MoO ₃ and MoO ₃ .

In the above-mentioned hydrofinishing catalyst, the relative content of the active metal component and the carrier may adopt a conventional ratio. In a preferred embodiment, based on the total weight of the catalyst as 100wt%, the catalyst comprises 60wt%-80wt% of the carrier and 20wt%-40wt% of the active metal component.

In the above hydrorefining catalyst, in a preferred embodiment, the active metal components include NiO and WO ₃ ; the contents of the two are 2wt%-13wt% and 8wt%-37wt% respectively based on the total weight of the catalyst.

In the above hydrorefining catalyst, when the active metal is supported on the carrier, a conventional method in the art can be used. In a preferred embodiment provided by the present invention, the impregnation method is used to support; for example, the support can be impregnated with a metal salt solution containing one or both of Ni and W. In specific implementation, the equal volume dipping method can be used.

The hydrorefining catalyst provided by the present invention adopts a carrier comprising Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , so that the catalyst has suitable surface acidity and a large specific surface area, which can provide more the active center. It can effectively improve the hydrodesulfurization and denitrification reaction activity of the catalyst.

The present invention also provides a method for preparing the above-mentioned hydrorefining catalyst, wherein the method comprises the following steps:

The Sn(II)AlPO ₄ -5 molecular sieve is mixed with the precursor for preparing γ-Al ₂ O ₃ , and then the carrier is prepared by molding and calcining;

The support is impregnated with a soluble metal salt solution containing one or more of Co, Mo, Ni and W, followed by drying and calcination to obtain the hydrofinishing catalyst.

In the solution provided by the present invention, the introduction of Sn(II)AlPO ₄ -5 molecular sieve into the alumina carrier can effectively improve the interaction between the carrier and the metal active component, and improve the activity of the catalyst. Compared with the traditional gasoline and diesel hydrogenation catalysts, the preparation process provided by the present invention can add corresponding Sn(II)AlPO ₄ -5 molecular sieve in the preparation process of the carrier under the premise of basically not changing the existing production process. The structure and acidity of the carrier are adjusted, so that the catalyst has a higher hydrogenation reaction activity for desulfurization and denitrification.

The present invention also provides the application of the above hydrotreating catalyst in the hydrotreating reaction of gasoline and diesel. The above-mentioned hydrotreating catalyst adopts the active metals (Co, Mo, Ni and W) in the gasoline and diesel hydrotreating catalysts, and the oxides of the active metals can be sulfided to obtain higher hydrogenation activity. Especially the bimetallic catalyst prepared by supporting the active metal Co/Mo combination, Ni/W combination and Co/Mo/W combination on the composite carrier has a very good effect on the hydrorefining of diesel oil. Diesel quality is positive.

The present invention also provides a carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , wherein the Sn(II)AlPO ₄ - 5. The weight of molecular sieve accounts for 5wt%-60wt%; the carrier is prepared by the following method: mixing Sn(II) _AlPO4-5 molecular sieve with the precursor for preparing γ _{- Al2O3} , and calcining to obtain the vector. The performance of the carrier prepared by the above-mentioned special method is obviously better than that of the carrier prepared by directly mixing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ . The precursor for preparing γ-Al ₂ O ₃ can be a conventional material in the field, and in a preferred embodiment, pseudo-boehmite is selected.

In the above-mentioned carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , the calcination conditions mainly consider the formation of γ-Al ₂ O ₃ . In a preferred embodiment, the roasting conditions are: roasting at 450-650° C. for 2-8 hours. In addition, the molding can be carried out in a conventional manner in the art, such as kneading molding. After molding, it can be dried for a period of time (eg, at 90-120° C.), and then calcined.

In the above-mentioned carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , all alumina in the carrier is not required to be γ-Al ₂ O ₃ , and other forms of alumina are also allowed. Of course, the carrier may also contain adjuvants such as dispersing aids, binders and other adjuvants conventional in the art to improve their corresponding properties. In the present invention, the molding shape of the carrier is not particularly limited, and can be adjusted according to specific needs.

In the above-mentioned carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , preferably, based on the total weight of the carrier as 100 wt %, the Sn(II)AlPO ₄ -5 molecular sieve The weight accounts for 15wt%-45wt%.

The present invention also provides a Sn(II)AlPO ₄ -5 molecular sieve, wherein the Sn(II)AlPO ₄ -5 molecular sieve is prepared by the following method: (1) combining a divalent tin source with a source for preparing AlPO The raw materials of the _4-5 molecular sieve are mixed to prepare a mixed gel; (2) the mixed gel is crystallized and calcined to obtain the Sn(II)AlPO _4-5 molecular sieve.

Among the above Sn(II)AlPO ₄ -5 molecular sieves, most soluble divalent tin sources can be used. In a preferred embodiment, the divalent tin source used is stannous chloride or stannous acetate.

In the above Sn(II)AlPO ₄ -5 molecular sieve, in general, in the conventional method for preparing AlPO ₄ -5 molecular sieve, a divalent tin source is added to the raw material to prepare gel, and then co-crystallized to obtain Sn(II)AlPO _4-5 molecular sieve. The crystallization treatment method commonly used in the preparation of AlPO ₄ -5 molecular sieves can be adopted. In a preferred embodiment, a conventional hydrothermal crystallization treatment method is adopted, so that a product with a relatively stable quality can be obtained, and furthermore, the process and equipment can be kept unchanged.

In the above Sn(II)AlPO ₄ -5 molecular sieve, preferably, the conditions of the hydrothermal crystallization treatment are: crystallization at 140-200° C. for 14-36 h. Preferably, the conditions of the roasting treatment are: roasting at 450-650° C. for 2-8 hours.

In the above Sn(II)AlPO ₄ -5 molecular sieve, in a preferred embodiment, the Sn(II)AlPO ₄ -5 molecular sieve is based on SnO, and the content is 0.1wt%-4.0wt%; preferably 0.2wt%- 2.0 wt%.

In the above Sn(II)AlPO ₄ -5 molecular sieve, the gel can be prepared by adding the corresponding divalent tin source according to the conventional method for preparing AlPO ₄ -5 molecular sieve in the prior art. In a preferred embodiment, the raw materials for preparing AlPO ₄ -5 molecular sieves include: water, aluminum source, phosphorus source and templating agent. Preferably, the aluminum source includes pseudoboehmite, the phosphorus source includes phosphoric acid (generally concentrated phosphoric acid), and the template agent includes triethylamine, triethanolamine, tetraethylammonium bromide or tetraethylhydrogen Ammonium oxide. Further preferably, the water, aluminum source, phosphoric acid, tin source and templating agent are respectively based on H ₂ O, Al ₂ O ₃ , P ₂ O ₅ , SnO and templating agent, and the molar ratio of each component is 30-70 :1:0.9-1.7:0.01-0.2:1-3.

In the above Sn(II)AlPO ₄ -5 molecular sieve, the step of preparing the Sn(II)AlPO ₄ -5 molecular sieve includes:

(1) At room temperature to 60 ℃, after the pseudo-boehmite and water are mixed uniformly, phosphoric acid and divalent tin source are added to fully dissolve them. After the phosphoric acid is added dropwise, continue stirring for 0.3-3 hours, and then slowly add the template agent , after mixing and stirring for 1-10h, a mixed gel is obtained;

(2) The mixed gel is crystallized in an autoclave at 140-200° C. for 14-36 hours, and the crystallized product is washed, filtered, dried and calcined to obtain Sn(II)AlPO ₄ -5 molecular sieve.

Detailed ways

In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solutions of the present invention are now described in detail below, but should not be construed as limiting the scope of implementation of the present invention.

Example 1

The present embodiment provides a hydrogenation catalyst, which is prepared by an impregnation method, and specifically includes the following steps:

(1) 5.87g pseudo-boehmite, 10.00g concentrated phosphoric acid (85% by mass), 6.00g triethylamine, 1.00g SnCl ₂ ·2H ₂ O and 29.00g deionized water were mixed to form a mixed The gel was dynamically crystallized in a 100 mL autoclave for 20 h, washed, filtered, dried, and calcined to obtain Sn(II)AlPO ₄ -5 molecular sieve, wherein the molecular sieve mass was calculated as 100 wt %, and the SnO content was 1.1 wt %;

(2) mixing Sn(II)AlPO ₄ -5 molecular sieve and pseudo-boehmite according to a mass ratio of 4:6, extruding, drying naturally, and calcining at 550° C. for 4 hours to obtain a carrier;

(3) Dissolve 1.57g of nickel nitrate and 3.16g of ammonium metatungstate in 7.00g of deionized water to configure a co-dipping solution;

(4) adding the co-dipping solution dropwise to the above-mentioned carrier with a diameter of 1.5 mm extruded from 7.00 g to obtain a catalyst semi-finished product;

(5) above-mentioned catalyst semi-finished product was left standstill in air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 4°C/min, roasted at 500°C, under air atmosphere for 4 hours to obtain a hydrogenation catalyst F-1.

The total amount of nickel-tungsten oxides in the catalyst F-1 was measured to be 31.0 wt % (based on the total weight of the catalyst F-1). The measurement and calculation methods for the total content of oxides of active component metals and promoter metals in the catalyst are all known measurement and calculation methods in the art.

Comparative Example 1

This comparative example provides a diesel hydrogenation catalyst as a comparative catalyst.

The preparation method of this comparative catalyst comprises the following steps:

(1) Dissolve 4.74g of ammonium metatungstate and 2.26g of nickel nitrate in 10mL of deionized water to prepare an immersion solution;

(2) this dipping solution is added dropwise to 10.0 g of extruded alumina bars with a diameter of 1.5 mm to obtain a catalyst semi-finished product;

(3) the catalyst semi-finished product was allowed to stand in the air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 5°C/min, and roasted at 500°C in an air atmosphere for 4 hours to obtain the described The comparative catalyst 1. The total amount of nickel-tungsten oxide in the comparative catalyst was determined to be 31.0 wt % (based on the total weight of the catalyst F-1).

Example 2

The present embodiment provides a hydrogenation catalyst, which is prepared by an impregnation method, and specifically includes the following steps:

(1) 5.87g pseudo-boehmite, 10.00g concentrated phosphoric acid (85% by mass), 6.00g triethylamine, 2.00g SnCl ₂ ·2H ₂ O and 29.00g deionized water were mixed to form a mixed The gel was dynamically crystallized in a 100 mL autoclave for 20 hours, washed, filtered, dried, and calcined to obtain Sn(II)AlPO ₄ -5 molecular sieve, wherein the molecular sieve mass was calculated as 100 wt %, and the SnO content was 2.7 wt %;

(2) mixing Sn(II)AlPO ₄ -5 molecular sieve and pseudo-boehmite in a mass ratio of 3:7, extruding, drying naturally, and calcining at 550° C. for 4 hours to obtain a carrier;

(3) Dissolve 1.57g of nickel nitrate and 3.16g of ammonium metatungstate in 4.00g of deionized water to form a co-dipping solution;

(4) this co-dipping solution is added dropwise to the above-mentioned carrier with a diameter of 1.5 mm extruded from 4.0 g to obtain a catalyst semi-finished product;

(5) above-mentioned catalyst semi-finished product was left standstill in air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 4°C/min, roasted at 500°C, under air atmosphere for 4 hours to obtain a hydrogenation catalyst F-2.

The total amount of nickel-tungsten oxides in the catalyst F-2 was measured to be 42.9 wt % (based on the total weight of the catalyst F-2). The measurement and calculation methods for the total content of oxides of active component metals and promoter metals in the catalyst are all known measurement and calculation methods in the art.

Comparative Example 2

This comparative example provides a diesel hydrogenation catalyst as a comparative catalyst.

The preparation method of this comparative catalyst comprises the following steps:

(1) Dissolve 3.16g of ammonium metatungstate and 1.57g of nickel nitrate in 4.0mL of deionized water to prepare an immersion solution;

(2) this dipping solution is added dropwise to 4.0g of extruded alumina bars with a diameter of 1.5mm to obtain a catalyst semi-finished product;

(3) the catalyst semi-finished product was allowed to stand in the air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 5°C/min, and roasted at 500°C in an air atmosphere for 4 hours to obtain the described The comparative catalyst 2. The total content of nickel-tungsten oxides in the comparative catalyst was measured to be 42.9 wt % (all based on the total weight of the comparative catalyst).

Example 3

The present embodiment provides a hydrogenation catalyst, which is prepared by an impregnation method, and specifically includes the following steps:

(1) Mix 5.97g of pseudoboehmite, 10.5g of concentrated phosphoric acid, 6.4g of triethylamine, 4.0g of stannous acetate and 29.9g of deionized water to form a mixed gel after stirring and mixing, and a 100mL autoclave dynamic crystal 20h, washed, filtered, dried and roasted to obtain Sn(II)AlPO ₄ -5 molecular sieve, wherein the molecular sieve mass was calculated as 100wt%, and the SnO content was 3.5wt%;

(2) mixing Sn(II)AlPO ₄ -5 molecular sieve and pseudo-boehmite in a mass ratio of 5:5, extruding, drying naturally, and calcining at 550° C. for 4 hours to obtain a carrier;

(3) Dissolve 1.57g of nickel nitrate and 3.16g of ammonium metatungstate in 7.0g of deionized water to configure a co-dipping solution;

(4) this co-dipping solution is added dropwise to the above-mentioned carrier with a diameter of 1.5 mm extruded into 9.0 g to obtain a catalyst semi-finished product;

(5) above-mentioned catalyst semi-finished product was left standstill in air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 4°C/min, roasted at 500°C, under air atmosphere for 4 hours to obtain a hydrogenation catalyst F-3.

The total amount of nickel-tungsten oxides in the catalyst F-3 was measured to be 25.0 wt % (based on the total weight of the catalyst F-3). The measurement and calculation methods for the total content of oxides of active component metals and promoter metals in the catalyst are all known measurement and calculation methods in the art.

Comparative Example 3

This comparative example provides a diesel hydrogenation catalyst as a comparative catalyst.

The preparation method of this comparative catalyst comprises the following steps:

(1) Dissolve 3.16g of ammonium metatungstate and 1.57g of nickel nitrate in 9.0mL of deionized water to prepare an immersion solution;

(2) this dipping solution is added dropwise to 9.0g of extruded alumina bars with a diameter of 1.5mm to obtain a catalyst semi-finished product;

(3) the catalyst semi-finished product was allowed to stand in the air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 5°C/min, and roasted at 500°C in an air atmosphere for 4 hours to obtain the described The comparative catalyst 3. The total content of nickel-tungsten tungsten oxide in the comparative catalyst was measured to be 25.0 wt % (all based on the total weight of the comparative catalyst).

Example 4

The present embodiment provides a hydrogenation catalyst, which is prepared by an impregnation method, and specifically includes the following steps:

(1) Mix 5.97g pseudo-boehmite, 10.5g concentrated phosphoric acid (85% by mass), 6.4g triethylamine, 0.5g stannous acetate and 29.9g deionized water to form a mixed gel , 100mL autoclave was dynamically crystallized for 20h, washed, filtered, dried, and calcined to obtain Sn(II)AlPO ₄ -5 molecular sieve. Calculated according to the molecular sieve mass of 100wt%, the SnO content was 0.3wt%;

(2) mixing Sn(II)AlPO ₄ -5 molecular sieve and pseudo-boehmite according to a mass ratio of 2:8, extruding, drying naturally, and calcining at 550° C. for 4 hours to obtain a carrier;

(3) Dissolve 1.57g of nickel nitrate and 3.16g of ammonium metatungstate in 7.0g of deionized water to configure a co-dipping solution;

(4) this co-dipping solution is added dropwise to the above-mentioned carrier with a diameter of 1.5 mm extruded into 9.0 g to obtain a catalyst semi-finished product;

(5) above-mentioned catalyst semi-finished product was left standstill in air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 4°C/min, roasted at 500°C, under air atmosphere for 4 hours to obtain a hydrogenation catalyst F-4.

The total amount of nickel-tungsten oxides in the catalyst F-4 was measured to be 25.0 wt % (based on the total weight of the catalyst F-4). The measurement and calculation methods for the total content of oxides of active component metals and promoter metals in the catalyst are all known measurement and calculation methods in the art.

Comparative Example 4

This comparative example provides a diesel hydrogenation catalyst as a comparative catalyst.

The preparation method of this comparative catalyst comprises the following steps:

(1) Dissolve 3.16g of ammonium metatungstate and 1.57g of nickel nitrate in 9.0mL of deionized water to prepare an immersion solution;

(2) this dipping solution is added dropwise to 9.0g of extruded alumina bars with a diameter of 1.5mm to obtain a catalyst semi-finished product;

(3) the catalyst semi-finished product was allowed to stand in the air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 5°C/min, and roasted at 500°C in an air atmosphere for 4 hours to obtain the described The comparative catalyst 4. The total content of nickel-tungsten tungsten oxide in the comparative catalyst was measured to be 25.0 wt % (all based on the total weight of the comparative catalyst).

Example 5

The present embodiment provides a hydrogenation catalyst, which is prepared by an impregnation method, and specifically includes the following steps:

(1) Mix 5.97g pseudo-boehmite, 10.5g concentrated phosphoric acid (85% by mass), 6.4g triethylamine, 0.5g stannous acetate and 29.9g deionized water to form a mixed gel , 100mL autoclave was dynamically crystallized for 20h, washed, filtered, dried, and calcined to obtain Sn(II)AlPO ₄ -5 molecular sieve. Calculated according to the molecular sieve mass of 100wt%, the SnO content was 0.3wt%;

(2) mixing Sn(II)AlPO ₄ -5 molecular sieve and pseudo-boehmite according to a mass ratio of 2:8, extruding, drying naturally, and calcining at 550° C. for 4 hours to obtain a carrier;

(3) Dissolve 1.57g of cobalt nitrate and 2.27g of ammonium molybdate in 8.0g of deionized water, and configure it into a dipping solution;

(4) this dipping solution is added dropwise to the above-mentioned carrier with a diameter of 1.5 mm extruded from 8.5 g to obtain a catalyst semi-finished product;

(5) above-mentioned catalyst semi-finished product was left standstill in air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 4°C/min, roasted at 500°C, under air atmosphere for 4 hours to obtain a hydrogenation catalyst F-5.

The total amount of cobalt and molybdenum oxides in the catalyst F-5 was measured to be 20.5 wt % (based on the total weight of the catalyst F-5). The measurement and calculation methods for the total content of oxides of active component metals and promoter metals in the catalyst are all known measurement and calculation methods in the art.

Comparative Example 5

This comparative example provides a diesel hydrogenation catalyst as a comparative catalyst.

The preparation method of this comparative catalyst comprises the following steps:

(1) Dissolve 2.27g of ammonium molybdate and 1.57g of cobalt nitrate in 9.0mL of deionized water to prepare an immersion solution;

(2) this dipping solution is added dropwise to 8.5g of extruded alumina bars with a diameter of 1.5mm to obtain a catalyst semi-finished product;

(3) the catalyst semi-finished product was allowed to stand in the air for 24 hours, then dried in an oven at 120°C, then heated at a rate of 5°C/min, and roasted at 500°C in an air atmosphere for 4 hours to obtain the described The comparative catalyst 5. The total content of nickel-tungsten tungsten oxide in the comparative catalyst was measured to be 20.5 wt % (all based on the total weight of the comparative catalyst).

Test Example 1

This test example provides a test experiment for the hydrotreating of the above catalyst for coking diesel.

The above-mentioned five catalysts of the embodiment and the corresponding five kinds of comparative catalysts are tested and tested, and the reaction process is as follows: pre-sulfide treatment is carried out before application, so that the catalyst has better hydrogenation effect. The pre-sulfidation was carried out using a 10 mL high-temperature and high-pressure hydrogenation micro-reaction device, which was in-situ pre-sulfurization by wet method, that is, wet-method pre-sulfurization was adopted, and the catalyst was not discharged after pre-sulfidation, and the hydrogenation reaction was continued directly in the reactor. The pre-vulcanized oil was a n-decane solution containing 5wt% CS ₂ , the pre-vulcanization temperature was 300°C, the pressure was 4MPa, the liquid hourly space velocity was 1.5h ^-1 , and the volume ratio of hydrogen to oil was 300.

The hydroprocessing of this test example was carried out using a 10 mL high temperature and high pressure hydrogenation micro-reaction device. As the raw material for evaluation, Daqing coking diesel oil was used. The specific gravity (d ₄ ²⁰ ) of the coking diesel oil was 0.8196, the sulfur content was 1187 ppm, and the total nitrogen content was 837 ppm. The raw material is pumped by a plunger pump, and the reacted oil sample is cooled by the high separator, and then collected and analyzed in the low separator. The temperature of hydrotreating is 280°C, the pressure is 4MPa, the liquid hourly space velocity is 1.0h ^-1 , and the volume ratio of hydrogen to oil is 800. Under the conditions of the same active metal content, the evaluation results of the hydrogenation catalyst are shown in Table 1.

Table 1 Catalyst evaluation results after hydrotreating

From the data in Table 1, it can be seen that the catalyst prepared by using the composite carrier shows better desulfurization and denitrification activity. It shows that this type of catalytic activity has higher catalytic activity than existing catalysts.

Test case 2

This test example provides a test experiment for the hydrotreating of catalytically cracked diesel fuel by the above catalyst.

The above-mentioned five catalysts of the embodiment and the corresponding five kinds of comparative catalysts are tested and tested, and the reaction process is as follows: all of the catalysts are pre-sulfided before application, so that the catalysts have better hydrogenation effect. The pre-sulfidation was carried out using a 10 mL high-temperature and high-pressure hydrogenation micro-reaction device, which was in-situ pre-sulfurization by wet method, that is, wet-method pre-sulfurization was adopted, and the catalyst was not discharged after pre-sulfidation, and the hydrogenation reaction was continued directly in the reactor. The pre-vulcanized oil was a n-decane solution containing 5wt% CS ₂ , the pre-vulcanization temperature was 300°C, the pressure was 4MPa, the liquid hourly space velocity was 1.5h ^-1 , and the volume ratio of hydrogen to oil was 300.

The hydrogenation treatment of this test example was carried out with a 10 mL high temperature and high pressure hydrogenation micro-reaction device. As the raw material for evaluation, Daqing catalytically cracked diesel oil was used. The specific gravity (d ₄ ²⁰ ) of the catalytically cracked diesel oil was 0.8796, the sulfur content was 1078 ppm, and the total nitrogen content was 829 ppm. The raw material is pumped by a plunger pump, and the reacted oil sample is cooled by the high separator, and then collected and analyzed in the low separator. The temperature of hydrotreating is 280°C, the pressure is 4MPa, the liquid hourly space velocity is 1.0h ^-1 , and the volume ratio of hydrogen to oil is 800. Table 2 shows the results of the catalyst evaluation after hydroprocessing.

Table 2 Catalyst evaluation results after hydrotreating

From the data in Table 2, it can be seen that the catalyst prepared by using the composite carrier shows better desulfurization and denitrification activity. It shows that this type of catalytic activity has higher catalytic activity than existing catalysts.

Claims (10)

1. A hydrofinishing catalyst, wherein, based on the total weight of the catalyst as 100wt%, the catalyst comprises 50wt%-95wt% of a carrier and 5wt%-50wt% of an active metal component; The carrier includes Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ ; The active metal components include oxides and/or sulfides of one or more of Co, Mo, Ni and W. 2. The hydrofinishing catalyst according to claim 1, wherein, based on the total weight of the carrier as 100wt%, the content of the Sn(II) _AlPO4-5 molecular sieve is 5wt%-60wt%; preferably 15wt%-45wt%. 3. The hydrofinishing catalyst according to claim 1, wherein the carrier is prepared by the following method: The carrier is prepared by mixing Sn(II)AlPO ₄ -5 molecular sieve with the precursor for preparing γ-Al ₂ O ₃ , and then forming and calcining. 4. The hydrorefining catalyst according to claim 1, wherein, in the Sn(II)AlPO ₄ -5 molecular sieve, in terms of SnO, the content is 0.1wt%-4.0wt%; preferably 0.2wt%- 2.0 wt%. 5. The hydrofinishing catalyst according to claim 1, wherein the active metal components are oxides and/or sulfides of Co and Mo, oxides and/or sulfides of Ni and W, Co and Mo and oxides and/or sulfides of W; Preferably, the active metal components are selected from oxides of corresponding active metals; Preferably, the content of the active metal group is 20wt%-40wt% of the total weight of the catalyst. 6. the preparation method of the hydrorefining catalyst described in any one of claim 1-5, wherein, this method comprises the following steps: The Sn(II)AlPO ₄ -5 molecular sieve is mixed with the precursor for preparing γ-Al ₂ O ₃ , and then the carrier is prepared by molding and calcining; The hydrofinishing catalyst is prepared by impregnating the support with a soluble metal salt solution containing Co, Mo, Ni and/or W, and then drying and calcining. 7. the application of the hydrotreating catalyst described in any one of claim 1-5 in gasoline, diesel oil hydrotreating reaction; Preferably, the active metal components in the hydrofinishing catalyst are oxides and/or sulfides of Co and Mo, oxides and/or sulfides of Ni and W, oxides and/or oxides of Co and Mo and W or sulfide. 8. A carrier containing Sn(II)AlPO ₄ -5 molecular sieve and γ-Al ₂ O ₃ , wherein, based on the total weight of the carrier as 100 wt %, the Sn(II)AlPO ₄ -5 molecular sieve The weight accounts for 5wt%-60wt%; preferably 15wt%-45wt%; The carrier is prepared by the following method: The carrier is prepared by mixing Sn(II)AlPO ₄ -5 molecular sieve with the precursor for preparing γ-Al ₂ O ₃ and calcining; Preferably, the precursor is pseudo-boehmite; Further preferably, the roasting conditions are: roasting at 450-650° C. for 2-8 hours. 9. A Sn(II)AlPO _4-5 molecular sieve, wherein the Sn(II)AlPO _4-5 molecular sieve is prepared by the following method: (1) the divalent tin source is mixed with the raw material for preparing AlPO ₄ -5 molecular sieve to prepare mixed gel; (2) crystallizing and calcining the mixed gel to obtain the Sn(II)AlPO ₄ -5 molecular sieve; Preferably, the divalent tin source comprises stannous chloride or stannous acetate; Further preferably, the crystallization treatment is hydrothermal crystallization treatment; More preferably, the conditions of the hydrothermal crystallization treatment are: crystallization at 140-200° C. for 14-36 hours; More preferably, the conditions of the roasting treatment are: roasting at 450-650° C. for 2-8 hours. 10. The Sn(II)AlPO ₄ -5 molecular sieve according to claim 9, wherein, in step (1), the raw materials for preparing the AlPO ₄ -5 molecular sieve include: water, aluminum source, phosphorus source and templating agent; Preferably, the aluminum source includes pseudoboehmite, the phosphorus source includes phosphoric acid, and the template agent includes triethylamine, triethanolamine, tetraethylammonium bromide or tetraethylammonium hydroxide; Further preferably, the water, aluminum source, phosphoric acid, tin source and templating agent are respectively based on H ₂ O, Al ₂ O ₃ , P ₂ O ₅ , SnO and templating agent, and the molar ratio of each component is 30-70 :1:0.9-1.7:0.01-0.2:1-3.