WO2023116391A1 - B acid-containing hydrogenation catalyst carrier, and preparation and use thereof - Google Patents

Abstract

A B acid-containing hydrogenation catalyst carrier, and the preparation and use thereof. The B acid-containing hydrogenation catalyst carrier is prepared with a commercial alumina carrier and a B acid-containing alumina material as raw materials, wherein on the basis that the total weight of the raw materials is 100%, the B acid-containing hydrogenation catalyst carrier comprises 50-95% of the commercial alumina carrier, and 5-50% of the B acid-containing alumina material. By introducing the B acid-containing alumina material into the catalyst carrier, a carrier material containing rich B acid centers is prepared, and the B acid is mainly weak acid and moderately strong acid. An activity evaluation result of an Ni-W catalyst prepared from the B acid-containing hydrogenation catalyst carrier shows that the catalyst has a high hydrodesulfurization activity, and improves the direct desulfurization and isomerization-direct desulfurization reaction paths of 4,6-DMDBT without obvious influence on the liquid yield, indicating that no obvious cracking reaction occurs during the hydrogenation reaction process.

Description

A hydrogenation catalyst carrier containing B acid and its preparation and application technical field

The invention relates to a hydrogenation catalyst carrier containing B acid and its preparation and application, belonging to the technical field of petroleum refining hydrogenation.

Background technique

With the continuous upgrading of oil quality, increasingly stringent environmental protection regulations, and increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied all over the world. With the implementation of the National VI diesel standard, the severity of the diesel hydrogenation unit has increased, and the operating cycle of the unit has been shortened. In order not to affect the operating period of the unit, higher requirements are placed on the catalyst activity. B acid centers are introduced into the catalyst to change the hydrogenation of sulfides. The key to solving this problem is to increase the efficiency of the hydrogenation reaction and reduce the reaction temperature.

At present, the catalyst carrier for diesel hydrotreating is generally dominated by alumina, and the unmodified alumina carrier surface only has L acid. In order to increase the B acid on the catalyst surface, researchers added F, B, Zr and other elements to increase the B acid content of the carrier, but the B acid centers formed by these modification methods are random and the acid content is uncontrollable. Diesel hydrorefining catalysts should not have too strong requirements on the strength of the carrier acid, and weak acids should be the main ones to avoid cracking during the hydrogenation process and affect the yield of refined diesel oil. For cracking and isomerization catalysts, molecular sieves and amorphous silica-alumina are generally added to the carrier to adjust the acidity and acidity of the carrier. Generally, this type of catalyst requires stronger acidity.

Chinese patent CN104646073A discloses a hydrogenation catalyst carrier, which is molecular sieve 10-70wt%, alumina 10-40wt%, silicon dioxide 5-30wt% by weight percentage, and the rest is binder; hydrogenation catalyst carrier specific surface area is 380-573m ² /g, pore volume 0.63-0.94cc/g, infrared acid content 0.10-0.45mmol/g, ratio of B acid to L acid 2.3-0.9:1; molecular sieve is mesoporous amorphous silicon aluminum The multi-level porous composite molecular sieve coated with microporous Beta molecular sieve has a sodium oxide content of ≤0.05 wt%, and an infrared acid content of 0.23-0.58 mmol/g.

Chinese patent CN108262066A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein, the specific surface area of the hydrogenation catalyst carrier is 220-430m ² /g, and the total pore volume is 0.35- 0.70mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, the The content of the solid acid component is 10-80%, and the content of the amorphous heat-resistant oxide is 20-90%; wherein, the solid acid component is MCM-22 molecular sieve, and its silicon-aluminum ratio is 10-50, The specific surface area is 400-700m ² /g, and the pore volume is 0.35-0.75mL/g.

Chinese patent CN106311309A discloses a hydrogenation catalyst carrier, including an alumina carrier and a molecular sieve, the weight ratio of the alumina carrier to the molecular sieve is 7:1; the preparation method of the above-mentioned hydrogenation catalyst carrier includes the following steps: a. Aluminum carrier and molecular sieve are dissolved in deionized water to form a mixed slurry; b. The mixed slurry is roasted to obtain a finished catalyst carrier; the pore volume of the alumina carrier is 0.2-0.5mL/g, and the specific surface area is 400-500m ² /g , the pores with a diameter of 5-8nm account for 90% of the total pore volume, the crushing strength is 300N/cm-500N/cm, the total infrared acid content is 0.30-0.45mmol/g, and the medium-strong acid content/infrared total acid content is 0.56-0.81, L acid content/B acid content is 1.40-2.30.

Chinese patent CN108262076A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein: the specific surface area of the hydrogenation catalyst carrier is 220-450m ² /g, and the total pore volume is 0.35-0.70 mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, the solid acid The component content is 10-80%, and the amorphous heat-resistant oxide content is 20-90; wherein, the solid acid component is a mixture of MCM-22 molecular sieve and ZSM-5 molecular sieve, and the mixing ratio is 1:10-10 : 1; the silicon-aluminum ratio of the MCM-22 molecular sieve is 10-60, the specific surface area is 400-600m ² /g, and the pore volume is 0.35-0.75mL/g; the silicon-aluminum ratio of the ZSM-5 molecular sieve is 10 -60, the specific surface area is 300-500m ² /g, and the pore volume is 0.15-0.65mL/g.

Chinese patent CN108262074A discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, wherein: the specific surface area of the hydrogenation catalyst carrier is 220-450m ² /g, and the total pore volume is 0.35- 0.70mL/g, the amount of infrared acid is 0.50-1.0mmol/g, the ratio of B acid to L acid is 0.2-1.0, and the radial crush resistance is greater than 130N/cm; based on the total weight of the carrier, solid The acid component content is 10-80%, and the amorphous heat-resistant oxide content is 20-90%; wherein, the solid acid component is a mixture of MCM-22 molecular sieve and Y molecular sieve, and the mixing ratio is 1:10-10 : 1; the silicon-aluminum ratio of the MCM-22 molecular sieve is 10-60, the specific surface area is 400-600m ² /g, and the pore volume is 0.35-0.75mL/g; the silicon-aluminum ratio of the Y molecular sieve is 5-60 , the specific surface area is 500-800m ² /g, the pore volume is 0.8-1.0mL/g, and the unit cell parameter is 2.430-2.450nm.

Chinese patent CN105983445A discloses a hydrogenation catalyst carrier, wherein: aluminum oxide containing silicon and phosphorus is used as the hydrogenation catalyst carrier, the pore volume of the carrier is 0.7-1.5mL/g, the specific surface area is 250-450m ² /g, the catalyst The 20-30nm pore ratio of the carrier reaches more than 20%. The acid properties of the carrier surface are: the acid content is 0.2-0.7mmol/g, and the B acid is 0.1-0.3mmol/g.

Chinese patent CN103896318A discloses a B-rich acid-rich mesoporous alumina support material for catalytic cracking catalysts, which is prepared by modifying pseudo-boehmite with NH ₄ BF ₄ and adding P123 template agent. The material has mesoporous structure, the pore volume is 0.32-0.41mL/g, and the specific surface area is 200-237m ² /g; the defect of this technology or the deficiency relative to the present invention: the pore volume specific surface area of the material disclosed in the present invention has limitations, and the oxidation Aluminum material is used in catalytic cracking.

Chinese patent CN112619632A discloses a boron, phosphorus, fluorine, magnesium and other element-modified alumina carrier prepared by co-precipitation method. The amount of acid is 0.08-0.150mmol/g, and the amount of L acid is 0.10-0.40mmol/g.

In the literature "Preparation of B-rich Acid Alumina and Hydrodesulfurization Reaction Performance Using It as Carrier Catalyst", ammonium fluoroborate was used to modify pseudo-boehmite to prepare B-acid-rich alumina carrier, which was prepared by adjusting the F/Al ratio The alumina carrier with a B/L ratio of 0.17-1.06 is used for 4,6-DMDBT hydrogenation, which can improve the direct isomerization-direct desulfurization path of 4,6-DMDBT. However, the specific surface and pore structure of the support are obviously destroyed during the modification process of the support. When the B/L value is 1.06, the specific surface loss is 17.3%, and the pore volume loss is 7.9%. Such a support is not conducive to the dispersion of active metals and reactants. diffusion.

In summary, at present, B acid is introduced into the catalyst carrier in this field, and most of them are added various molecular sieves containing B acid in the carrier, but the catalyst carrier containing molecular sieve has strong acidity and is suitable for preparing cracking catalyst; Introducing elements such as F, B, Zr, etc., the acid centers of the carrier prepared by this method are randomly formed, and the amount of acid is uncontrollable. When increasing the amount of carrier B acid, the total acid amount of the carrier is too large, or the ratio of B acid amount is increased but the amount of B acid is not significantly increased. In addition, the specific surface area of the carrier is increased while the carrier pore size is increased. The loss is too great.

Therefore, providing a novel B-acid-containing hydrogenation catalyst support and its preparation and application has become an urgent technical problem in this field.

Contents of the invention

In order to solve the above-mentioned shortcomings and deficiencies, an object of the present invention is to provide a hydrogenation catalyst carrier containing B acid.

Another object of the present invention is to provide a method for preparing the above-mentioned hydrogenation catalyst carrier containing B acid.

Another object of the present invention is to provide a hydrorefining catalyst whose carrier is the above-mentioned B acid-containing hydrogenation catalyst carrier.

Another object of the present invention is to provide the application of the above-mentioned hydrorefining catalyst in the hydrorefining process in the field of petroleum refining.

In order to achieve the above object, on the one hand, the present invention provides a hydrogenation catalyst carrier containing B acid, wherein, the hydrogenation catalyst carrier containing B acid is based on a commercial alumina carrier and an alumina material containing B acid The raw material is prepared, wherein, based on the total weight of the raw material being 100%, it includes 50-95% of commercial alumina carrier and 5-50% of alumina material containing B acid.

As a specific embodiment of the B-acid-containing hydrogenation catalyst carrier of the present invention, wherein, based on the total weight of the B-acid-containing hydrogenation catalyst carrier as 100%, it includes 60-75% of commercial oxidation Aluminum support and 25-40% alumina material containing B acid.

As a specific embodiment of the above-mentioned B-acid-containing hydrogenation catalyst carrier of the present invention, wherein, the B/L acid value of the B-acid-containing alumina material is 0.3-2.5, and the specific surface area is 200-300m ² / g, the pore volume is 0.55-0.90mL/g.

As a specific embodiment of the B-acid-containing hydrogenation catalyst carrier mentioned above in the present invention, the B/L acid value of the B-acid-containing alumina material is 0.8-1.6.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, wherein the alumina material containing B acid is made of common pseudo-boehmite as a raw material and passed through _NH4 by sol-gel method Modified BF ₄ , including:

First prepare pseudo-boehmite into a uniform alumina sol slurry with an acid solution, then add a saturated solution of NH ₄ BF ₄ at room temperature to the alumina sol slurry dropwise under stirring conditions to form a gel, and then prepare the gel Carry out vacuum drying and then roast to obtain the alumina material containing B acid.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, the pseudo-boehmite is prepared into a uniform aluminum sol slurry with an acid solution at a temperature of 70-80°C.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, the acid solution includes an inorganic acid solution or an organic acid solution. In some embodiments of the present invention, the inorganic acid solution may be, for example, concentrated nitric acid.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, the specific surface area of the pseudo-boehmite is 300-600m ² /g, and the pore volume is 0.40-0.70mL/g.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, wherein, the dropping rate of the NH ₄ BF ₄ saturated solution is 3-5 mL/min.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, wherein the F/Al molar ratio is controlled to be 0.06-0.18.

As a specific embodiment of the B-acid-containing hydrogenation catalyst carrier mentioned above in the present invention, the calcination temperature is 350-450°C, preferably 400-450°C.

The present invention controls the calcination temperature in the preparation process of the B-acid-containing alumina material within the above-mentioned range, which can ensure that the B-acid content on the surface of the B-acid-containing alumina material is not destroyed.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, the specific surface area of the commercial alumina carrier is 380-600m ² /g, and the pore volume is 0.40-0.60mL/g.

As a specific embodiment of the hydrogenation catalyst carrier containing B acid mentioned above in the present invention, wherein, the specific surface area of the hydrogenation catalyst carrier containing B acid is 220-450m ² /g, and the pore volume is 0.45-0.70mL /g;

Preferably, the specific surface area is 300-400m ² /g, and the pore volume is 0.50-0.60mL/g.

As a specific embodiment of the B-acid-containing hydrogenation catalyst carrier described above in the present invention, wherein, the B/L acid value of the B-acid-containing hydrogenation catalyst carrier is between 0.01-0.8, and the infrared acid content at 150°C is It accounts for 60-70% of the total acid content, of which B acid accounts for 5-40% of the infrared acid content; 250°C infrared acid accounts for 20-30% of the total acid content, of which B acid accounts for 4-4% of the infrared acid content 40%; 350 ℃ infrared acid accounts for 5-15% of the total acid, of which B acid accounts for 2-35% of the infrared acid;

Preferably, the B/L acid value of the hydrogenation catalyst carrier containing B acid is between 0.3-0.59, and the amount of infrared acid at 150°C accounts for 63-68% of the total acid amount, wherein the amount of B acid accounts for 10% of the amount of infrared acid 20-40%; 250°C infrared acid accounts for 23-28% of the total acid amount, of which B acid accounts for 20-40% of the infrared acid amount; 350°C infrared acid amount accounts for 8-12% of the total acid amount, of which The amount of B acid accounts for 12-34% of the amount of infrared acid.

Wherein, the "infrared acid content" in the present invention is the sum of "B acid content" and "L acid content", "total acid content" refers to the sum of infrared acid content at different temperature points, and the infrared acid content at different temperature points The ratio to the total acid refers to the ratio of the infrared acid corresponding to the temperature point to the total acid.

On the other hand, the present invention also provides the preparation method of the hydrogenation catalyst carrier containing B acid mentioned above, wherein, the preparation method comprises:

Mix the commercial alumina carrier and the alumina material containing B acid according to the proportion, add the safflower powder, dry mix and make the powder mix uniformly, and obtain the dry mixed sample;

The nitric acid solution is added to the dry mixed sample for wet mixing to obtain a wet mixed sample;

The wet-mixed sample is molded, and then the molded product is dried and roasted to obtain the hydrogenation catalyst carrier containing B acid.

In the present invention, the commercial alumina carrier and the alumina material containing B acid are mixed in a certain proportion to prepare the hydrogenation catalyst carrier containing B acid, and the alumina material containing B acid can be introduced into the carrier of the catalyst, thereby realizing B on the catalyst carrier. Controllable preparation of acidity.

The present invention does not make any adjustments to the amount of scallop powder used in the preparation process of the hydrogenation catalyst carrier containing B acid, the concentration and amount of nitric acid solution, the dry mixing time, the wet mixing time, the molding method, drying and roasting conditions, etc. For specific requirements, those skilled in the art can reasonably set these parameters according to actual operation needs, as long as the purpose of preparing the hydrogenation catalyst carrier containing B acid can be realized.

In yet another aspect, the present invention also provides a hydrofinishing catalyst, wherein the carrier of the hydrofinishing catalyst is the above-mentioned B acid-containing hydrogenation catalyst carrier.

As a specific embodiment of the hydrotreating catalyst mentioned above in the present invention, the strength of the hydrotreating catalyst is >130 N/cm. In some preferred embodiments of the present invention, the strength of the hydrofining catalyst is ≥ 160 N/cm.

In another aspect, the present invention also provides the application of the above-mentioned hydrorefining catalyst in the hydrorefining process in the field of petroleum refining.

As a specific implementation of the above-mentioned application of the present invention, wherein, the hydrofinishing process in the field of petroleum refining comprises gasoline and diesel hydrofinishing.

The present invention firstly synthesizes an alumina material containing a high amount of B acid by a sol-gel method, and then mixes an appropriate proportion of the alumina material containing B acid with a commercial alumina carrier to prepare the hydrogenation catalyst carrier containing B acid. A method of introducing B acid into the hydrogenation catalyst carrier makes the acid strength and acid amount of B acid on the carrier all within a controllable range, and the appropriate acid strength and acid amount on the carrier can promote the distillate oil with steric hindrance. The difficult-to-remove sulfides are removed through the direct desulfurization reaction path, thereby increasing the hydrodesulfurization reaction rate, reducing the reaction temperature, and simultaneously promoting the simultaneous removal of sulfur, nitrides, and aromatics.

The beneficial technical effect that the present invention can reach comprises:

(1) In the present invention, by introducing the alumina material containing B acid into the catalyst carrier, a carrier material rich in B acid centers is prepared, and the carrier material is mainly weak acid and medium strong acid.

(2) The Ni-W catalyst activity evaluation result that adopts the hydrogenation catalyst carrier preparation that contains B acid provided by the present invention shows that this catalyst hydrodesulfurization activity is high, and has improved the direct desulfurization of 4,6-DMDBT and iso Structure-direct desulfurization reaction path, and did not significantly affect the liquid yield, indicating that no obvious cracking reaction occurred during the hydrogenation reaction. The reason or mechanism for this beneficial effect is: 4,6-DMDBT has a large steric hindrance, and the hydrogenation active center is difficult to contact with the sulfur atom, resulting in a low reaction rate and desulfurization rate in the direct hydrodesulfurization reaction. The B in the catalyst The existence of the acid center promotes the methyl transfer of 4 and 6 positions of 4,6-DMDBT and improves the direct desulfurization and isomerization-direct desulfurization reaction pathways, greatly improving the desulfurization efficiency and desulfurization activity.

Detailed ways

It should be noted that the term "comprising" and any variations thereof in the specification and claims of the present invention are intended to cover non-exclusive inclusion, for example, a process, method, system, product or process that includes a series of steps or units. The apparatus is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to the process, method, product or apparatus.

The "ranges" disclosed herein are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively. A given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.

In the present invention, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.

In the present invention, if there is no special description, all the embodiments and preferred embodiments mentioned in the present invention can be combined with each other to form a new technical solution.

In the present invention, if there is no special description, all the technical features and preferred features mentioned in the present invention can be combined with each other to form a new technical solution.

In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the accompanying tables and examples. The following described embodiments are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

Example 1

This embodiment provides a series of alumina materials containing B acid, which are prepared by a preparation method comprising the following steps:

First 20g of pseudo-boehmite powder (CL0) is added to 285mL of deionized water, while stirring, about 10g of concentration is added dropwise to the concentrated nitric acid of 68wt% (the same below); then heated to 80°C, then added dropwise with concentrated nitric acid to Complete gelation to obtain a uniform aluminum sol slurry, and control the pH value of the aluminum sol slurry to <2.

Weigh a certain mass of NH ₄ BF ₄ , and prepare a saturated NH ₄ BF ₄ solution at room temperature.

Pour different amounts of NH ₄ BF ₄ saturated solutions into the rate-control injector, and gradually drop them into the vigorously stirred aluminum sol slurry. During the dropping process, adjust the dropping speed to 4mL/min. Afterwards, stir vigorously until the aluminum sol slurry forms a gel, then vacuum-dry the gel at 110°C for 10 hours (vacuum degree less than 80mmHg), and then roast it at 400°C for 4 hours, and the product obtained after roasting is B-containing acid alumina material.

Wherein, the F/Al molar ratios obtained by elemental analysis of the alumina material containing B acid are respectively 0.06, 0.09, 0.12, 0.15, and 0.18. Correspondingly, the alumina material containing B acid is recorded as CL1-CL5, and the pseudo-boehmite aluminum blank sample is recorded as CL0, and the pore structure properties and acidity of CL0 and CL1-CL5 are shown in Table 1.

Table 1 Physical property data of alumina material containing B acid

Note: The specific surface area (S _BET ), pore volume (V) and B/L acid value in Table 1 are all measured by conventional methods in the art.

It can be seen from the above Table 1 that the alumina material containing B acid was successfully prepared in Example 1, the B/L acid value is 0.3-2.5, the specific surface area is 200-300m ² /g, and the pore volume is 0.55-0.7mL/ g.

It can also be known from the above table 1 that after the modification of pseudo-boehmite powder with NH ₄ BF ₄ , the B acid increases, but at the same time, the specific surface has a certain negative impact, and the specific surface gradually decreases with the increase of the F/Al molar ratio , the pore volume continues to increase; but there is an inflection point in the B/L ratio. When F/Al=0.15, B/L reaches 2.45, and when F/Al continues to increase to 0.18, B/L drops to 1.54.

Example 1-1

This example provides a series of alumina materials containing B acid. The difference between the preparation method and the preparation method provided in Example 1 is: this example prepares F/Al= by controlling the addition of _{NH4BF4 saturated} solution 0.15 B acid alumina material;

The physical property data of the pseudo-boehmite (DLO and ELO) used are shown in Table 2 below.

The physical property data of different pseudo-boehmite used in this embodiment and the physical property data of the prepared B-acid alumina material with F/Al=0.15 are shown in Table 2 below.

Table 2 Different pseudo-boehmite and the physical property data of the obtained alumina material containing B acid

It can be seen from the above Table 2 that the specific surface area of the B acid-containing alumina materials DL1 and EL1 synthesized in this example is in the range of 200-300m ² /g, and the pore volume is in the range of 0.7-0.9mL/g.

In the following examples, a series of alumina hydrogenation catalyst supports containing B acid were prepared by using commercial alumina, wherein the specific surface area of commercial alumina powder was 425 m ² /g, and the pore volume was 0.52 mL/g.

Example 2

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 95g of commercial alumina, 5g of CL2 (or CL3, CL4) materials, add 3g of scallop powder and dry mix them in a large crucible for 20 minutes, so that the powders are evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-1, ZT3-1, and ZT4-1.

Example 3

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 90g of commercial alumina, 10g of CL2 (or CL3, CL4) materials, add 3g of scallop powder and dry mix them in a large crucible for 20min, so that the powders are evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-2, ZT3-2, and ZT4-2.

Example 4

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 85g of commercial alumina, 15g of CL2 (or CL3, CL4) materials, add 3g of scallop powder and dry mix them in a large crucible for 20 minutes, so that the powders are evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-3, ZT3-3, and ZT4-3.

Example 5

The present embodiment provides a series of B acid-containing hydrogenation catalyst supports, which are prepared by a preparation method comprising the following steps:

Take 80g of commercial alumina, 20g of CL2 (or CL3, CL4) material, add 3g of turnip powder and dry mix in a large crucible for 20 minutes, so that the powder is mixed evenly, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-4, ZT3-4, and ZT4-4.

Example 6

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 70g of commercial alumina, 30g of CL2 (or CL3, CL4) material, add 3g of scallop powder and dry mix them in a large crucible for 20min, so that the powder is evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-5, ZT3-5, and ZT4-5.

Example 7

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 60g of commercial alumina, 40g of CL2 (or CL3, CL4) materials, add 3g of scallop powder and dry mix them in a large crucible for 20 minutes, so that the powders are evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-6, ZT3-6, and ZT4-6.

Example 8

This embodiment provides a series of hydrogenation catalyst supports containing B acid, which are prepared by a preparation method comprising the following steps:

Take 50g of commercial alumina and 50g of CL2 (or CL3, CL4) material, add 3g of scallop powder and dry mix them in a large crucible for 20min to make the powder mix evenly and obtain a dry mixed sample;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8mm. After drying in a blast drying oven at 120°C for 4 hours, the program Raise the temperature to 450°C and roast for 4 hours to obtain hydrogenation catalyst supports containing B acid, which are respectively denoted as ZT2-7, ZT3-7, and ZT4-7.

Comparative example 1

This comparative example provides a kind of hydrogenation catalyst carrier, and it is to make by the preparation method comprising the following steps:

Take 100g of commercial alumina (specific surface area is 425m ² /g, pore volume is 0.52mL/g), add 3g of Selina powder into a large crucible and carry out dry mixing for 20min, so that the powder is evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 85g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C and calcined for 4 hours to obtain a hydrogenation catalyst carrier, which was designated as ZT-0.

Comparative example 2

This comparative example provides a hydrogenation catalyst carrier containing B acid, which is prepared by a preparation method comprising the following steps:

Take 100 g of the alumina material CL1 containing B acid prepared in Example 1, add 3 g of turnip powder in a large crucible and carry out dry mixing for 20 minutes, so that the powder is evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 80g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C and calcined for 4 hours to obtain a hydrogenation catalyst support containing B acid, which was designated as ZT-B1.

Comparative example 3

This comparative example provides a hydrogenation catalyst carrier containing B acid, which is prepared by a preparation method comprising the following steps:

Take 100 g of the alumina material DL1 containing B acid prepared in Example 1-1, add 3 g of turnip powder in a large crucible and carry out dry mixing for 20 minutes, so that the powder is evenly mixed, and a dry mixed sample is obtained;

Add 0.15g of concentrated nitric acid into 80g of deionized water, fully dissolve it, then slowly add it to the dry-mixed sample, and wet-mix the powder for 20 minutes to obtain a wet-mixed sample;

The wet-mixed sample was extruded with a twin-screw extruder, and the final extruded sample was a clover strip carrier with an outer diameter of 1.8 mm. After drying in a blast drying oven at 120 ° C for 4 hours, the The temperature was raised to 450°C, and calcined for 4 hours to obtain a hydrogenation catalyst support containing B acid, which was designated as ZT-B2.

The physical property parameters and acid distribution of the hydrogenation catalyst carrier containing B acid provided by Example 2-Example 8 of the present invention and Comparative Example 2-Comparative Example 3 and the hydrogenation catalyst carrier provided by Comparative Example 1 are shown in Table 3 and Table 4 .

Table 3 Embodiment 2-Example 8 and Comparative Example 2-Comparative Example 3 provide the hydrogenation catalyst carrier containing B acid and the physical parameters of the hydrogenation catalyst carrier that Comparative Example 1 provides

Note: The specific surface area (S _BET ), pore volume (V) and B/L acid value in Table 3 are all measured by conventional methods in the art.

Table 4 Example 2-Example 8 and Comparative Example 2-Comparative Example 3 The hydrogenation catalyst carrier containing B acid provided by Comparative Example 3 and the acid distribution of the hydrogenation catalyst carrier provided by Comparative Example 1

Note: The experimental data in Table 4 are all measured by conventional methods in this field, and in Table 4, the percentage data of LAS acid content and the percentage data of BAS acid content at a certain temperature point are calculated based on the total acid content of.

It can be seen from Table 3 and Table 4 that the specific surface area of the hydrogenation catalyst carrier containing B acid is ^220-450m2 /g, the pore volume is 0.45-0.70mL/g, and the B/L acid value is between 0.01- Between 0.8 and 150°C, infrared acid accounts for 60-70% of the total acid, of which B acid accounts for 5-40%; at 250°C, infrared acid accounts for 20-30% of the total acid, of which B acid accounts for 4-40% %; 350 ℃ infrared acid accounts for 5-15% of the total acid, of which B acid accounts for 2-35%.

It can also be seen from Table 3 and Table 4 that in the embodiment of the present invention, by introducing the alumina material containing B acid into the catalyst carrier, a carrier material rich in B acid centers is prepared, and the carrier material is mainly weak acid and medium strong acid.

Example 9

This example provides a series of W-Ni catalysts, which are ZT2-3 (B/L=0.11), ZT3-4 (B/L=0.27), ZT3-6 (B/L=0.27) prepared above 0.50), ZT3-7(B/L=0.59), ZT4-7(B/L=0.80) are prepared as carriers, and their preparation methods specifically include:

(1) The nickel nitrate of 17.1g and the ammonium metatungstate of 46.0g are dissolved in the deionized water of 540.0g, are mixed with impregnation solution;

(2) Weigh 50g of ZT2-3 (B/L=0.11), ZT3-4 (B/L=0.27), ZT3-6 (B/L=0.50), ZT3-7 (B/L=0.59) ), ZT4-7 (B/L=0.80) hydrogenation catalyst carrier containing B acid, the impregnation solution prepared in step (1) is added to the 50g carrier by the method of equal volume impregnation, and the catalyst precursor obtained after each impregnation The body was placed in an ultrasonic oscillator for 20 minutes, then dried at 110°C for 4 hours, and then calcined at 480°C for 4 hours in an air atmosphere to prepare W-Ni catalysts, which were named CAT-1 and CAT-2 respectively. , CAT-3, CAT-4, CAT-5.

Comparative example 4

This comparative example provides a kind of W-Ni catalyst, and it is made with ZT-0 that above-mentioned preparation obtains as carrier, and its preparation method specifically comprises:

(1) The nickel nitrate of 17.1g and the ammonium metatungstate of 46.0g are dissolved in the deionized water of 540.0g, are mixed with impregnation solution;

(2) Weigh 50 g of the ZT-0 carrier, and add the impregnation solution prepared in step (1) to the 50 g carrier by equal volume impregnation, and put the catalyst precursor obtained after each impregnation into an ultrasonic oscillator for 20 Minutes, then dried at 110°C for 4 hours, and then calcined at 480°C for 4 hours in an air atmosphere to prepare a W-Ni catalyst named CAT-0.

Comparative example 5

This comparative example provides a kind of W-Ni catalyst, and it is prepared by using ZT-B1 prepared above as a carrier, and its preparation method specifically includes:

(1) The nickel nitrate of 17.1g and the ammonium metatungstate of 46.0g are dissolved in the deionized water of 540.0g, are mixed with impregnation solution;

(2) Weigh 50 g of the ZT-B1 carrier, and add the impregnation solution prepared in step (1) to the 50 g carrier by equal volume impregnation, and put the catalyst precursor obtained after each impregnation into an ultrasonic oscillator for 20 Minutes, then dried at 110°C for 4 hours, and then calcined at 480°C for 4 hours in an air atmosphere to prepare a W-Ni catalyst named CAT-B1.

Comparative example 6

This comparative example provides a kind of W-Ni catalyst, and it is prepared with the above-mentioned ZT-B2 that obtains as carrier, and its preparation method specifically comprises:

(1) The nickel nitrate of 17.1g and the ammonium metatungstate of 46.0g are dissolved in the deionized water of 540.0g, are mixed with impregnation solution;

(2) Weigh 50g of the ZT-B2 carrier, and add the impregnation solution prepared in step (1) to the 50g carrier by equal volume impregnation, and put the catalyst precursor obtained after each impregnation into an ultrasonic oscillator for 20 Minutes, then dried at 110°C for 4 hours, and then calcined at 480°C for 4 hours in an air atmosphere to prepare a W-Ni catalyst named CAT-B2.

The W-Ni catalysts CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 provided in Example 9 and the W-Ni catalysts CAT-0, CAT-B1, CAT-B1 provided in Comparative Examples 4-6 The relevant physical parameters of CAT-B2 are shown in Table 5.

Table 5W-Ni catalyst related physical parameters

Note: The specific surface area (S _BET ), pore volume (V) and B/L acid value in Table 5 are all measured by conventional methods in the art.

As can be seen from the above Table 5, compared with the W-Ni catalyst CAT-0 provided in Comparative Example 4, the W-Ni catalyst prepared with the hydrogenation catalyst support containing B acid provided by the embodiment of the present invention as a carrier CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 have higher B/L acid value; And along with the increase of the B/L value of the added B acid alumina material, the obtained The strength of the W-Ni catalyst has various degrees of decline, but the strength of the W-Ni catalyst CAT-1-CAT-5 provided by the embodiments of the present invention can all meet the needs of industrial production (wherein, usually, the diesel oil used in industrial installations requires The strength of the hydrogenation catalyst is greater than 140 N/cm).

It can also be seen from the above Table 5 that the strengths of the catalysts CAT-B1 and CAT-B2 respectively provided by Comparative Example 5 and Comparative Example 6 are significantly lower than other catalysts, and catalysts of this strength cannot meet the needs of industrial production.

Catalyst Evaluation Example 10

This embodiment provides W-Ni catalyst CAT-1, CAT-2, CAT-3, CAT-4 and the W-Ni catalyst CAT-0, CAT-B1, CAT provided in the comparative example 4-6 that the embodiment of the present invention provides The catalytic performance of -B2 was evaluated, including:

The evaluation is a 2mL micro-reaction evaluation, the amount of catalyst used is 1g, and the n-decane solution model compound of 4,6-dibenzothiophene (DBT) and quinoline (Q) (which contains sulfur 1000mg/kg and nitrogen 500mg/kg) as the raw material, the reaction temperature is 340°C, the partial pressure of hydrogen is 6.4MPa, the volume ratio of hydrogen to oil is 500:1, and the volume space velocity is 2.0h ^-1 .

In this embodiment, the micro-reaction evaluation results of the catalyst are shown in Table 6.

Micro-reverse evaluation results of the catalyst in table 6

As can be seen from the above table 6, the Ni-W catalyst activity evaluation result prepared by the hydrogenation catalyst carrier containing B acid provided by the present invention shows that compared with the W-Ni catalyst CAT-0 provided by Comparative Example 4 , the W-Ni catalyst containing B acid provided by the embodiment of the present invention, that is, CAT-1, CAT-2, CAT-3, CAT-4, CAT-5 has high hydrodesulfurization and denitrogenation activities, and can realize sulfur Nitrogen was removed at the same time, and the liquid yield was not significantly affected, indicating that no obvious cracking reaction occurred during the hydrogenation reaction. The reason or mechanism for this beneficial effect is: 4,6-DMDBT has a large steric hindrance, and it is difficult for the hydrogenation active center to contact the sulfur atom, resulting in a low reaction rate and desulfurization rate in the direct hydrodesulfurization reaction. The B in the catalyst The existence of the acid center promotes the 4, 6 methyl transfer of 4,6-DMDBT and improves the direct desulfurization and isomerization-direct desulfurization reaction pathways, greatly improving the desulfurization efficiency and desulfurization activity.

It can also be seen from the above Table 5-Table 6 that Comparative Example 5 and Comparative Example 6 adopt two catalysts prepared by a hydrogenation catalyst carrier containing B acid (made only from alumina materials containing B acid), that is, CAT The desulfurization and denitrification activities of -B1 and CAT-B2 are significantly improved compared with the W-Ni catalyst CAT-0 provided in Comparative Example 4, but because the modification process causes a certain degree of loss in contrast surface and pore structure, resulting in CAT-B1 , CAT-B2 these two catalysts are not strong enough, not suitable for mass production and industrial applications.

The above is only a specific embodiment of the present invention, and cannot limit the scope of the invention, so the replacement of its equivalent components, or the equivalent changes and modifications made according to the patent protection scope of the present invention, should still fall within the scope of this patent. category. In addition, the technical features and technical features, technical features and technical inventions, and technical inventions and technical inventions in the present invention can be used in free combination.

Claims (12)

1. A hydrogenation catalyst carrier containing B acid, characterized in that, the hydrogenation catalyst carrier containing B acid is made from a commercial alumina carrier and an alumina material containing B acid, wherein the The total weight of raw materials is 100%, which includes 50-95% commercial alumina carrier and 5-50% alumina material containing B acid.
2. The hydrogenation catalyst carrier containing B acid according to claim 1, characterized in that, based on the total weight of the hydrogenation catalyst carrier containing B acid as 100%, it includes 60-75% commercial alumina carrier And 25-40% alumina material containing B acid.
3. The hydrogenation catalyst carrier containing B acid according to claim 1, characterized in that, the B/L acid value of the B acid-containing alumina material is 0.3-2.5, and the specific surface area is ^200-300m2 /g, The pore volume is 0.55-0.90mL/g;

   Preferably, the B/L acid value of the alumina material containing B acid is 0.8-1.6.
4. According to the hydrogenation catalyst carrier containing B acid described in any one of claims 1-3, it is characterized in that, the described alumina material containing B acid is made by sol-gel method, comprising:

   First prepare pseudo-boehmite into a uniform alumina sol slurry with an acid solution, then add a saturated solution of NH ₄ BF ₄ at room temperature to the alumina sol slurry dropwise under stirring conditions to form a gel, and then prepare the gel Carry out vacuum drying and then roast to obtain the alumina material containing B acid.
5. The hydrogenation catalyst carrier containing B acid according to claim 4, characterized in that, under the temperature condition of 70-80 ° C, the pseudo-boehmite is prepared into a uniform aluminum sol slurry with an acid solution;

   Preferably, the acid solution includes an inorganic acid solution or an organic acid solution;

   Also preferably, the specific surface area of the pseudo-boehmite is 300-600m ² /g, and the pore volume is 0.40-0.70mL/g;

   Also preferably, the dropping rate of the NH ₄ BF ₄ saturated solution is 3-5 mL/min;

   Also preferably, the F/Al molar ratio is controlled to be 0.06-0.18;

   Also preferably, the calcination temperature is 350-450°C, more preferably 400-450°C.
6. The hydrogenation catalyst carrier containing B acid according to claim 1 or 2, characterized in that the specific surface area of the commercial alumina carrier is 380-600m ² /g, and the pore volume is 0.40-0.60mL/g.
7. The hydrogenation catalyst carrier containing B acid according to claim 1 or 2, characterized in that, the specific surface area of the hydrogenation catalyst carrier containing B acid is ^220-450m2 /g, and the pore volume is 0.45-0.70mL /g;

   Preferably, the specific surface area is 300-400m ² /g, and the pore volume is 0.50-0.60mL/g.
8. The hydrogenation catalyst carrier containing B acid according to claim 1 or 2, characterized in that, the B/L acid value of the hydrogenation catalyst carrier containing B acid is between 0.01-0.8, and the infrared acid content at 150°C is It accounts for 60-70% of the total acid content, of which B acid accounts for 5-40% of the infrared acid content; 250°C infrared acid accounts for 20-30% of the total acid content, of which B acid accounts for 4-4% of the infrared acid content 40%; 350 ℃ infrared acid accounts for 5-15% of the total acid, of which B acid accounts for 2-35% of the infrared acid;

   Preferably, the B/L acid value of the hydrogenation catalyst carrier containing B acid is between 0.3-0.59, and the amount of infrared acid at 150°C accounts for 63-68% of the total acid amount, wherein the amount of B acid accounts for 10% of the amount of infrared acid 20-40%; 250°C infrared acid accounts for 23-28% of the total acid amount, of which B acid accounts for 20-40% of the infrared acid amount; 350°C infrared acid amount accounts for 8-12% of the total acid amount, of which The amount of B acid accounts for 12-34% of the amount of infrared acid.
9. The preparation method of the hydrogenation catalyst carrier containing B acid described in any one of claims 1-8, it is characterized in that, comprising:

   Mix the commercial alumina carrier and the alumina material containing B acid according to the proportion, add the safflower powder, dry mix and make the powder mix uniformly, and obtain the dry mixed sample;

   The nitric acid solution is added to the dry mixed sample for wet mixing to obtain a wet mixed sample;

   The wet-mixed sample is molded, and then the molded product is dried and roasted to obtain the hydrogenation catalyst carrier containing B acid.
10. A hydrorefining catalyst, characterized in that the carrier of the hydrorefining catalyst is the hydrogenation catalyst carrier containing B acid described in any one of claims 1-8.
11. The application of the hydrofinishing catalyst described in claim 10 in the hydrofinishing process in the petroleum refining field.
12. The application according to claim 11, characterized in that the hydrofinishing process in the field of petroleum refining includes gasoline and diesel hydrofinishing.