CN118185659A

CN118185659A - Boiling bed heavy oil hydrogenation catalyst and preparation method and application thereof

Info

Publication number: CN118185659A
Application number: CN202211601966.1A
Authority: CN
Inventors: 金浩; 朱慧红; 吕振辉; 杨光; 生青青
Original assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2022-12-14
Filing date: 2022-12-14
Publication date: 2024-06-14

Abstract

The invention discloses a fluidized bed heavy oil hydrogenation catalyst, a preparation method and application thereof. The preparation method comprises the following steps: (1) balling pseudo-boehmite powder to obtain a carrier precursor A; (2) Mixing an organic high molecular polymer A, a nitrogenous weak alkali compound and pseudo-boehmite powder to obtain a mixed material; (3) Preparing a carrier precursor B by mixing the carrier precursor A with a mixed material and an aqueous solution of the organic high-molecular polymer B after heating treatment; (4) carrying out low-temperature heat treatment on the carrier precursor B to obtain a carrier precursor C; (5) Mixing the carrier precursor C with a soluble zirconium salt solution, and roasting in an inert atmosphere to obtain a carrier; (6) Introducing active metal components into a carrier, and drying and roasting to obtain the hydrogenation catalyst. The catalyst of the invention not only has higher hydrodemetallization activity and metal-containing and other impurity capacities, but also can ensure the stability of the catalyst in the long-period running process of the device.

Description

Boiling bed heavy oil hydrogenation catalyst and preparation method and application thereof

Technical Field

The invention belongs to the technical field of oil refining and chemical industry, relates to a hydrogenation catalyst and a preparation method thereof, and in particular relates to a boiling bed heavy oil hydrogenation catalyst and a preparation method thereof.

Background

In recent years, as the quality of crude oil is increasingly poor, heavy oil deep processing is developed, the added value of products is increased, and the method has important practical significance. In recent years, the ebullated bed hydrogenation technology has rapidly developed, and can use inferior and low-cost heavy oil as a raw material, so that the production cost is lower, and the economic benefit is remarkable. As the boiling bed has the function of on-line adding and discharging the catalyst, the consumption of the catalyst is larger in the running process, so that higher requirements are put on the performance and the cost of the catalyst. The reactivity of hydrogenation catalysts depends both on the inherent catalytic properties of the active components and is closely related to the nature of the catalyst support. The specific surface area, pore structure, surface acidity, etc. of the carrier have important effects on the dispersity of the active component, the interaction between the active component and the carrier, the diffusion of reactant molecules, and the poisoning resistance of the catalyst. At present, the most widely used carrier in the heavy oil hydrogenation field is alumina, which has the advantages of good mechanical property and low price, but also has the disadvantages of low specific surface area, strong action with active metal and the like. Therefore, a great deal of alumina modification research work has been carried out by numerous researchers.

CN201810893969.4 discloses a method for preparing a boiling bed hydrotreating catalyst. The method comprises the following steps: (1) Kneading pseudo-boehmite and basic ammonium aluminum carbonate for adsorbing a carbon precursor solution to form a formed product, and drying the formed product; (2) Spraying and dipping the material obtained in the step (1) by using a solution containing a carbon precursor, and drying and roasting the sprayed and dipped material to obtain an alumina carrier; (3) Impregnating the alumina carrier obtained in the step (2) with impregnating solution containing hydrogenation active components, drying and roasting after impregnation to obtain the ebullated bed hydrotreating catalyst. The catalyst prepared by the method has higher strength and wear resistance, and is particularly suitable for the heavy oil ebullated bed hydrotreatment process. However, the reaming effect of the carbon-containing precursor is not strong, the effect of the alumina carrier and the active metal is strong, and the utilization rate is not high.

US4448896 discloses a hydrodesulfurization and demetallization catalyst, which is prepared by loading active components onto an alumina carrier with a specific surface area of 100-350 m ²/g, a pore radius of 3.75-7500 nm and a pore volume of 0.5-1.5 mL/g, and the preparation method of the carrier is to mix, mold and bake active alumina or an active alumina precursor with carbon black. The patent uses carbon black for reaming, and the pore volume of the carrier is increased, but the expansion of macropores is limited, so that the metal capacity of the catalyst is required to be improved.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention mainly aims to provide a boiling bed heavy oil hydrogenation catalyst and a preparation method and application thereof. The catalyst has uneven pore distribution, and active metal of the catalyst also has uneven distribution, and is especially suitable for heavy oil and residual oil hydrotreatment. The catalyst not only has higher hydrodemetallization activity and metal-containing impurity capacity, but also has higher desulfurization activity, and the catalyst is not easy to be blocked by metal-containing impurities, so that the stability of the catalyst in the long-period running process of the device can be ensured.

The invention provides a preparation method of a boiling bed heavy oil hydrogenation catalyst, which comprises the following steps:

(1) Balling and molding pseudo-boehmite powder to obtain a carrier precursor A;

(2) Mixing an organic high molecular polymer A, a nitrogenous weak alkali compound and pseudo-boehmite powder to obtain a mixed material;

(3) Putting the carrier precursor A obtained in the step (1) into a ball rolling machine, and uniformly adding the mixed material obtained in the step (2) and the aqueous solution of the organic high-molecular polymer B after heating treatment in the rolling process to obtain a carrier precursor B;

(4) Carrying out low-temperature heat treatment on the carrier precursor B obtained in the step (3), and obtaining a carrier precursor C after the treatment;

(5) Mixing the carrier precursor C obtained in the step (4) with a soluble zirconium salt solution, uniformly mixing, and roasting in an inert atmosphere to obtain a carrier;

(6) Introducing active metal components into the carrier obtained in the step (5), and drying and roasting to obtain the hydrogenation catalyst.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the pseudo-boehmite powder in the step (1) and the step (2) can be commercially available products or prepared according to the existing method.

In the method for preparing the boiling bed heavy oil hydrogenation catalyst, the pseudo-boehmite powder in the step (1) and the step (2) can be pseudo-boehmite powder with the same property or pseudo-boehmite powder with different properties.

Further, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, the balling forming in the step (1) may be any one of the existing balling forming modes in the field, and specifically may be one or more of extrusion ball casting forming, rolling forming and spray drying forming modes.

Further, in the above-mentioned method for producing a ebullated-bed heavy oil hydrogenation catalyst, the particle diameter of the carrier precursor A in the step (1) is 0.1 to 1.0mm, preferably 0.3 to 0.7mm.

Further, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, the organic high molecular polymer A in the step (2) is one or more of starch, cellulose ether, sugar and flour, preferably starch. More specifically, the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, preferably corn starch and/or potato starch; the cellulose ether may be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose, preferably methyl cellulose; the saccharide is one or more of monosaccharide, disaccharide and polysaccharide, preferably glucose.

In the method for preparing the boiling bed heavy oil hydrogenation catalyst, the nitrogenous weak alkali compound in the step (2) is one or a mixture of more than two of ammonia water, ammonium carbonate and ammonium bicarbonate, and preferably ammonia water. Further, the concentration of the aqueous solution of the weakly basic compound containing nitrogen is 2 to 40wt%, preferably 5 to 30wt%.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the mass ratio of the organic high molecular polymer A to the nitrogenous weak alkali compound aqueous solution in the step (2) is 1:0.05-1:0.5.

Further, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, the addition amount (in mass) of the organic high molecular polymer A and the nitrogenous weak alkali compound in the step (2) is 5-40 wt%, preferably 10-30 wt% of the dry matrix amount of pseudo-boehmite powder.

In the method for preparing the catalyst for hydrogenation of heavy oil in ebullated bed, when the organic high molecular polymer a, the nitrogen-containing weak alkali compound and the pseudo-boehmite powder are mixed in the step (2), the organic high molecular polymer a and the nitrogen-containing weak alkali compound are preferably mixed first and then mixed with the pseudo-boehmite powder.

Further, in the above-mentioned method for preparing a boiling bed heavy oil hydrogenation catalyst, the concentration of the aqueous solution of the organic high molecular polymer B after the heat treatment in the step (3) is 0.5wt% to 8wt%, preferably 1wt% to 5wt%. The preparation method comprises the following steps: adding the organic high polymer B into water, heating and mixing for 10-40 min at 60-100 ℃, and obtaining the aqueous solution of the organic high polymer B after the heating treatment after the organic high polymer B is completely dissolved.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the mass ratio of the addition amount of the aqueous solution of the organic high molecular polymer B after the heating treatment in the step (3) to the mixed material is 0.5-1.5.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the organic high molecular polymer B in the step (3) is one or more of starch, sugar, cellulose ether and flour, preferably starch. Further, the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, preferably corn starch and/or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose, preferably methyl cellulose; the saccharide is one or more of monosaccharide, disaccharide and polysaccharide, preferably glucose.

Further, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, the low-temperature heat treatment temperature in the step (4) is 100-300 ℃, preferably 150-250 ℃; the treatment time is 3-12 h.

Further, in the preparation method of the ebullated bed heavy oil hydrogenation catalyst, the soluble zirconium salt in the step (5) is one or more of zirconium nitrate, zirconium chloride, zirconium sulfate and the like.

Further, in the preparation method of the ebullated bed heavy oil hydrogenation catalyst, the drying temperature in the step (5) is 60-120 ℃.

Further, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, the inert atmosphere in the step (5) is one or more of nitrogen, helium, neon, argon, krypton and xenon, preferably nitrogen; the roasting temperature is 600-900 ℃ and the roasting time is 1-5 h.

Further, in the above-mentioned method for producing a ebullated-bed heavy oil hydrogenation catalyst, the carrier particle diameter in the step (5) is 0.2 to 2.0mm, preferably 0.3 to 1.8mm.

Further, in the above preparation method of the ebullated-bed heavy oil hydrogenation catalyst, any one or more of the methods existing in the art may be used for introducing the active metal component in the step (6), specifically, at least one of kneading, dipping, etc. methods may be used, and a dipping method is preferred.

Further, in the preparation method of the ebullated-bed heavy oil hydrogenation catalyst, the active metal component in the step (6) is one or more of group VIB metals and/or group VIII metals, wherein the group VIB metals are typically Mo and/or W, and the group VIII metals are typically Ni and/or Co.

Further, in the above-mentioned method for producing an ebullated-bed heavy oil hydrogenation catalyst, the active metal components in step (6) are preferably Mo and Ni.

Furthermore, in the preparation method of the boiling bed heavy oil hydrogenation catalyst, an auxiliary agent P can be introduced during the introduction of the active metal component in the step (6),

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the drying in the step (6) is performed for 4-12 hours at 80-120 ℃.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the roasting temperature in the step (6) is 400-600 ℃, and the roasting time is 1-5 h. The calcination is carried out in the presence of an oxygen-containing atmosphere, such as under air conditions.

In the preparation method of the boiling bed heavy oil hydrogenation catalyst, when the active metal component in the step (6) adopts an impregnation method, firstly, uniformly mixing a precursor containing the active metal component, water and optionally a phosphorus-containing compound to obtain an aqueous solution containing the hydrogenation metal component and P, then uniformly mixing the aqueous solution with a carrier, and standing, drying and roasting to obtain the catalyst. Specifically, the precursor containing the active metal component is a compound containing VIB group metal and/or VIII group metal, the compound containing VIB group metal can be one or more of molybdenum-containing compounds and tungsten-containing compounds, and the compound containing VIII group metal is one or more of nickel-containing compounds and cobalt-containing compounds. The molybdenum-containing compound may be molybdenum oxide and/or ammonium heptamolybdate; the nickel-containing compound is basic nickel carbonate and/or nickel nitrate; the cobalt-containing compound is basic cobalt carbonate and/or cobalt nitrate. The phosphorus-containing compound can be one or more of phosphoric acid, monoammonium phosphate and monoammonium phosphate; the concentration of the hydrogenation metal component in the aqueous solution containing the hydrogenation metal component and the P is 0.03-0.5 g/mL (calculated by hydrogenation metal oxide), and the concentration of the P is 0-0.05 g/mL, preferably 0.002-0.05 g/mL. The standing time is 1-3 h.

The invention also provides the ebullated bed heavy oil hydrogenation catalyst obtained by the preparation method.

Further, in the ebullated-bed heavy oil hydrogenation catalyst, the ebullated-bed heavy oil hydrogenation catalyst comprises an active metal component, an auxiliary metal component, optionally phosphorus pentoxide and a carrier, wherein the active metal is one or more of a group VIB metal and/or a group VIII metal, the auxiliary metal is zirconium, the carrier is alumina, and the active metal and the auxiliary metal exist on the carrier in the form of oxides.

Further, in the boiling bed heavy oil hydrogenation catalyst, the content of the metal component of the VIB group is 2-15 wt% based on the weight of the catalyst and calculated by oxide; the content of the metal component of the VIII group is 0.5 to 5 weight percent; the content of the auxiliary metal component is 0.1-2 wt%; the content of phosphorus pentoxide is 0.4wt% -4wt%.

Further, in the ebullated-bed heavy oil hydrogenation catalyst, the group VIB metal is typically Mo and/or W, and the group VIII metal is typically Ni and/or Co.

Further, in the above ebullated bed heavy oil hydrogenation catalyst, the metal component is more preferably Mo and Ni.

Further, in the above ebullated-bed heavy oil hydrogenation catalyst, the properties of the ebullated-bed heavy oil hydrogenation catalyst are as follows: the specific surface area is 120-250 m ²/g, the pore volume is 0.60-0.90 mL/g, and the proportion of the pore volume of the pores with the pore diameter larger than 50nm to the total pore volume is more than 3%, preferably 5-15%.

Further, in the ebullated-bed heavy oil hydrogenation catalyst, the active metals of the ebullated-bed heavy oil hydrogenation catalyst are distributed relatively less on the outside and relatively more on the inside, and are unevenly distributed.

The third aspect of the invention provides an application of the ebullated-bed heavy oil hydrogenation catalyst in a heavy oil hydrotreating process.

Further, in the application of the ebullated bed heavy oil hydrogenation catalyst in the heavy oil hydrogenation treatment process, the heavy oil is at least one or more of atmospheric residuum, vacuum residuum, catalytic slurry oil and coal tar.

Further, in the application of the ebullated bed heavy oil hydrogenation catalyst in the heavy oil hydrotreating process, the hydrotreating process has the following process conditions: the reaction pressure is 10-20 MPa, the temperature is 300-500 ℃, the liquid hourly space velocity is 0.1-1.5 h ^-1, and the hydrogen-oil volume ratio is 300-1000.

Compared with the prior art, the ebullated bed heavy oil hydrogenation catalyst and the preparation method thereof provided by the invention have the following advantages:

1. In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the organic high molecular polymer A is mixed with pseudo-boehmite powder after being acted with the weak alkali compound, only plays a role of reaming, and has poor cohesiveness; the organic high molecular polymer B after the heat treatment is decomposed into small molecules in water, so that the aqueous solution has high cohesiveness, the mixed material A and the carrier precursor A have stronger interaction, the interaction force between pseudo-boehmite powder can be enhanced, namely the interaction force between carrier aluminas is enhanced, and the strength and the abrasion resistance of the carrier are improved.

2. In the preparation method of the boiling bed heavy oil hydrogenation catalyst, ammonia in the nitrogen-containing weak alkali compound which is reacted with the organic high molecular polymer A is volatilized after low-temperature treatment, the ammonia interacts with the strong acid site on the alumina to be adsorbed, and the addition of the soluble zirconium salt interacts with the ammonia on the alumina to be adsorbed on the strong acid site of the alumina, so that the carrier precursor B occupies the strong acid site of the alumina after roasting, the interaction between active metal and the carrier alumina can be weakened, and the utilization rate of the active metal is improved.

3. In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the organic high molecular polymer A is baked in inert atmosphere or nitrogen atmosphere to become a macroporous carbon material, and the organic high molecular polymer B decomposed into small molecules is baked in inert atmosphere or nitrogen atmosphere to become a small pore carbon material, wherein the macroporous carbon material can play a role in reaming the outer layer of alumina, and the small pore carbon material can improve the structural stability of the outer layer of alumina and improve the strength of a carrier. Because the water absorption rate of the macroporous carbon material is lower than that of the alumina, and the pore canal of a part of the outer-layer alumina is blocked by the small pore carbon material, the water absorption rate of the outer-layer alumina carrier is reduced due to the existence of the carbon material. In the process of impregnating active metals, the active metals on the outer layer of the carrier are adsorbed relatively less, the alumina on the inner layer of the carrier is adsorbed relatively more active metals, the prepared catalyst active metals are unevenly distributed, the active metals in the catalyst are more distributed, the active metals outside the catalyst are relatively less distributed, the activity of the catalyst is in gradient distribution, metal impurities can be uniformly deposited on the catalyst, the outer pore channels of the catalyst are not easy to be blocked, the utilization rate of the active metals is improved, and meanwhile, the catalyst has better stability.

4. In the preparation method of the boiling bed heavy oil hydrogenation catalyst, the macroporous carbon material generated by the organic high molecular polymer A on the carrier alumina is completely burnt in the roasting process of the catalyst, so that the number of macropores on the outer layer of the alumina carrier is increased, the reaming effect on the outer layer of the alumina carrier is achieved, the catalyst has uneven pore distribution, the catalyst is not easy to be blocked by impurities such as metal and the like, the problem that the hydrodemetallization activity, hydrodesulphurization activity and metal containing and other impurity capacity of the conventional hydrogenation catalyst are not matched is solved, the stability of the catalyst in the long-period running process of the device can be ensured, and the catalyst is particularly suitable for the heavy oil and residual oil hydrogenation field.

Drawings

FIG. 1 is a schematic diagram of a catalyst cross-section electron probe.

FIG. 2 shows the distribution of electron probe scanning catalyst cross-section MoO ₃.

Detailed Description

The technical scheme and effect of the present invention are further described below by means of specific examples. In the invention, the weight percent is the mass fraction.

According to the invention, a high-speed air jet method is adopted to test the wear index of the microsphere carrier of <0.8mm (see ASTM D5757-00), a rotary drum method is adopted to measure the wear index of the microsphere carrier of >0.8mm, and a KM-ZV abrasion instrument is used; the side pressure strength was measured using a ZQJ-II intelligent particle strength tester.

The specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen physical adsorption method, and are specifically measured by adopting a low-temperature nitrogen adsorption instrument of ASAP2420 model of America microphone company; the specific process comprises the following steps: and (3) taking a small amount of samples, carrying out vacuum treatment for 3-4 hours at 300 ℃, and finally, placing the products under the condition of low temperature (-200 ℃) of liquid nitrogen for nitrogen adsorption-desorption test. Wherein the surface area is obtained according to the BET equation and the pore size distribution is obtained according to the BJH model.

The distribution of the active metal of the catalyst was measured by using a JXA-8230 electron probe microanalyzer available from Japanese electric Co.

Example 1

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; mixing 31.5g of corn starch with 30g of ammonia water with the concentration of 10wt%, and then mixing with 300g of pseudo-boehmite powder to obtain a mixed material; weighing 3.5g of corn starch, adding into 100g of water, and heating at 70 ℃ for 20min to obtain an aqueous solution of an organic high molecular polymer B; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, the mixture and the aqueous solution of the organic high molecular polymer B are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, the carrier precursor B with the thickness of 0.6-0.7 mm is prepared. And carrying out low-temperature heat treatment on the carrier precursor B at the temperature of 200 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 4.93g of zirconium nitrate was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 750℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.6 to 0.7mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

1.57G of phosphoric acid H ₃PO₄ (with the concentration of 85 wt%) is dissolved in 50mL of water, then 4.27g of molybdenum trioxide and 1.88g of basic nickel carbonate are added, the temperature is raised to 100 ℃ and the mixture is stirred and refluxed for 2.0H, and the constant volume is 85mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.

Adding all Mo-Ni-P aqueous solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the catalyst, wherein the MoO ₃ content is 4.0wt%, the NiO content is 1.0wt% and the P content is 0.4wt%. The physical and chemical properties of the catalyst are shown in Table 2.

(3) Catalyst evaluation

The catalyst is subjected to long-period activity evaluation by adopting a small-scale hydrogenation device, and the operation time is 1500 hours. The catalyst evaluation conditions were: the reaction temperature is 420 ℃, the reaction pressure is 15.0MPa, the volume space velocity is 0.3h ^-1, and the hydrogen-oil volume ratio is 500:1. The properties of the raw oil are shown in Table 3, and the evaluation results are shown in Table 4.

Example 2

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; mixing 42.0g of corn starch with 50g of ammonium carbonate aqueous solution with the concentration of 15wt% and then mixing with 300g of pseudo-boehmite powder to obtain a mixed material; weighing 3.5g of corn starch, adding into 100g of water, and heating at 70 ℃ for 20min to obtain an aqueous solution of an organic high molecular polymer B; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, the mixture and the aqueous solution of the organic high molecular polymer B are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, the carrier precursor B with the thickness of 0.6-0.7 mm is prepared. And carrying out low-temperature heat treatment on the carrier precursor B at the temperature of 200 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 2.71g of zirconium chloride was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 800℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.6 to 0.7mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

2.43G of phosphoric acid H ₃PO₄ (with the concentration of 85 wt%) is dissolved in 50mL of water, then 6.59g of molybdenum trioxide and 2.91g of basic nickel carbonate are added, the temperature is raised to 100 ℃ and the mixture is stirred and refluxed for 2.0H, and the constant volume is 85mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.

Adding all Mo-Ni-P aqueous solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the catalyst, wherein the MoO ₃ content is 6.0wt%, the NiO content is 1.5wt% and the P content is 0.6wt%. The physical and chemical properties of the catalyst are shown in Table 2.

(3) Catalyst evaluation

Example 3

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; 52.5g of corn starch and 50g of ammonium bicarbonate aqueous solution with the concentration of 25wt% are mixed and then are mixed with 300g of pseudo-boehmite powder to obtain a mixed material; weighing 3.5g of corn starch, adding into 100g of water, and heating at 70 ℃ for 20min to obtain an aqueous solution of an organic high molecular polymer B; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, the mixture and the aqueous solution of the organic high molecular polymer B are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, the carrier precursor B with the thickness of 0.6-0.7 mm is prepared. And carrying out low-temperature heat treatment on the carrier precursor B at the temperature of 200 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 4.08g of zirconium sulfate was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 850℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.6 to 0.7mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

4.30G of phosphoric acid H ₃PO₄ (with the concentration of 85 wt%) is dissolved in 50mL of water, then 11.68g of molybdenum trioxide and 5.16g of basic nickel carbonate are added, the temperature is raised to 100 ℃ and the mixture is stirred and refluxed for 2.0H, and the constant volume is 85mL after filtration, thus obtaining the Mo-Ni-P aqueous solution.

Adding all Mo-Ni-P aqueous solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the catalyst, wherein the MoO ₃ content is 10.0wt%, the NiO content is 2.5wt% and the P content is 1.0wt%. The physical and chemical properties of the catalyst are shown in Table 2, and the distribution of MoO ₃ on the catalyst is shown in FIG. 1 and FIG. 2.

(3) Catalyst evaluation

Example 4

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; mixing 175g of corn starch with 150g of ammonium bicarbonate aqueous solution with the concentration of 25wt% and then mixing with 1000g of pseudo-boehmite powder to obtain a mixed material; weighing 3.5g of corn starch, adding into 100g of water, and heating at 70 ℃ for 20min to obtain an aqueous solution of an organic high molecular polymer B; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, the mixture and the aqueous solution of the organic high molecular polymer B are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, 0.9-1.0 mm of carrier precursor B is prepared. And carrying out low-temperature heat treatment on the carrier precursor B at the temperature of 200 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 4.93g of zirconium nitrate was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 850℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.9 to 1.0mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

Adding all Mo-Ni-P aqueous solution into 100g of prepared carrier, uniformly mixing, standing for 3h, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the catalyst, wherein the MoO ₃ content is 10.0wt%, the NiO content is 2.5wt% and the P content is 1.0wt%. The physical and chemical properties of the catalyst are shown in Table 2.

(3) Catalyst evaluation

Example 5

Substantially the same as in example 3, except that 52.5g of corn starch was changed to 52.5g of potato starch, 3.5g of corn starch was changed to 3.5g of potato starch, 4.08g of zirconium sulfate was changed to 4.93g of zirconium nitrate, spherical carriers having a particle diameter of 0.6 to 0.7mm were produced, and the carrier yield and abrasion data are shown in Table 1. The catalyst was obtained, wherein the MoO ₃ content was 10.0wt%, the NiO content was 2.5wt% and the P content was 1.0wt%. The physical and chemical properties of the catalyst are shown in Table 2.

The catalyst was evaluated in the same manner as in example 3, the properties of the raw oil used are shown in Table 3, and the evaluation results are shown in Table 4.

Example 6

Substantially the same as in example 3, except that 52.5g of corn starch was changed to 44.19g of methylcellulose and 3.5g of corn starch was changed to 2.95g of methylcellulose, spherical carriers having a particle diameter of 0.6 to 0.7mm were produced, and the carrier yields and abrasion data are shown in Table 1. The catalyst was obtained, wherein the MoO ₃ content was 10.0wt%, the NiO content was 2.5wt% and the P content was 1.0wt%. The physical and chemical properties of the catalyst are shown in Table 2.

Comparative example 1

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; mixing 31.5g of corn starch with 15g of ammonia water with the concentration of 5wt%, and then mixing with 300g of pseudo-boehmite powder to obtain a mixed material; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, mixed materials, 3.5g of corn starch and water are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, 0.6-0.7 mm of carrier precursor B is prepared. And carrying out low-temperature heat treatment on the carrier precursor B at the temperature of 200 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 4.93g of zirconium nitrate was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 750℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.6 to 0.7mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

(3) Catalyst evaluation

Comparative example 2

(1) Carrier preparation

Rolling and forming pseudo-boehmite powder (the specific surface is 308m ²/g, the pore volume is 1.02 mL/g) in a ball rolling machine to prepare a spherical carrier precursor A with the thickness of 0.4-0.5 mm; mixing 31.5g of corn starch with 300g of pseudo-boehmite powder to obtain a mixed material; weighing 3.5g of corn starch, adding into 100g of water, and heating at 70 ℃ for 20min to obtain an aqueous solution of an organic high molecular polymer B; 100g of carrier precursor A is weighed and put into a ball rolling machine, in the rolling process, the mixture and the aqueous solution of the organic high molecular polymer B are uniformly scattered, the rotating speed of the ball rolling machine is 30 revolutions per minute, and after the ball forming is finished, the carrier precursor B with the thickness of 0.6-0.7 mm is prepared. And drying the carrier precursor B at 120 ℃ for 4 hours to obtain a carrier precursor C. 50mL of an aqueous solution containing 4.93g of zirconium nitrate was added to 100g of carrier precursor C, dried at 90℃for 8 hours, and then calcined at 750℃for 3 hours under a nitrogen atmosphere to obtain spherical carriers having a particle diameter of 0.6 to 0.7mm, and the carrier yield and abrasion data are shown in Table 1.

(2) Catalyst preparation

(3) Catalyst evaluation

TABLE 1 Carrier yield and attrition

TABLE 2 physicochemical Properties of the catalysts

TABLE 3 Properties of raw oil

Table 4 results of catalyst evaluation

The results of the evaluation after the comparison with the activity of comparative example are shown in Table 4, with the activity of comparative example 1 being 100.

Claims

1. The preparation method of the boiling bed heavy oil hydrogenation catalyst comprises the following steps:

(1) Balling and molding pseudo-boehmite powder to obtain a carrier precursor A;

2. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the pseudo-boehmite powder in the step (1) and the step (2) are pseudo-boehmite powder with the same property or pseudo-boehmite powder with different properties.

3. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the ball forming in the step (1) adopts one or more of extrusion ball throwing forming, rolling forming and spray drying forming modes.

4. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the particle size of the carrier precursor A in the step (1) is 0.1 to 1.0mm, preferably 0.3 to 0.7mm.

5. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the organic high molecular polymer A in the step (2) is one or more of starch, sugar, cellulose ether and flour, preferably starch.

6. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 6, wherein: the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, preferably corn starch and/or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose, preferably methyl cellulose; the saccharide is one or more of monosaccharide, disaccharide and polysaccharide, preferably glucose.

7. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the nitrogenous weak alkali compound in the step (2) is one or a mixture of more than two of ammonia water, ammonium carbonate and ammonium bicarbonate, and is preferably ammonia water.

8. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the concentration of the aqueous solution of the nitrogen-containing weakly basic compound in the step (2) is 2 to 40wt%, preferably 5 to 30wt%.

9. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the mass ratio of the organic high molecular polymer A to the weak base compound containing nitrogen in the step (2) is 1:0.05-1:0.5.

10. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the addition amount of the organic high molecular polymer A and the nitrogenous weak alkali compound in the step (2) is 5-40 wt% of the dry matrix amount of the pseudo-boehmite powder by mass, and preferably 10-30 wt%.

11. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the concentration of the aqueous solution of the organic high molecular polymer B after the heating treatment in the step (3) is 0.5 to 8 weight percent, preferably 1 to 5 weight percent; the preparation method comprises the following steps: adding the organic high polymer B into water, heating and mixing for 10-40 min at 60-100 ℃, and obtaining the aqueous solution of the organic high polymer B after the heating treatment after the organic high polymer B is completely dissolved.

12. The ebullated-bed heavy oil hydrogenation catalyst according to claim 1

The preparation method of the chemical agent is characterized by comprising the following steps: the mass ratio of the addition amount of the aqueous solution of the organic high molecular polymer B to the mixed material in the step (3) is 0.5-1.5.

13. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the organic high molecular polymer B in the step (3) is one or more of starch, sugar, cellulose ether and flour, preferably starch.

14. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 12, wherein: the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, preferably corn starch and/or potato starch; the cellulose ether can be at least one of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose and phenyl cellulose, preferably methyl cellulose; the saccharide is one or more of monosaccharide, disaccharide and polysaccharide, preferably glucose.

15. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the low-temperature heat treatment temperature in the step (4) is 100-300 ℃, preferably 150-250 ℃; the treatment time is 3-12 h.

16. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the soluble zirconium salt in the step (5) is one or more of zirconium nitrate, zirconium chloride and zirconium sulfate.

17. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the drying temperature in the step (5) is 60-120 ℃; roasting in the inert atmosphere in the step (5), wherein the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon, and is preferably nitrogen; the roasting temperature is 600-900 ℃ and the roasting time is 1-5 h.

18. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the carrier particle size in the step (5) is 0.2 to 2.0mm, preferably 0.3 to 1.8mm.

19. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the active metal component in the step (6) is one or more of VIB group metal and/or VIII group metal, wherein the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.

20. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the active metal components in the step (6) are Mo and Ni.

21. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the auxiliary agent P is introduced in the introduction of the active metal component described in the step (6).

22. The method for preparing the ebullated-bed heavy oil hydrogenation catalyst according to claim 1, wherein: the drying in the step (6) is that the drying is carried out for 4 to 12 hours at the temperature of 80 to 120 ℃; the roasting temperature in the step (6) is 400-600 ℃, and the roasting time is 1-5 h; the calcination is carried out in the presence of an oxygen-containing atmosphere.

23. An ebullated bed heavy oil hydrogenation catalyst obtainable by the process of any one of claims 1 to 21.

24. The ebullated bed heavy oil hydrogenation catalyst according to claim 22, wherein: the boiling bed heavy oil hydrogenation catalyst comprises an active metal component, an auxiliary metal component, optional phosphorus pentoxide and a carrier, wherein the active metal is one or more of VIB group metal and/or VIII group metal, the auxiliary metal is zirconium, the carrier is alumina, and the active metal and the auxiliary metal exist on the carrier in the form of oxide.

25. The ebullated bed heavy oil hydrogenation catalyst according to claim 22, wherein: the VIB group metal is Mo and/or W, and the VIII group metal is Ni and/or Co.

26. The ebullated bed heavy oil hydrogenation catalyst according to claim 22, wherein: the active metal components are Mo and Ni.

27. The ebullated bed heavy oil hydrogenation catalyst according to claim 22, wherein: the boiling bed heavy oil hydrogenation catalyst has the following properties: the specific surface area is 140-250 m ²/g, the pore volume is 0.60-0.90 mL/g, and the proportion of the pore volume of the pores with the pore diameter larger than 50nm to the total pore volume is more than 3%.

28. Use of the ebullated-bed heavy oil hydrogenation catalyst of any one of claims 22-26 in a heavy oil hydroprocessing process.

29. The use according to claim 28, wherein: the heavy oil is one or more of atmospheric residuum, vacuum residuum, catalytic slurry oil and coal tar.

30. The use according to claim 28, wherein: the hydrotreating process has the following technological conditions: the reaction pressure is 10-20 MPa, the temperature is 300-500 ℃, the liquid hourly space velocity is 0.1-1.5 h ^-1, and the hydrogen-oil volume ratio is 300-1000.