Residual oil hydrodemetallization catalyst and preparation method thereof

Abstract

The invention discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The catalyst comprises an alumina carrier and a second active metal component, the alumina carrier contains a first active metal component, and the first active metal component is dispersed in a bulk phase of the alumina carrier; and the mass ratio of the first active metal component in terms of oxide to the alumina carrier is (0.01-0.10): 1. When the catalyst is used for heavy oil and residual oil hydrodemetallization reaction, the carbon deposition resistance, the demetallization activity and the metal capacity are greatly improved, and long-period stable operation of a device can be ensured.

Description

Technical Field

[0001] The invention relates to a hydrodemetallization catalyst, in particular to a hydrodemetallization catalyst in a residual oil hydroprocessing process and a preparation method thereof. Background Art

[0002] As crude oil becomes heavier and inferior, and the market demand for light oil products increases, heavy oil hydrogenation technology has gradually become a focus of increasing attention in the petrochemical industry. Fixed-bed residue oil hydrogenation technology is advanced and has a wide range of applications. It is an important means to achieve clean and efficient utilization of vacuum residue oil. However, due to the presence of heteroatoms such as metals in the residue oil, the residue oil hydrogenation catalyst is easily deactivated due to the deposition of metals and carbon deposits during the reaction process. The demetallization catalyst is relatively forward in the fixed-bed residue oil hydrogenation catalyst grading system and bears more reaction load. Therefore, it is particularly important to develop a hydroprocessing catalyst with a longer life and better hydrogenation performance, especially a hydrodemetallization catalyst.

[0003] At present, the research on hydrodemetallization catalysts is basically focused on the pore size of the carrier. For example, pore expanders and acid treatment are introduced during the preparation of the carrier. The carrier surface acidity obtained by the above means is unevenly distributed, and the introduction of additives destroys the original pores of the carrier, which is not conducive to the dispersion of active metals in the subsequent impregnation process. The catalyst has poor hydrogenation performance, poor resistance to metal deposition, and poor resistance to carbon deposition.

[0004] CN104549331A discloses a method for preparing a hydrodemetallization catalyst, comprising the following steps: (1) preparing a mixture of alumina dry rubber powder and water; (2) treating the material obtained in step (1) with a dual-frequency microwave, wherein the treatment temperature is 100 to 300° C., preferably 150 to 250° C., the treatment time is 1 to 6 hours, preferably 2 to 4 hours, and the frequency difference of the dual-frequency microwave is 1 to 50 kHz, preferably 5 to 35 kHz; filtering and drying are performed after the treatment; and (3) kneading the material obtained in step (2) with a salt solution containing active metals to obtain a hydrodemetallization catalyst after drying and calcining.

[0005] CN104646007A discloses a residual oil hydrodemetallization catalyst and its preparation and application. First, the activated carbon carrier is subjected to two pretreatment processes of hydrochloric acid washing and nitric acid oxidation; then, the composite auxiliary agent, activated carbon and alumina are mixed and extruded to prepare an activated carbon / alumina composite; finally, the carrier is loaded with metal by the hydrotalcite method, that is, equal volumes of a mixed solution of terephthalic acid, nickel nitrate, urea and ammonium nitrate in a molar ratio of 2:1:(2.5-5):(1-5) are impregnated, crystallized, washed several times, dried, and nickel salt water talc microcrystals are obtained, and then placed in a Mo salt solution for full replacement, filtered and washed to obtain green solid particles, dried, and roasted to obtain a residual oil hydrodemetallization catalyst.

[0006] CN105709765A discloses a method for preparing a residual oil hydrodemetallization catalyst, comprising the following steps: (1) kneading a pore-enlarging agent, pseudo-boehmite dry rubber powder, an extrusion aid, and a peptizing agent into a plastic body, extruding and drying; (2) unsaturated spray impregnating the carrier dried in step (1) with a mixed solution of phosphoric acid and ammonium oxalate, and sealing and heating the impregnated carrier, wherein the treatment pressure is the autogenous pressure under the sealing condition, the treatment temperature is 120-160° C., and the treatment time is 6-12 hours. The treated carrier is dried and calcined to obtain an alumina carrier; (3) the alumina prepared in step (2) is impregnated with active components, and after impregnation, it is dried and calcined to obtain an alumina carrier of the residual oil hydrodemetallization catalyst.

[0007] The hydrogenation activity and stability of the hydrodemetallization catalyst prepared by the above method need to be further improved. Summary of the invention

[0008] In view of the shortcomings of the prior art, the present invention provides a residual oil hydrodemetallization catalyst and a preparation method thereof. When the catalyst is used for the hydrodemetallization reaction of heavy and residual oils, it has strong hydrogenation activity, and its anti-carbon deposition performance, demetallization activity and metal tolerance are greatly improved, which can ensure the long-term stable operation of the device.

[0009] The first aspect of the present invention provides a residual oil hydrodemetallization catalyst, which includes an alumina carrier and a second active metal component. The alumina carrier contains a first active metal component, and the first active metal component is dispersed in the alumina carrier phase; the mass ratio of the first active metal component in terms of oxide to the alumina carrier is 0.01 to 0.10:1.

[0010] In the present invention, the first active metal is at least one of the Group VIII metals, and the Group VIII metal is preferably nickel. The second active metal component includes molybdenum and at least one selected from the Group VIII metals, and the Group VIII metal is preferably nickel.

[0011] In the present invention, based on the mass of the catalyst, the content of MoO3 is 10.0% to 28.0%, and the content of the Group VIII metal oxide is 2.0% to 20.0%. The mass ratio of the Group VIII metal in the first active metal component as oxide to the Group VIII metal in the second active metal component as oxide is 0.5 to 1.5:1.

[0012] In the present invention, the specific surface area of ​​the catalyst is 160 to 210 m 2 / g, pore volume is 0.50-0.90mL / g; preferably, the specific surface area of ​​the catalyst is 160-190m 2 / g, and the pore volume is 0.60~0.80mL / g.

[0013] In the present invention, the catalyst further comprises an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus. Further, in the catalyst, the content of the auxiliary component in terms of oxide is 1.0% to 6.0% based on the mass of the catalyst.

[0014] The second aspect of the present invention provides a method for preparing a residual oil hydrodemetallization catalyst, comprising the following steps:

[0015] (1) mixing pseudo-boehmite, a first active metal, an alkaline auxiliary agent, and deionized water, grinding, and filtering to obtain a solid material A;

[0016] (2) mixing the solid material A obtained in step (1) with an adhesive, forming, drying, and calcining to obtain a pre-support containing the first active metal;

[0017] (3) performing a surface carbon coating treatment on the pre-carrier obtained in step (2), and calcining to obtain a carrier B having a surface carbon coating;

[0018] (4) impregnating the carrier B obtained in step (3) with the second active metal impregnation solution to obtain a carrier C;

[0019] (5) The carrier C obtained in step (4) is dried and calcined to obtain the catalyst.

[0020] In step (1), the pseudo-boehmite is prepared by conventional methods, such as aluminum sulfate method, aluminum alcohol method, sol-gel method, etc. The mass content of aluminum oxide in the pseudo-boehmite is 60.0% to 75.0%.

[0021] In step (1), the alkaline auxiliary agent is one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carboxylate (such as sodium acetate, sodium formate, etc.).

[0022] In step (1), the first active metal is at least one of the metals of Group VIII, wherein the metal of Group VIII is preferably Ni, and the Ni source is selected from at least one of basic nickel carbonate, nickel sulfate, nickel nitrate, and the like.

[0023] In step (1), the mass ratio of pseudo-boehmite calculated as alumina: first active metal calculated as oxide: alkaline auxiliary agent: water is 200-240: 1.0-8.0: 6.0-15.0: 120-180.

[0024] In step (1), the grinding can be performed by ball milling, sand milling, etc. After grinding, the metal dispersion of the material is more uniform, and the alkaline additive forms a "first protective film" on the surface of the dried material. The filtering process is a conventional operation in the art. After grinding, a ground sample with an average particle size of 2.0 to 10.0 μm is obtained.

[0025] In step (1), the first active metal is a co-active metal, which can interact with the carrier during the calcination process to weaken the acid properties of the carrier, and can also synergistically act with the main active metal (Mo) in the second active metal component to facilitate the hydrogenation reaction.

[0026] In step (2), the adhesive may be an organic acid and / or an inorganic acid, the inorganic acid may be one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid may be one or more of tartaric acid, citric acid, and oxalic acid.

[0027] In step (2), the mass of the adhesive is 0.5% to 5.0% of the mass of the pseudo-boehmite in step (1) calculated as alumina.

[0028] In step (2), the forming method can be at least one of extrusion, tableting, and ball rolling. The shape after forming can be clover, four-leaf clover, butterfly, cylinder, sphere, strip, etc.

[0029] In step (2), according to the molding requirements, a molding aid, such as at least one of an extrusion aid and deionized water, etc., can be added during the molding process. The extrusion aid can be one or more of methyl cellulose, ethyl cellulose, sesbania powder, and starch. The mass of the extrusion aid added is 0.5% to 8.0% of the mass of pseudo-boehmite in terms of alumina. The amount of deionized water used can be 80% to 120% of the mass of pseudo-boehmite in terms of alumina in step (1).

[0030] In step (2), the drying temperature is 120 to 200° C., and the drying time is 2 to 12 hours.

[0031] In step (2), the calcination adopts a two-stage calcination process, the first stage calcination temperature is 350-450°C, the calcination time is 2-6 hours, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably air; the second stage calcination temperature is 450-750°C, the calcination time is 2-8 hours, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen. The second stage calcination temperature is 150-300°C higher than the first stage calcination temperature.

[0032] In step (3), the carbon coating treatment preferably uses an aqueous emulsion containing a polymer compound and water-soluble cellulose. In the aqueous emulsion, the mass content of the polymer compound is 5.0% to 15.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.0%.

[0033] In step (3), the polymer compound is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0034] In step (3), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

[0035] In step (3), the amount of the aqueous emulsion (measured by volume mL) and the pre-carrier (measured by mass g) is 0.8 to 1.5 mL / g.

[0036] In step (3), after the surface carbon coating treatment is completed, conventional filtration, washing and drying are first performed. The drying temperature is 120-200°C, and the drying time is 2.0-12.0 hours. The roasting conditions are: temperature is 500-700°C, time is 2.0-8.0 hours, and the roasting atmosphere is an inert atmosphere, preferably one or more of nitrogen and argon.

[0037] In step (4), the second active metal includes Mo and at least one selected from the group VIII metals (preferably Ni). Further, in the second active metal impregnation solution, the Mo source can be one or both of molybdenum oxide and ammonium heptamolybdate, and the Ni source can be one or both of basic nickel carbonate and nickel nitrate. Further, in the second active metal impregnation solution, the content of Mo in terms of MoO3 is 10.0 to 50.0 g / 100 mL, and the content of the group VIII metal in terms of oxide is 3.0 to 20.0 g / 100 mL. Among them, the mass of the group VIII metal in terms of oxide introduced into the catalyst by the second active metal impregnation solution accounts for 50.0% to 80.0% of the total group VIII metal loading in terms of oxide in the catalyst.

[0038] In step (4), at least one auxiliary agent selected from fluorine, phosphorus, silicon or boron may be introduced into the second active metal impregnation solution, and the content of the auxiliary agent in the second active metal impregnation solution is 3.0 to 18.0 g / 100 mL.

[0039] In step (4), preferably, the second active metal impregnation solution contains a water-soluble polymer J. The water-soluble polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose. The content of the water-soluble polymer J in the second active metal impregnation solution is 0.5 to 2.5 g / 100 mL.

[0040] In step (4), the impregnation method is saturated impregnation.

[0041] In step (5), the drying temperature is 120 to 200° C. and the drying time is 2 to 12 hours.

[0042] In step (5), the calcination process has a calcination temperature of 550-750° C. and a calcination time of 2-10 hours. The calcination is carried out in a mixed atmosphere of air and water vapor, wherein the volume ratio of air to water vapor is 0.1-5.0:1.0.

[0043] In step (5), the catalyst has a MoO3 content of 10.0% to 28.0% and a Group VIII metal oxide content of 2.0% to 20.0%, based on the mass of the catalyst.

[0044] In step (5), in the catalyst, the mass ratio of the Group VIII metal introduced into the catalyst by the first active metal component in terms of oxide to the Group VIII metal introduced into the catalyst by the second active metal component in terms of oxide is 0.5 to 1.5:1.

[0045] In step (5), preferably, in the catalyst, the content of the auxiliary agent in terms of oxide is 1.0% to 6.0% based on the mass of the catalyst.

[0046] The third aspect of the present invention provides the use of the above catalyst in the hydroprocessing of heavy oil and residual oil.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] Conventional active metal loading is impregnated once, and most of the active metals are distributed on the surface of the catalyst, resulting in a violent reaction on the catalyst surface. It is not easy for macromolecular reactants to enter the interior of the hydrodemetallization catalyst, which limits the utilization rate of the active metals. In addition, during the sulfurization process, the aggregated active metals have a low degree of sulfurization due to the aggregation of the metals, and the hydrogenation capacity of the active metals is limited. The present invention introduces part of the active metals during the carrier preparation process, so that the introduced part of the active metals is first dispersed in the alumina carrier phase, and this part of the active metals forms a state in which the active metals are more inside and less outside in the alumina carrier. When the catalyst reacts, on the one hand, it can reduce the reaction intensity on the catalyst surface and increase the ability of macromolecules to further enter the interior of the catalyst; on the other hand, it is conducive to improving the degree of sulfurization of the active metals on the final catalyst, thereby improving the hydrogenation capacity of the catalyst. Adding the first active metal (co-active metal) during grinding can make the dispersion more uniform, and the protective film formed by the alkaline additive introduced at the same time will weaken the interaction between nickel and alumina during the carrier molding process. Then, the above-mentioned carrier is coated with a carbon film. After the carbon film is formed, it can be ensured that the subsequent Mo (main active metal) does not contact the first active metal (auxiliary active metal) that has been loaded and dispersed during the impregnation process, and the main active metal is evenly dispersed on the carbon film. Finally, after mixed atmosphere roasting, air is introduced to remove the carbon film, and the main active metal is evenly dispersed on the carrier. This method can effectively avoid the problem of uneven distribution of active metals due to competitive adsorption on the carrier surface during mixed impregnation of two metals. In addition, a carbon coating treatment is carried out on the pre-carrier containing the first active metal, and it is roasted by inert gas, the water gradually evaporates, the latex particles are gradually squeezed to form a film, and the structure contains cross-linkable groups, which are cross-linked to form a three-dimensional mesh film. The film temporarily provides a loading position for the second active metal. After the catalyst is roasted, the film disappears, and the second active metal is evenly dispersed on the pre-carrier and cooperates with the first active metal, which is beneficial to improve the activity and stability of hydrogenation and demetallization. When the catalyst is roasted in a mixed atmosphere, air removes the carbon layer, allowing the main active metal to be evenly loaded, and water vapor ensures that the pores of the catalyst are further unblocked.

[0049] In summary, the method of the present invention, through the comprehensive coordination of various steps, finally obtains the heavy oil and residual oil hydrodemetallization catalyst, which has greatly improved anti-carbon deposition performance, demetallization activity and metal tolerance, and can ensure the long-term stable operation of the device. DETAILED DESCRIPTION

[0050] The technical solutions and effects of the present invention are further described below in conjunction with embodiments, but are not limited to the following embodiments.

[0051] In the present invention, the ASAP-2420 physical adsorption instrument produced by Michael Company is used to characterize the pore structure and specific surface area of ​​the catalyst.

[0052] Example 1

[0053] (1) 300 g of pseudo-boehmite (alumina mass content 74.0%), 9.8 g of the first active metal basic nickel carbonate (nickel oxide mass fraction 52.0%), 10.5 g of alkaline auxiliary agent NaOH, and 150 g of deionized water were mixed, ground (the average particle size of the sample after grinding was 5.0 μm), and filtered to obtain a solid material A;

[0054] (2) The solid material A obtained in step (1) is kneaded with 9.4 g of nitric acid, 6.0 g of sesbania powder, and 200 g of deionized water, and then extruded into a four-leaf clover shape, dried, and calcined (the drying temperature is 120° C. and the drying time is 6 h. The calcination process adopts a two-stage calcination process, the first stage calcination temperature is 400° C., the calcination time is 3 h, and the calcination atmosphere is air; the second stage calcination temperature is 650° C., the calcination time is 3 h, and the calcination atmosphere is nitrogen) to obtain a pre-support containing a portion of active metal Ni;

[0055] (3) The surface of the pre-carrier is subjected to carbon coating treatment, using an aqueous emulsion containing polyimide and hydroxymethyl cellulose, wherein the mass content of polyimide in the aqueous emulsion is 8.0%, and the mass content of hydroxymethyl cellulose is 0.8%. The amount of the aqueous emulsion (measured by volume mL) and the pre-carrier (measured by mass g) is 1.0 mL / g. After drying and calcination, wherein the drying temperature is 150°C and the drying time is 8 hours; calcination is performed in a nitrogen atmosphere, and the calcination conditions are: calcination at a temperature of 650°C for 5 hours, after calcination, a thin film with a three-dimensional network structure can be formed on the surface of the pre-carrier to obtain carrier B;

[0056] (4) impregnating the carrier B obtained in step (3) with an impregnation solution containing a second active metal in a saturated impregnation manner. In the impregnation solution containing the second active metal, the content of MoO3 is 14.7 g / 100 mL, the content of NiO is 3.17 g / 100 mL, the content of phosphoric acid is 9.16 g / 100 mL, and the content of polyacrylamide is 2.0 g / 100 mL, to obtain a carrier C;

[0057] (5) The carrier C obtained in step (4) was dried at a drying temperature of 150° C. for a drying time of 4 h, and calcined at 600° C. for 4 h. The calcination process adopted a mixed atmosphere in which the volume ratio of air to water vapor was 1:2. Finally, a hydrodemetallization catalyst CAT-1 was obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0058] Example 2

[0059] Compared with Example 1, the difference is that in step (3), the surface of the pre-carrier is subjected to carbon coating treatment, and an aqueous emulsion containing polyimide and hydroxymethyl cellulose is used, the mass content of polyimide in the aqueous emulsion is 10.0%, and the mass content of hydroxymethyl cellulose is 1.2%. The amount relationship of the aqueous emulsion (by volume mL) and the pre-carrier (by mass g) is 1.3mL / g. The roasting conditions are: roasting at 600°C for 4h under a nitrogen atmosphere, and a three-dimensional network structure film can be formed on the surface of the pre-carrier after roasting to obtain carrier B. Finally, a hydrodemetallization catalyst CAT-2 is obtained, and the physicochemical properties and composition of the catalyst are shown in Table 1.

[0060] Example 3

[0061] Compared with Example 1, the difference is that in step (1), 300g of pseudo-boehmite (alumina content 74.0%), 8.5g of alkaline auxiliary agent NaOH and 180g of deionized water are mixed; in step (2), 8.8g of nitric acid, 6.6g of sesbania powder and 240g of deionized water are extruded into a four-leaf clover shape, and then dried at 120°C for 6h, the first stage calcination temperature is 450°C, the calcination time is 4h, and the calcination atmosphere is air; the second stage calcination temperature is 650°C, the calcination time is 4h, and the calcination atmosphere is nitrogen. Finally, the hydrodemetallization catalyst CAT-3 is obtained, and the physicochemical properties and composition of the catalyst are shown in Table 1.

[0062] Example 4

[0063] Compared with Example 1, the difference is that in step (3), the surface of the pre-carrier is subjected to carbon coating treatment, and an aqueous emulsion containing polyimide and hydroxymethyl cellulose is used, the mass content of polyimide in the aqueous emulsion is 12.0%, and the mass content of hydroxymethyl cellulose is 1.5%. The amount of the aqueous emulsion (by volume mL) and the pre-carrier (by mass g) is 0.8 mL / g; the ratio of air to water vapor in the calcination atmosphere in step (5) is 2:1. Finally, a hydrodemetallization catalyst CAT-4 is obtained, and the physicochemical properties and composition of the catalyst are shown in Table 1.

[0064] Example 5

[0065] Compared with Example 1, the difference is that in step (1), the first active metal basic nickel carbonate is 12.2g (nickel oxide mass fraction is 52.0%); in the impregnation solution containing the second active metal in step (4), the content of MoO3 is 14.7g / 100mL, the content of NiO is 2.60g / 100mL, the amount of phosphoric acid added is 9.16g / 100mL, and the content of polyacrylamide is 2.0g / 100mL. The carrier B obtained in step (3) is impregnated in a saturated impregnation manner. Finally, the hydrodemetallization catalyst CAT-5 is obtained. The physicochemical properties and composition of the catalyst are shown in Table 1.

[0066] Example 6

[0067] Compared with Example 1, the difference is that the calcination process in step (2) adopts two-stage calcination, the first stage calcination temperature is 400°C, the calcination time is 5 hours, and the calcination atmosphere is air; the second stage calcination temperature is 700°C, the calcination time is 5 hours, and the calcination atmosphere is nitrogen, to obtain a pre-support containing part of the active metal Ni. Finally, the hydrodemetallization catalyst CAT-6 is obtained, and the physicochemical properties and composition of the catalyst are shown in Table 1.

[0068] Comparative Example 1

[0069] Compared with Example 1, the difference is that the mixed atmosphere is not used in the calcination process in step (5), the calcination temperature is 500°C, the calcination time is 3 hours, and the calcination atmosphere is air. Finally, the hydrodemetallization catalyst DAT-1 is obtained. The physicochemical properties and composition of the catalyst are shown in Table 2.

[0070] Comparative Example 2

[0071] Compared with Example 1, the difference is that the solution used in the carbon coating process in step (3) is changed to a glucose aqueous solution with a mass percentage of 8.8%, and the amount of the glucose aqueous solution (by volume mL) and the pre-support (by mass g) is 1.0 mL / g. Finally, the hydrodemetallization catalyst DAT-2 is obtained, and the physicochemical properties and composition of the catalyst are shown in Table 2.

[0072] Comparative Example 3

[0073] Compared with Example 1, the difference lies in the molding process, that is, all nickel is introduced in step (1), and only metal Mo and additive P are introduced into the second impregnation solution. Finally, the hydrodemetallization catalyst DAT-3 is prepared. The physicochemical properties and composition of the catalyst are shown in Table 2.

[0074] Comparative Example 4

[0075] Compared with Example 1, the difference is that the first active metal Ni is not added in step (1), the amount of MoO3 introduced into the catalyst by the second impregnation liquid in step (4) is 100% of the total MoO3 loading in the catalyst, and the amount of NiO introduced into the catalyst by the second impregnation liquid is 100% of the total NiO loading in the catalyst. Finally, the hydrodemetallization catalyst DAT-4 is prepared, and the physicochemical properties and composition of the catalyst are shown in Table 2.

[0076] Comparative Example 5

[0077] Compared with Example 1, the difference is that in step (1), no alkaline auxiliary agent is introduced during the preparation of solid material A. Finally, a hydrodemetallization catalyst DAT-5 is obtained. The physicochemical properties and composition of the catalyst are shown in Table 2.

[0078] Comparative Example 6

[0079] Compared with Example 1, the difference is that step (3) is omitted, that is, the surface carbon coating treatment is not performed, but the second active metal is directly impregnated and loaded. Finally, the hydrodemetallization catalyst DAT-6 is prepared. The physicochemical properties and composition of the catalyst are shown in Table 2.

[0080] Table 1 Physicochemical properties and catalyst composition of the hydrodemetallization catalysts of various examples

[0081]

[0082] Table 2 Physicochemical properties and catalyst composition of the hydrodemetallization catalysts in each comparative example

[0083]

[0084]

[0085] Evaluation test

[0086] The activity stability tests of Examples 1-6 and Comparative Examples 1-6 were carried out on a 200 mL fixed bed hydrogenation test device. The raw oil was residual oil with a density of 987.8 kg / m 3 (20°C), S content 2.35wt%, metal Ni and V contents 35.4μg / g and 64.1μg / g respectively, CCR content 12.6wt%, the demetallization rate of Example 1 when running for 2000h is 100%, and the others are relative demetallization rates. Specific test conditions are shown in Table 3, and test results are shown in Table 4 and Table 5.

[0087] Table 3 Test conditions

[0088] Reaction temperature, °C 385 Reaction pressure, MPa 15.7 <![CDATA[Liquid hourly space velocity, h -1 > 1.0 Hydrogen to oil ratio, V / V 750

[0089] Table 4 Test results of hydrodemetallization catalysts of various embodiments

[0090]

[0091] Table 5 Test results of the hydrodemetallization catalysts of the comparative examples

[0092]

[0093] It can be seen from Tables 1-5 that the hydrodemetallization catalyst prepared by the method of the present invention has a higher specific surface area and pore volume, and has higher hydrogenation activity and stability, and can well meet the requirements of heavy and residual oil hydrodemetallization processes.

Claims

1. A residual oil hydrodemetallization catalyst, the catalyst comprising an alumina carrier and a second active metal component, the alumina carrier containing a first active metal component, the first active metal component being dispersed in the alumina carrier phase; the mass ratio of the first active metal component in terms of oxide to the alumina carrier is 0.01 to 0.10:

1.

2. The catalyst according to claim 1, characterized in that: The first active metal is at least one of the Group VIII metals, and the Group VIII metal is preferably nickel; And / or, the second active metal component includes molybdenum and at least one selected from Group VIII metals, and the Group VIII metal is preferably nickel.

3. The catalyst according to claim 2, characterized in that: Based on the mass of the catalyst, the content of MoO3 is 10.0% to 28.0%, and the content of the Group VIII metal oxide is 2.0% to 20.0%.

4. The catalyst according to claim 2, characterized in that: The mass ratio of the Group VIII metal in the first active metal component calculated as oxide to the Group VIII metal in the second active metal component calculated as oxide is 0.5 to 1.5:

1.

5. The catalyst according to claim 1, characterized in that: The catalyst includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus; And / or, in the catalyst, the content of the auxiliary component in terms of oxide is 1.0% to 6.0% based on the mass of the catalyst.

6. The catalyst according to claim 1, characterized in that: The specific surface area of ​​the catalyst is 160 to 210 m 2 / g, pore volume is 0.50-0.90mL / g; preferably, the specific surface area of ​​the catalyst is 160-190m 2 / g, and the pore volume is 0.60~0.80mL / g.

7. A method for preparing a residual oil hydrodemetallization catalyst, comprising the following steps: (1) mixing pseudo-boehmite, a first active metal, an alkaline auxiliary agent, and deionized water, grinding, and filtering to obtain a solid material A; (2) mixing the solid material A obtained in step (1) with an adhesive, forming, drying, and calcining to obtain a pre-support containing the first active metal; (3) performing a surface carbon coating treatment on the pre-carrier obtained in step (2), and calcining to obtain a carrier B having a surface carbon film; (4) impregnating the carrier B obtained in step (3) with the second active metal impregnation solution to obtain a carrier C; (5) The carrier C obtained in step (4) is dried and calcined to obtain the catalyst.

8. The preparation method according to claim 7, characterized in that: In step (1), the alkaline auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; And / or, in step (1), the first active metal is at least one of the Group VIII metals; wherein the Group VIII metal is preferably Ni, and the Ni source is selected from at least one of basic nickel carbonate, nickel sulfate, and nickel nitrate; And / or, in step (2), the adhesive is an organic acid and / or an inorganic acid, the inorganic acid is one or more of nitric acid, sulfuric acid, boric acid, and phosphoric acid, and the organic acid is one or more of tartaric acid, citric acid, and oxalic acid; And / or, in step (3), the coating treatment uses an aqueous emulsion containing a polymer compound and water-soluble cellulose; the polymer compound is one or more of polyimide, polyfurfuryl alcohol, and phenolic resin; the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

9. The preparation method according to claim 7, characterized in that: In step (1), the mass ratio of pseudo-boehmite calculated as alumina: first active metal calculated as oxide: alkaline auxiliary agent: water is 200-240: 1.0-8.0: 6.0-15.0: 120-180; And / or, in step (2), the mass of the adhesive is 0.5% to 5.0% of the mass of the pseudo-boehmite in step (1) in terms of alumina; Optionally, in step (2), an extrusion aid and deionized water are added during the molding process; wherein the mass of the extrusion aid is 0.5% to 8.0% of the mass of the pseudo-boehmite in step (1) calculated as alumina, and the amount of deionized water is 80% to 120% of the mass of the pseudo-boehmite in step (1) calculated as alumina; Preferably, the extrusion aid is one or more of methyl cellulose, ethyl cellulose, sesbania powder and starch.

10. The preparation method according to claim 7, characterized in that: In step (2), the calcination adopts a two-stage calcination process, the first stage calcination temperature is 350-450° C., the calcination time is 2-6 hours, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably air; the second stage calcination temperature is 450-750° C., the calcination time is 2-8 hours, and the calcination atmosphere is one or more of air, nitrogen, or water vapor, preferably nitrogen; Preferably, the second stage roasting temperature is 150-300° C. higher than the first stage roasting temperature.

11. The preparation method according to claim 8, characterized in that: In step (3), in the aqueous emulsion, the mass content of the polymer compound is 5.0% to 15.0%, and the mass content of the water-soluble cellulose is 0.5% to 3.0%; And / or, in step (3), the amount of the aqueous emulsion measured by volume mL and the pre-carrier measured by mass g is 0.8 to 1.5 mL / g.

12. The preparation method according to claim 7, characterized in that: In step (3), the calcination conditions are: temperature of 500-700°C, time of 2.0-8.0h, and calcination atmosphere of inert atmosphere, preferably one or more of nitrogen and argon; And / or, in step (5), the calcination temperature is 550-750° C., the calcination time is 2-10 hours, and the calcination is carried out in a mixed atmosphere of air and water vapor, wherein the volume ratio of air to water vapor is 0.1-5.0:1.

0.

13. The preparation method according to claim 7, characterized in that: The second active metal includes Mo and at least one selected from Group VIII metals; the Group VIII metal is preferably Ni; Preferably, at least one auxiliary agent selected from fluorine, phosphorus, silicon or boron is introduced into the second active metal impregnation solution; Preferably, the second active metal impregnation solution contains a water-soluble polymer J; the water-soluble polymer J is one or more of polyethylene glycol, polyvinyl alcohol, polyacrylamide and methyl cellulose.

14. The preparation method according to claim 13, characterized in that: In the second active metal impregnation solution, the content of Mo calculated as MoO3 is 10.0 to 50.0 g / 100 mL, and the content of Group VIII metal calculated as oxide is 3.0 to 20.0 g / 100 mL; and / or, the mass of the Group VIII metal introduced into the catalyst by the second active metal impregnation solution as oxide accounts for 50.0% to 80.0% of the total Group VIII metal loading as oxide in the catalyst; and / or, the content of the auxiliary agent in the second active metal impregnation solution is 3.0 to 18.0 g / 100 ml, preferably 5.0 to 15.0 g / 100 ml; And / or, the content of the water-soluble polymer J in the second active metal impregnation solution is 0.5 to 2.5 g / 100 ml.

15. The preparation method according to claim 6, characterized in that: The catalyst has a MoO3 content of 10.0% to 28.0% and a Group VIII metal oxide content of 2.0% to 20.0% based on the mass of the catalyst; Preferably, in the catalyst, the mass ratio of the Group VIII metal introduced into the catalyst by the first active metal component in terms of oxide to the Group VIII metal introduced into the catalyst by the second active metal component in terms of oxide is 0.5 to 1.5:1; Preferably, in the catalyst, the content of the additive in terms of oxide is 1.0% to 6.0% based on the mass of the catalyst.

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