Distillate hydrofining catalyst, method for making and use thereof

Abstract

The present application provides a distillate oil hydrogenation catalyst and a preparation method and application thereof, comprising 1-30% of molecular sieve, 5-15% of modified amorphous aluminum silicate, 20-40% of heteropoly acid compound in terms of metal oxide, and the rest is aluminum oxide, with the mass of the catalyst being 100%; the heteropoly acid compound is selected from at least one of Ni3[H4P2Mo 12 Ni9O 56 (L)7]、[{Ni(L)2}2Mo8O 26 ] at least one of wherein HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid, 3-amino-2,5-dihydroxybenzoic acid. The catalyst has a highly dispersed II type active phase, and can be applied to distillate oil hydrotreating, realizing efficient hydrogenation.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst technology, and particularly relates to a distillate oil hydrogenation catalyst, a preparation method and application thereof. BACKGROUND

[0002] Hydrofining can improve the quality of oil products, and make oil products undergo hydrogenation desulfurization, hydrogenation denitrification, hydrogenation saturation and the like, and remove impurities such as sulfur and nitrogen in the oil products. Currently, the catalysts in the hydrofining process are generally based on alumina and magnesia as carriers, and group VIII and group VIB metal elements as active components.

[0003] Patent document CN1133723C discloses a distillate oil hydrofining catalyst and a preparation method thereof, which is based on alumina small spheres containing silica as a carrier, contains 21-28wt% of MoO3, 22-8wt% of NiO and 0.03-2.0wt% of CoO, and is prepared by two-stage spraying and impregnation. The preparation route is complex, and the hydrogenation activity of the catalyst is not high.

[0004] Patent document CN1101454C discloses a distillate oil hydrodesulfurization catalyst and a preparation method thereof. The catalyst is based on alumina or silica-containing alumina as a carrier, and Mo-Ni as an active component, and adds a phosphorus additive. The carrier is segmented and co-impregnated by using an alkaline Mo-Ni-P co-impregnation solution. The preparation route of the catalyst is complex, and the hydrogenation activity is not high.

[0005] Patent document CN1472283A discloses a catalyst for selective hydrodesulfurization of olefin-containing naphtha and a preparation method thereof. The catalyst is mainly prepared by using a single-layer dispersion method, and the component ratio is: CoO+MoO3: 6-20wt%; MgO: 8-20wt%; Al2O3: 40-86wt%, and the Mo / Co atomic ratio in the mixture of CoO and MoO3 is 1-6:1.

[0006] Patent document WO2007084438 discloses a selective hydrodesulfurization catalyst, which contains 8-30wt% of molybdenum selected from group VIB, 2-8wt% of cobalt selected from group VIII, and an appropriate amount of an organic compound as a complexing agent loaded on a silicon carrier. The catalyst is used to treat a catalytic cracking gasoline raw material, and the olefin saturation rate is low. The defects of the technology are that the preparation route is complex, and the hydrogenation activity is not high.

[0007] Patent document CN1049679C discloses a diesel oil hydroconversion catalyst, which is based on alumina and Y-type molecular sieve as a carrier, contains at least one metal of group VIB and at least one metal of group VIII, and is suitable for the hydroconversion of petroleum distillates at 150-400℃. The catalytic activity of the catalyst is not high when used for the hydroprocessing of high-sulfur and high-nitrogen oil products.

[0008] Patent document US5441630 discloses a kind of water slide stone as carrier component is added to A12O3, calcined water slide stone has large surface area, basicity, after Co, Mo is shown with high HDS activity, low olefin saturation percentage after carrier impregnation;This technology has a large amount of olefin loss.

[0009] Patent document CN107282053A discloses a kind of high-nitrogen diesel oil hydrogenation catalyst and its preparation method, which comprises taking alumina as carrier, Mo and Ni as active component, and adding complexing agent and additive, then after modification, catalyst is obtained.

[0010] Patent document CN101172261A discloses a kind of W-Mo-Ni hydrogenation catalyst prepared by body phase method. The catalyst uses active metal Ni, W component and the salt mixed solution of auxiliary agent to generate Ni x W y O z Composite oxide precursor, then mixed with MoO3, filter, shape, activation as final catalyst, the hydrogenation performance of the catalyst W-Ni-Mo system active metal combination is good, some easy desulfurization, denitrification reaction is realized through hydrogenation path, thereby excessive consumption of hydrogen, increase processing cost, in addition, W-Mo-Ni and Al coprecipitation can form some active metal and Al with strong aluminate, which is not easy to reduce sulfide, reduce the utilization rate of active metal.

[0011] The above hydrogenation catalyst has low catalytic activity and poor denitrification and desulfurization rate when used for hydrogenation treatment of high-sulfur and high-nitrogen oil. SUMMARY

[0012] The present application provides a kind of fraction oil hydrogenation catalyst and its preparation method and application, the catalyst has highly dispersed II class active phase, the catalyst can be applied to fraction oil hydrogenation treatment, realizes high-efficiency hydrogenation, effectively overcome the defects of prior art.

[0013] The first aspect of the present application provides a kind of fraction oil hydrogenation catalyst, comprising 1%-30% of molecular sieve, 5%-15% of modified amorphous aluminum silicate, 20%-40% of heteropoly acid compound calculated as metal oxide and the rest is alumina, based on 100% of the mass of catalyst;Heteropoly acid compound is selected from at least one of Ni3[H4P2Mo 12 Ni9O 56 (L)7]、[{Ni(L)2}2Mo8O 26 ]Wherein HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid and 3-amino-2,5-dihydroxybenzoic acid.

[0014] According to an embodiment of the present application, the heteropolyacid compound is Ni3[H4P2Mo 12 Ni9O 56 (L)7] is obtained by a preparation method comprising the following process: uniformly mixing NaL, (NH4) 12 [H2P2Mo 12 O 48 ], a nickel salt, and water, adjusting the pH to 2.2-2.6, and thermostating at 80-100°C for 1-3h to obtain Ni3[H4P2Mo 12 Ni9O 56 (L)7], wherein the molar ratio of NaL, (NH4) 12 [H2P2Mo 12 O 48 ] and the nickel salt is 10:1:15; and / or, [{Ni(L)2}2Mo8O 26 ] is obtained by a preparation method comprising the following process: uniformly mixing NaL, (NH4)6Mo7O 24 , a nickel salt, and water, adjusting the pH to 1.5-1.8, heating to boiling for 1-3h to obtain [{Ni(L)2}2Mo8O 26 ], wherein the molar ratio of NaL, (NH4)6Mo7O 24 , and the nickel salt is 4:1:2.

[0015] According to an embodiment of the present application, the heteropolyacid compound is a mixture of Ni3[H4P2Mo 12 Ni9O 56 (L)7], and [{Ni(L)2}2Mo8O 26 ], wherein the molar ratio of Ni3[H4P2Mo 12 Ni9O 56 (L)7] and [{Ni(L)2}2Mo8O 26 ] is 1:(5-15).

[0016] According to an embodiment of the present application, the modified amorphous aluminosilicate is obtained by a preparation method comprising the following process: impregnating the amorphous aluminosilicate in an impregnation solution containing tetrabutyl titanate.

[0017] According to an embodiment of the present application, the diameter of the catalyst is 0.8-2.0mm or greater than 2.5mm.

[0018] In a second aspect of the present application, a preparation method of the above hydrogenation catalyst is provided, comprising the following steps: uniformly mixing pseudo-boehmite, molecular sieve, modified amorphous aluminosilicate, and water, and obtaining a calcination product after calcination; impregnating the calcination product in an impregnation solution containing a heteropolyacid compound and an inorganic acid, and obtaining the hydrogenation catalyst after drying.

[0019] According to an embodiment of the present application, the calcination condition is: temperature is 400-550℃, time is 2-6h.

[0020] According to an embodiment of the present application, the impregnation condition is: temperature is 50-70℃, time is 1-3h.

[0021] According to an embodiment of the present application, the drying condition is: temperature is 100-150℃, time is 2-4h.

[0022] In a third aspect of the present application, a hydrogenation method is provided, comprising: hydrogenating a raw material containing distillate oil under the action of a catalyst to obtain a hydrogenation product; the catalyst comprises the hydrogenation catalyst or the hydrogenation catalyst prepared by the preparation method.

[0023] The present application has at least the following beneficial effects:

[0024] The distillate oil hydrogenation catalyst of the present application contains a heteropolyacid compound with a specific configuration, and the special configuration of the heteropolyacid compound itself has dispersibility, so that the hydrogenation catalyst has a highly dispersed II-type active phase; when the hydrogenation catalyst is used in hydrofining, the active metal can be in contact with more hydrogenation raw materials, and the catalytic activity of the hydrogenation catalyst is significantly improved; due to the high catalytic activity of the hydrogenation catalyst, high-efficiency hydrogenation can be achieved with less catalyst, and the cost of hydrogenation treatment is reduced. The hydrogenation catalyst of the present application has high catalytic activity and can be used in the hydrogenation treatment of oil products, especially in high-sulfur and high-nitrogen oil products.

[0025] The preparation method of the distillate oil hydrogenation catalyst provided by the present application comprises the following steps: uniformly mixing pseudo-boehmite, molecular sieve, modified amorphous aluminum silicate and water, and obtaining a calcination product after calcination; and then impregnating the calcination product in an impregnation solution containing a heteropolyacid compound and an inorganic acid, and obtaining the hydrogenation catalyst after drying. The method of calcination first and then impregnation makes the active metal and the carrier only have weak van der Waals force, and further improves the dispersibility of the active component of the catalyst, so that the reaction activity of the catalyst can be effectively improved, and a catalyst with high activity and stability is obtained.

[0026] In addition, the preparation method of the distillate oil hydrogenation catalyst provided by the present application also has the advantages of simple preparation process, easy operation, etc., and is beneficial to industrial production and application. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is the adsorption isotherm and pore size distribution graph of the distillate oil hydrogenation catalyst C of Example 3;

[0028] Figure 2is a transmission electron microscope image of the fraction oil hydrogenation catalyst C of Example 3. DETAILED DESCRIPTION

[0029] The following detailed description is merely exemplary in nature and is not intended to limit the scope of the application, as described. The application is described with regard to the embodiments, however, all modifications and alterations of the application will become apparent to those having ordinary skill in the art from the detailed description. If not otherwise stated, all percentages are by weight and all measurements are at 25°C.

[0030] The present application provides a fraction oil hydrogenation catalyst, comprising 1%-30% of molecular sieve, 5%-15% of modified amorphous aluminum silicate, 20%-40% of heteropoly acid compound calculated as metal oxide, and the rest is alumina, based on 100% of the mass of the catalyst; the structural formula of the heteropoly acid compound is selected from at least one of Ni3[H4P2Mo 12 Ni9O 56 (L)7]、[{Ni(L)2}2Mo8O 26 ]and at least one of wherein HL is at least one of acetic acid, 4-methyl-3,5-dihydroxybenzoic acid, 3-amino-2,5-dihydroxybenzoic acid

[0031] The above-mentioned heteropoly acid compound contains metals Ni and Mo, and the mass of the heteropoly acid compound is calculated as the metal oxide, which is nickel oxide and molybdenum trioxide.

[0032] The above-mentioned hydrogenation catalyst has a highly dispersed Class II active phase, and in the hydrogenation catalyst, alumina, molecular sieve, and modified amorphous aluminum silicate are collectively used as the carrier of the catalyst; the heteropoly acid compound is used as the active component of the catalyst, and the above-mentioned specific configuration of the heteropoly acid compound itself has high dispersity, the use of the specific configuration of the heteropoly acid compound can improve the utilization rate of the active metal, reduce the cost, and significantly improve the hydrogenation activity of the hydrogenation catalyst. The above-mentioned catalyst can be applied in hydrofining.

[0033] In some embodiments, Ni3[H4P2Mo 12 Ni9O 56 (L)7]is obtained by a preparation method comprising the following process: uniformly mixing NaL, (NH4) 12 [H2P2Mo 12 O 48 ], a nickel salt, and water, adjusting the pH to 2.2-2.6, and keeping the temperature at 80-100°C for 1-3h to obtain Ni3[H4P2Mo 12 Ni9O 56 (L)7], wherein NaL, (NH4) 12 [H2P2Mo 12 O 48a molar ratio of 10:1:15.

[0034] In the above embodiments, NaL is mixed with water to form a solution containing NaL, (NH4)6Mo7O 12 [H2P2Mo 12 O 48 a mixture solution, the pH of the mixture solution is adjusted to 2.2-2.6, and the mixture solution is heated to promote the reaction, after the reaction is completed, the obtained precipitate product is washed and dried to obtain Ni3[H4P2Mo 12 Ni9O 56 (L)7], wherein the nickel salt comprises nickel nitrate; the reaction temperature is 80-100°C, for example, 80°C, 82°C, 85°C, 88°C, 90°C, 92°C, 95°C, 98°C, 100°C, or a range defined by any two of them; and the reaction time is 1-3h, for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, or a range defined by any two of them.

[0035] In some embodiments, the heteropolyacid compound is Ni3[H4P2Mo 26 ] is obtained by a preparation method comprising the following process: NaL, (NH4)6Mo7O 24 , a nickel salt, and water are mixed uniformly, the pH is adjusted to 1.5-1.8, and heated to boiling for 1-3h to obtain the [{Ni(L)2}2Mo8O 26 ], wherein the molar ratio of NaL, (NH4)6Mo7O 24 , and the nickel salt is 4:1:2.

[0036] In the above embodiments, NaL is mixed with water to form a solution containing NaL, (NH4)6Mo7O 24 , a nickel salt to obtain a mixture solution, the pH of the mixture solution is adjusted to 1.5-1.8, and the mixture solution is heated to promote the reaction, after the reaction is completed, the obtained precipitate product is washed and dried to obtain [{Ni(L)2}2Mo8O 26 ], wherein the nickel salt comprises nickel nitrate; and the reaction time is 1-3h, for example, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, or a range defined by any two of them.

[0037] In some embodiments, the heteropolyacid compound is Ni3[H4P2Mo 12 Ni9O 56 (L)7], a mixture of [{Ni(L)2}2Mo8O 26 ], and Ni3[H4P2Mo 12 Ni9O56 (L)7] and [{Ni(L)2}2Mo8O 26 ] in a molar ratio of 1 : (5-15), for example 1 :5, 1 :6, 1 :7, 1 :8, 1 :9, 1 :10, 1 :11, 1 :12, 1 :13, 1 :14, 1 :15 or a range consisting of any two of them.

[0038] In some embodiments, the molecular sieve comprises a mesoporous ETS-10 molecular sieve, the framework of which is composed of six-coordinated (TiO6) 2- and four-coordinated (SiO4) structures, in some embodiments, the mesoporous ETS-10 molecular sieve has a pore volume of 0.25 cm 3 / g.

[0039] In the above embodiments, the mesoporous ETS-10 molecular sieve can be obtained by a conventional method, using the synthesis method of mesoporous ETS-10 disclosed in patent document CN109264738A.

[0040] The hydrogenation catalyst of the present application further comprises an extrusion aid, wherein the extrusion aid can be at least one of amaranth powder, polyvinyl alcohol, methyl cellulose, polyethylene glycol, and the extrusion aid is 1-10% based on 100% of the mass of the catalyst.

[0041] The hydrogenation catalyst of the present application further comprises a binder, which can be at least one of nitric acid, citric acid, and the binder is 1-10% based on 100% of the mass of the catalyst.

[0042] In the present application, the modified amorphous aluminum silicate is obtained by a preparation method comprising the process of impregnating amorphous aluminum silicate in an impregnation solution containing tetrabutyl titanate. The addition of the modified amorphous aluminum silicate can adjust the acidity of the hydrogenation catalyst and improve the desulfurization and denitrification rate of the hydrogenation catalyst. The B acid / L acid of the modified amorphous aluminum silicate is 0.98, wherein the B acid is the ability to give H + and the L acid is the ability to accept an electron pair.

[0043] The particle size of the catalyst is regulated according to actual needs, in some embodiments, the diameter of the catalyst is 0.8-2.0 mm, for example 0.8 mm, 0.9 mm, 1 mm, 1.2 mm, 1.3 mm, 1.5 mm, 1.8 mm, 2 mm or a range consisting of any two of them. When the catalyst is applied to large-scale production, in other embodiments, the diameter of the catalyst is greater than 2.5 mm.

[0044] To achieve the above object, the application further provides a preparation method of the hydrogenation catalyst, comprising the following steps: uniformly mixing pseudo-boehmite, molecular sieve, modified amorphous aluminum silicate and water, and obtaining a calcined product after calcination; and impregnating the calcined product in an impregnation solution containing a heteropolyacid compound and an inorganic acid, and obtaining the hydrogenation catalyst after drying.

[0045] The preparation method of the hydrogenation catalyst provided by the application comprises the following steps: calcining pseudo-boehmite, molecular sieve and modified amorphous aluminum silicate to obtain a carrier of the catalyst, and then impregnating the carrier with a heteropolyacid compound having a specific configuration to obtain the catalyst. The above process of calcination followed by impregnation can weaken the interaction between the carrier and the active component, and further accurately control the active phase structure of the catalyst, so that highly dispersed type II hydrogenation active centers are formed.

[0046] In the above preparation method, the pseudo-boehmite, molecular sieve and modified amorphous aluminum silicate are uniformly mixed with water to obtain a mixture, and a binder and a binder can also be added to the mixture to promote the combination of the pseudo-boehmite and molecular sieve, so that the mixture is calcined to obtain a calcined product, i.e. the carrier of the catalyst.

[0047] Before the above calcination, the mixture is also subjected to extrusion molding, which comprises extruding the mixture through a nozzle with a certain shape, and then drying and molding. The specific shape obtained is adjusted according to the shape of the actual catalyst, for example, the shape of the product can be controlled to be strip-shaped, clover-shaped, granular or tooth ball-shaped during the extrusion molding.

[0048] In the above embodiment, the drying and molding conditions are as follows: the temperature is 80-150℃, for example, 80℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃ or a range formed by any two of them; in some embodiments, the calcination conditions are as follows: the temperature is 400℃-550℃, for example, 400℃, 410℃, 420℃, 430℃, 450℃, 460℃, 470℃, 480℃, 490℃, 500℃, 510℃, 520℃, 530℃, 540℃, 550℃ or a range formed by any two of them; and the time is 2h-6h, for example, 2h, 3h, 4h, 5h, 6h or a range formed by any two of them.

[0049] In the application, the impregnation process comprises the following steps: first, forming an inorganic acid solution by mixing an inorganic acid with water, then mixing the heteropolyacid compound with the inorganic acid solution, stirring uniformly to form an impregnation solution, and then mixing the calcined product meeting the above requirements with the impregnation solution to make the calcined product fully contact with the impregnation solution, so as to realize the impregnation process.

[0050] Specifically, in the impregnation process, the calcined product is fully contacted with the impregnation solution, and the heteropolyacid compound in the impregnation solution is loaded on the calcined product. In addition, the calcined product is impregnated in the above-mentioned impregnation solution system containing inorganic acid, which includes phosphoric acid, so that the catalyst has appropriate acidity, which helps to improve its hydrogenation catalytic activity.

[0051] In the above embodiments, the impregnation process can be carried out by using the equal volume impregnation method or the excess impregnation method, and the equal volume impregnation method is preferred.

[0052] In specific operation, the saturation adsorption amount of the prepared calcined product can be detected first, and then the volume of the impregnation solution is determined according to the adsorption amount of the calcined product, and the impregnation is carried out according to the above-mentioned equal volume method or excess impregnation method.

[0053] In some embodiments, the impregnation conditions are as follows: the temperature is 50-70℃, for example, 50℃, 55℃, 60℃, 65℃, 70℃ or a range formed by any two of them; the time is 1-3h, for example, 1h, 1.5h, 2h, 2.5h, 3h or a range formed by any two of them.

[0054] In the above embodiments, the drying is to remove the residual moisture on the impregnated product, and in some embodiments, the drying conditions are as follows: the temperature is 100-150℃, for example, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃ or a range formed by any two of them; the time is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, 4h or a range formed by any two of them.

[0055] The present application provides a hydrogenation method, which comprises: hydrogenating a raw material containing distillate oil under the action of a catalyst to obtain a hydrogenation product; the catalyst comprises the hydrogenation catalyst or is prepared by the above-mentioned method.

[0056] Specifically, the catalyst is placed in a reactor, and a hydrogenation raw material containing distillate oil is introduced into the reactor to contact with the catalyst, and a hydrogenation catalytic reaction is carried out to obtain a hydrogenation product. In the above embodiments, the catalyst needs to be presulfurized before contacting with the hydrogenation raw material, so as to further improve the hydrogenation activity of the catalyst.

[0057] In order to achieve the above-mentioned purpose, the hydrogenation reaction conditions are as follows: the reaction temperature is 300-400℃, for example, 300℃, 320℃, 350℃, 380℃, 400℃ or a range formed by any two of them; the hydrogen partial pressure is 6-12MPa, for example, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa or a range formed by any two of them; the hydrogen / oil volume ratio is 300:1-600:1, and the volume space velocity is 0.5-2h-1 -2.0h -1 .

[0058] The hydrogenation method provided by the application can realize high desulfurization and denitrification rates, and can improve the oil product and reduce environmental pollution.

[0059] In order to make the purpose, technical scheme and advantages of the application clearer, the technical scheme in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application.

[0060] In each embodiment and comparative example, other chemicals used are commercially available chemical pure reagents;

[0061] Example 1

[0062] (1) 100 g of pseudo-boehmite, 0.9 g of mesoporous ETS-10 molecular sieve and 16.4 g of modified amorphous silica-alumina are uniformly mixed, and then 4 g of sesbania powder, 4 g of nitric acid and 4 g of an aqueous solution of citric acid are added to form 1.5 mm three-leaf clover-shaped extrudates, which are dried and molded at a temperature of 120 DEG C, and then calcined at a temperature of 550 DEG C for 4 h to obtain a calcined product, i.e., a carrier.

[0063] (2) (NH4) 12 [H2P2Mo 12 O 48 ] is uniformly mixed with CH3COONa and water, and then Ni(NO3)3 is added while stirring, and the mixture is uniformly mixed, and then the pH of the solution is adjusted to 2.2-2.6, and the solution is heated to 90 DEG C and reacted for 2 h, and then the reaction product is washed and dried to obtain Ni3[H4P2Mo 12 Ni9O 56 (CH3COO)7]; 12 [H2P2Mo 12 O 48 ] and Ni(NO3)3 are in a molar ratio of 10:1:15;

[0064] (3) Ni3[H4P2Mo 12 Ni9O 56 (CH3COO)7] and a phosphoric acid solution are mixed, and then the mixture is stirred at 60 DEG C for 1 h to obtain an impregnation solution.

[0065] The calcined product obtained in step (1) is impregnated in the impregnation solution in an equal volume, and then dried to obtain a distillate oil hydrogenation catalyst A.

[0066] Example 2

[0067] (1) 100g pseudo-boehmite, 70g mesoporous ETS-10 molecular sieve, 12.7g modified amorphous aluminum silicate are mixed uniformly, and then 4g sesbania powder, 4g nitric acid, 4g aqueous solution of citric acid are added to form 1.5mm three-leaf clover shape by extrusion, dried and molded, and then calcined to obtain a calcined product, i.e. a carrier; wherein the temperature for drying and molding is 120℃; the calcination conditions are: temperature 550℃, time 4h;

[0068] (2) (NH4) 12 [H2P2Mo 12 O 48 ] is mixed uniformly with 4-methyl-3, 5-dihydroxybenzoic acid sodium, water, and then Ni(NO3)3 is added while stirring, and then the mixture is uniformly mixed, the pH of the solution is adjusted to 2.2-2.6, heated to 90℃ and reacted for 2h, and then the reaction product is washed and dried to obtain Ni3[H4P2Mo 12 Ni9O 56 (L)7]; wherein the molar ratio of 4-methyl-3, 5-dihydroxybenzoic acid sodium, (NH4) 12 [H2P2Mo 12 O 48 ], and Ni(NO3)3 is 10:1:15; wherein HL is 4-methyl-3, 5-dihydroxybenzoic acid;

[0069] (3) Ni3[H4P2Mo 12 Ni9O 56 (L)7], and phosphoric acid solution are mixed to prepare an impregnation solution after stirring at 60℃ for 1h;

[0070] The calcined product prepared in step (1) is impregnated in the impregnation solution in equal volume, and then dried to obtain fraction oil hydrogenation catalyst B.

[0071] Example 3

[0072] (1) 100g pseudo-boehmite, 21.5g mesoporous ETS-10 molecular sieve, 14.7g amorphous aluminum silicate are mixed uniformly, and then 4g sesbania powder, 4g nitric acid, 4g aqueous solution of citric acid are added to form 1.5mm three-leaf clover shape by extrusion, dried and molded, and then calcined to obtain a calcined product, i.e. a carrier; wherein the temperature for drying and molding is 120℃; the calcination conditions are: temperature 550℃, time 4h;

[0073] (2) (NH4) 12 [H2P2Mo 12 O 48] and water, and then Ni(NO3)3 is added while stirring, and the mixture is uniformly mixed, and then the pH of the solution is adjusted to 2.2-2.6, and the solution is heated to 90°C and reacted for 2h, and the reaction product is washed and dried to obtain Ni3[H4P2Mo 12 Ni9O 56 (L)7]; wherein the molar ratio of sodium 3-amino-2,5-dihydroxybenzoate, (NH4) 12 [H2P2Mo 12 O 48 ] and Ni(NO3)3 is 10:1:15; wherein HL is 3-amino-2,5-dihydroxybenzoic acid

[0074] (3) Ni3[H4P2Mo 12 Ni9O 56 (L)7] and a phosphoric acid solution are mixed to prepare an impregnation solution;

[0075] The calcined product prepared in step (1) is impregnated in the impregnation solution in an equal volume, and then dried to prepare fraction oil hydrogenation catalyst C.

[0076] Example 4

[0077] Compared with Example 2, 70g of mesoporous ETS-10 molecular sieve and 12.7g of modified amorphous aluminosilicate in step (1) are replaced by 21.5g of mesoporous ETS-10 molecular sieve and 14.7g of modified amorphous aluminosilicate; other conditions remain unchanged to prepare hydrogenation catalyst D.

[0078] Example 5

[0079] Compared with Example 1, 0.9g of mesoporous ETS-10 molecular sieve and 16.4g of modified amorphous aluminosilicate in step (1) are replaced by 21.5g of mesoporous ETS-10 molecular sieve and 14.7g of modified amorphous aluminosilicate; other conditions remain unchanged to prepare fraction oil hydrogenation catalyst E.

[0080] Comparative Example 1

[0081] An impregnation solution prepared from nickel nitrate and ammonium molybdate is impregnated on an alumina carrier, dried at 100°C-120°C for 4h, and calcined at 500°C-600°C for 4h to prepare hydrogenation catalyst F.

[0082] Comparative Example 2

[0083] An impregnation solution prepared from nickel nitrate and ammonium molybdate is impregnated on an alumina carrier containing ETS-10 molecular sieve, dried at 100°C-120°C for 4h, and calcined at 500°C-600°C for 4h to prepare hydrogenation catalyst G.

[0084] Comparative Example 3

[0085] The hydrogenation catalyst H is prepared by impregnating the amorphous silica-alumina-containing alumina carrier with a co-impregnation solution of nickel nitrate and ammonium molybdate, drying at 100-120°C for 4 hours, and calcining at 500-600°C for 4 hours.

[0086] The physical and chemical properties of the catalysts prepared in Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0087] The catalysts of Examples 1-5 and Comparative Examples 1-3 were hydrogenated by the following hydrogenation methods, respectively:

[0088] Coking diesel oil having a sulfur content of 1260 ppm and a nitrogen content of 1178 ppm was used as the evaluation feedstock, and 8 g of the catalyst was hydrogenated in a 10 mL micro-reactor. During the hydrogenation, the reaction conditions were as follows: a reaction temperature of 340°C, a hydrogen partial pressure of 6.4 MPa, a hydrogen / oil volume ratio of 500:1, a volume space velocity of 2.0 h -1 The micro-reactor evaluation results of the hydrogenation catalysts obtained by hydrogenating coking diesel oil are shown in Table 2.

[0089] Wax oil (distillation range: 225-521°C) having a sulfur content of 900 ppm and a nitrogen content of 726 ppm was used as the evaluation feedstock, and 8 g of the catalyst was hydrogenated in a 10 mL micro-reactor. During the hydrogenation, the reaction conditions were as follows: a reaction temperature of 360°C, a hydrogen partial pressure of 12 MPa, a hydrogen / oil volume ratio of 800:1, a volume space velocity of 1.5 h -1 The micro-reactor evaluation results of the hydrogenation catalysts obtained by hydrogenating wax oil are shown in Table 3.

[0090] Table 1 Physical and chemical properties of the catalysts

[0091]

[0092] Table 2 Micro-reactor hydrogenation evaluation results

[0093]

[0094] Table 3 Micro-reactor hydrogenation evaluation results

[0095]

[0096] Figure 1 Adsorption isotherm and pore size distribution of the distillate oil hydrogenation catalyst C of Example 3; Figure 2 Transmission electron microscope image of the hydrogenation catalyst C of Example 3, according to Figure 2 As can be seen, the catalyst of the present application does not agglomerate, and forms a layered structure, and has high dispersibility.

[0097] According to Table 2 and Table 3, in the case of equal metal oxide loadings, the catalytic activity of the catalysts of the examples is obviously higher than that of the comparative examples, the catalysts of the present application can achieve a desulfurization rate of up to 99.2% and a denitrification rate of up to 99.2%, and have higher desulfurization and denitrification activity.

[0098] In summary, the heteropoly acid compound with a specific configuration in the distillate oil hydrogenation catalyst has high dispersibility, the distillate oil hydrogenation catalyst has a highly dispersed II-type active phase, has high catalytic activity, and can be used in the hydrogenation treatment of oil products, and can be especially used in oil products with high sulfur and nitrogen.

[0099] The preferred embodiments of the present application and the test verification are described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and changes without creative labor based on the concept of the present application. Therefore, any technical solution obtained by logical analysis, reasoning or limited experiment based on the existing technology according to the concept of the present application shall be within the protection scope determined by the claims.

Claims

1. A catalyst for the hydrogenation of distillate oil, characterized in that, The catalyst comprises, by mass, 1%-30% molecular sieve, 5%-15% modified amorphous aluminum silicate, 20%-40% heteropolyacid compounds (based on metal oxides), and the remainder being alumina; the modified amorphous aluminum silicate has a Brønsted acid / Low acid ratio of 0.

98. The heteropolyacid compound is Ni3[H4P2Mo] 12 Ni9O 56 [(L)7]、[{Ni(L)2}2Mo8O] 26 A mixture of Ni3[H4P2Mo] 12 Ni9O 56 [(L)7] and [{Ni(L)2}2Mo8O] 26 The molar ratio of ] is 1:(5-15); where L is at least one of acetate, 4-methyl-3,5-dihydroxybenzoate, and 3-amino-2,5-dihydroxybenzoate; The Ni3[H4P2Mo] 12 Ni9O 56 (L)7] is obtained by a preparation method including the following process: NaL, (NH4) 12 [H2P2Mo 12 O 48 The nickel salt and water are mixed evenly, the pH is adjusted to 2.2-2.6, and the mixture is kept at 80℃-100℃ for 1-3 hours to obtain the Ni3[H4P2Mo] 12 Ni9O 56 [(L)7], of which NaL and (NH4) 12 [H2P2Mo 12 O 48 The molar ratio of nickel salts is 10:1:15; and / or, The [{Ni(L)2}2Mo8O 26 It is obtained through a preparation method including the following processes: NaL, (NH4)6Mo7O 24 The nickel salt and water are mixed evenly, the pH is adjusted to 1.5-1.8, and the mixture is heated to boiling for 1-3 hours to obtain the [{Ni(L)2}2Mo8O] 26 ], including NaL, (NH4)6Mo7O 24 The molar ratio of nickel salt is 4:1:

2.

2. The hydrogenation catalyst according to claim 1, characterized in that, The modified amorphous aluminum silicate is obtained by a preparation method comprising the following process: impregnating the amorphous aluminum silicate in an impregnation solution containing tetrabutyl titanate.

3. The hydrogenation catalyst according to claim 1 or 2, characterized in that, The catalyst has a diameter of 0.8 mm to 2.0 mm or greater than 2.5 mm.

4. The method for preparing the hydrogenation catalyst according to any one of claims 1-3, characterized in that, Includes the following steps: The pseudoboehmite, molecular sieve, modified amorphous aluminum silicate, and water were mixed evenly and then calcined to obtain the calcined product. The calcined product is impregnated in an impregnation solution containing heteropolyacid compounds and inorganic acids, and then dried to obtain the hydrogenation catalyst.

5. The preparation method according to claim 4, characterized in that, The roasting conditions are: temperature 400℃-550℃, time 2h-6h.

6. The preparation method according to claim 4, characterized in that, The impregnation conditions are: temperature 50℃-70℃, time 1h-3h.

7. The preparation method according to claim 4, characterized in that, The drying conditions are: temperature 100℃-150℃, time 2h-4h.

8. A hydrogenation method, characterized in that, include: The feedstock containing distillate oil is subjected to a hydrogenation reaction under the action of a catalyst to obtain a hydrogenated product; the catalyst includes the hydrogenation catalyst according to any one of claims 1-3 or the hydrogenation catalyst prepared by the preparation method according to any one of claims 4-7.

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