A diesel hydro-upgrading catalyst, its preparation method and application

Abstract

The present disclosure relates to a diesel hydro-upgrading catalyst, a preparation method and application thereof, the catalyst comprising a carrier and an active metal component supported on the carrier; the active metal component comprising a Group VIII metal element and a Group VIB metal element; the carrier comprising a composite molecular sieve and a heat-resistant inorganic oxide matrix, the composite molecular sieve comprising a first molecular sieve and a second molecular sieve, the first molecular sieve being a Y molecular sieve, and the second molecular sieve being a molecular sieve with an N value greater than 0.6 and a Db value greater than 1; the N value being defined as the ratio of the adsorption amount of the molecular sieve to bicyclic aromatic hydrocarbons and derivatives thereof to the adsorption amount of a standard molecular sieve to bicyclic aromatic hydrocarbons and derivatives thereof; and the Db value being defined as the ratio of the square of the adsorption amount of the molecular sieve to butylbenzene to the product of the adsorption amount of the molecular sieve to methylindane and the adsorption amount to benzene. The catalyst of the present disclosure can realize directional hydrogenation ring-opening of polycyclic aromatic hydrocarbons in the diesel fraction, thereby improving the cetane number of the diesel product.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the field of catalysts, in particular, to a diesel hydro-upgrading catalyst and a preparation method and application thereof. BACKGROUND

[0002] Due to increasingly stringent fuel oil quality standards, the quality requirements for diesel fuel are also increasingly stringent in terms of sulfur content, polycyclic aromatic hydrocarbon content, cetane number, and density. The proportion of catalytic diesel in the existing diesel pool is high, but catalytic diesel is rich in aromatic hydrocarbons and mainly polycyclic aromatic hydrocarbons, has low cetane number and high density; and is affected by the increasing severity of heavy (inferior) crude oil and catalytic cracking units, the quality of catalytic diesel is continuously declining. Therefore, under the dual pressure of inferior raw materials and high-quality products, efficient conversion of polycyclic aromatic hydrocarbons in catalytic diesel into high-cetane components is the key to producing diesel blending components from catalytic diesel.

[0003] Hydro-upgrading technology can convert non-ideal components of high density and low cetane number, polycyclic aromatic hydrocarbons, in diesel into ideal high-cetane components, long-side-chain alkylbenzene, through selective hydrogenation saturation combined with selective ring-opening reaction, while also meeting the goal of reducing the polycyclic aromatic hydrocarbon content and density of high-quality diesel. Polycyclic aromatic hydrocarbon hydrogenation ring-opening is a complex process involving a series of parallel sequential reactions including hydrogenation, isomerization, ring-opening, cracking, polymerization, etc. Precise control of the reaction process and depth, and directional strengthening of the ring-opening reaction of polycyclic aromatic hydrocarbons are key challenges in the hydro-upgrading process. The hydro-upgrading process is a heterogeneous catalytic process, and the reactants need to go through diffusion, adsorption, reaction, desorption, and diffusion processes. Effective regulation of the diffusion, adsorption / desorption performance of reactant, reaction intermediate, and product molecules from the reaction time and spatial scale, and the high-activity and high-selectivity conversion of polycyclic aromatic hydrocarbons into ring-opening products, i.e. long-side-chain alkylbenzene or long-side-chain alkylcycloalkane, are the core of precise control of the polycyclic aromatic hydrocarbon hydrogenation ring-opening reaction process.

[0004] Chinese patent document 201210194486.8 discloses a diesel hydro-upgrading catalyst, which also has a rare earth modified USY molecular sieve, amorphous silicon aluminum, a large pore alumina, and a hydrogenation active component. Among them, the content of the rare earth modified USY molecular sieve is 5-60%, the amorphous silicon aluminum is 5-80%, and the Group VIII metal is 0.1-10%, based on the catalyst. The catalyst can improve the cetane number of diesel under mild hydrogenation conditions.

[0005] Chinese patent document 201210109193.5 discloses a diesel oil cracking diesel oil hydro-upgrading catalyst, which comprises a hydrogenation active metal component and a carrier of modified Y molecular sieve, amorphous silicon aluminum and alumina, the content of Y molecular sieve is 5-20% by weight of the catalyst, amorphous silicon aluminum accounts for 10-20%, the content of SiO2 in amorphous silicon aluminum is 20-75%, the pore volume is 0.25-0.80 mL / g, the specific surface area is 150-500 m 2 / g, the average grain size of Y molecular sieve is less than 100 nm, the molar ratio of SiO2 / Al2O3 is 9-20:1, the relative crystallinity is greater than 75%, and the specific surface area is 500-800 m 2 / g. The catalyst can be used to catalyze diesel oil hydro-upgrading, which can improve the cetane number while maintaining high diesel yield.

[0006] Chinese patent document 201610288647.8 discloses a modified Y-Beta composite molecular sieve, a preparation method and application thereof. The modified Y-Beta composite molecular sieve has the following characteristics: the total pore volume is 0.56-1.25 mL / g, preferably 0.65-1.10 mL / g; the mesopore volume is 0.45-0.95 mL / g, preferably 0.550-0.85 mLg; the mesopore volume accounts for 55%-80% of the total pore volume, preferably 60%-75%. The modified molecular sieve is beneficial to the hydro-de-ring opening conversion of polycyclic aromatic hydrocarbons in the hydrocracking process.

[0007] The catalysts provided by the above patent documents can improve the cetane number of diesel products to some extent, but the overall hydro-upgrading effect of diesel is still not ideal. SUMMARY

[0008] The purpose of the present disclosure is to provide a diesel hydro-upgrading catalyst to realize directional hydro-de-ring opening of polycyclic aromatic hydrocarbons in diesel fraction, thereby improving the cetane number of diesel products, reducing the density and polycyclic aromatic hydrocarbon content.

[0009] To achieve the above object, the first aspect of the present disclosure provides a diesel hydro-upgrading catalyst, which comprises a carrier and an active metal component supported on the carrier; the active metal component comprises a Group VIII metal element and a Group VIB metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, and the second molecular sieve is a molecular sieve with an N value greater than 0.6 and a Db value greater than 1; wherein the N value of a to-be-tested molecular sieve is defined as the ratio of the adsorption amount of the to-be-tested molecular sieve to bicyclic aromatic hydrocarbons and their derivatives to the adsorption amount of a standard molecular sieve to bicyclic aromatic hydrocarbons and their derivatives, the standard molecular sieve is a HY molecular sieve, the molar ratio of SiO2 and Al2O in the standard molecular sieve is 5.4, and the cell constant is 24.60 angstroms; the Db value of a to-be-tested molecular sieve is defined as the ratio of the square of the adsorption amount of the to-be-tested molecular sieve to butylbenzene to the product of the adsorption amount of the to-be-tested molecular sieve to methylindane and the adsorption amount of the to-be-tested molecular sieve to benzene.

[0010] Optionally, the Db value of the second molecular sieve is 1-10, and the N value is 1-10; preferably, the Db value of the second molecular sieve is 1-8, and the N value is 1-5; optionally, the pore volume of the second molecular sieve is 0.4-0.8 cm 3 / g, and the acid density is 0.8-2.5 μmol / m 2 .

[0011] Optionally, the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve is 1:9-9:1, preferably 1:1-9:1.

[0012] Optionally, the content of the composite molecular sieve in the carrier is 5-60% by weight, and the content of the heat-resistant inorganic oxide matrix is 40-95% by weight, based on the total weight of the carrier.

[0013] Optionally, the catalyst contains 40-75% by weight of the carrier, 1.5-6% by weight of the Group VIII metal element, and 10-35% by weight of the Group VIB metal element, based on the catalyst, in terms of oxides.

[0014] Optionally, the first molecular sieve is selected from at least one of HY molecular sieve, rare earth Y molecular sieve REY, rare earth HY molecular sieve REHY, ultra-stable Y molecular sieve USY, partially amorphous USY, rare earth ultra-stable Y molecular sieve REUSY, titanium-containing Y molecular sieve, phosphorus-containing Y molecular sieve, and at least one of Y and USY type molecular sieve and HY type molecular sieve and dealuminized Y type molecular sieve; preferably, the first molecular sieve is selected from at least one of HY molecular sieve, rare earth Y molecular sieve, rare earth HY molecular sieve, ultra-stable Y molecular sieve, rare earth ultra-stable Y molecular sieve, partially amorphous Y molecular sieve, titanium-containing Y molecular sieve, and phosphorus-containing Y type molecular sieve; the second molecular sieve is selected from at least one of ITQ-33 molecular sieve, UCR-20 molecular sieve, and ITQ-40 molecular sieve; and the heat-resistant inorganic oxide matrix is selected from at least one of alumina, silica, and silica-alumina.

[0015] The second aspect of the present disclosure provides a method for preparing a catalyst, the method comprising:

[0016] S1, mixing the first molecular sieve, the second molecular sieve, the heat-resistant inorganic oxide matrix, and the auxiliary agent, then performing kneading and extrusion to obtain extruded strips; performing first drying and first calcination on the extruded strips to obtain a carrier; the auxiliary agent is selected from at least one of inorganic binder and extrusion aid;

[0017] S2, impregnating the carrier with an aqueous solution containing a Group VIII metal-containing compound and a Group VIB metal-containing compound to obtain an impregnated carrier; and performing second drying and activation treatment on the impregnated carrier.

[0018] Optionally, the weight ratio of the first molecular sieve, the second molecular sieve, and the heat-resistant inorganic oxide matrix is 1-20:4-40:40-95.

[0019] Optionally, in step S1, the first drying treatment conditions include: a drying temperature of 80-300℃, preferably 100-200℃; a drying time of 1-12 hours, preferably 2-8 hours; and the first calcination conditions include: a calcination temperature of 350-850℃, preferably 450-650℃; a calcination time of 1-12 hours, preferably 2-6 hours; in step S2, the impregnation conditions include: an impregnation temperature of room temperature-150℃, and an impregnation time of 1-6 hours; the second drying conditions include: a temperature of 100-300℃, preferably 100-150℃; and a time of 2-8 hours; and the activation treatment conditions include: a temperature of 100-350℃, preferably 120-250℃; and a time of 1-12 hours, preferably 2-6 hours.

[0020] The third aspect of the present disclosure provides a method for diesel hydro-upgrading, the method comprising: contacting diesel and hydrogen with the hydrocracking catalyst described above to perform a hydrocracking reaction.

[0021] By the above technical solution, the catalyst of the present disclosure can realize the directional hydrogenation ring-opening of polycyclic aromatic hydrocarbons in the diesel fraction, thereby improving the cetane number of the diesel product, while reducing the density and polycyclic aromatic hydrocarbon content.

[0022] Other features and advantages of the present disclosure will be described in detail in the subsequent specific embodiments section. DETAILED DESCRIPTION

[0023] The specific embodiments of the present disclosure are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and are not used to limit the present disclosure.

[0024] The first aspect of the present disclosure provides a diesel hydro-upgrading catalyst, the catalyst comprising a carrier and an active metal component supported on the carrier; the active metal component comprising a Group VIII metal element and a Group VIB metal element; the carrier comprising a composite molecular sieve and a heat-resistant inorganic oxide matrix, the composite molecular sieve comprising a first molecular sieve and a second molecular sieve, the first molecular sieve being a Y molecular sieve, and the second molecular sieve being a molecular sieve with an N value greater than 0.6 and a Db value greater than 1; wherein the N value of a certain molecular sieve to be tested is defined as the ratio of the adsorption amount of the molecular sieve to be tested to double-ring aromatic hydrocarbons and their derivatives to the adsorption amount of a standard molecular sieve to double-ring aromatic hydrocarbons and their derivatives, the standard molecular sieve being a HY molecular sieve, and the molar ratio of SiO2 and Al2O in the standard molecular sieve being 5.4, and the cell constant being 24.60 angstroms; the Db value of a certain molecular sieve to be tested is defined as the ratio of the square of the adsorption amount of the molecular sieve to be tested to butylbenzene to the product of the adsorption amount of the molecular sieve to be tested to methylindane and the adsorption amount of the molecular sieve to be tested to benzene.

[0025] The N value and the Db value described in the present disclosure are obtained by the adsorption molar ratio test method, wherein the test method of the N value is as follows: first, accurately measure tetralin solution (100 milliliters, room temperature), then add a certain amount of molecular sieve material (5 grams), seal and stir under the protection of inert gas (N2) at 1 atmosphere and 360℃ for 10 hours, then filter, reconstitute the filtrate, cool to room temperature, and then measure the solution volume again with a measuring cylinder to obtain the adsorption volume difference ΔV of the test molecular sieve. The calculation formula of N is:

[0026] N = (ΔV test molecular sieve * M test molecular sieve) / (ΔV Y type molecular sieve * MY type molecular sieve)

[0027] wherein ΔV test molecular sieve and ΔV Y type molecular sieve are the volume differences of the adsorption of tetralin by the test molecular sieve and the standard molecular sieve, respectively, and M test molecular sieve and MY type molecular sieve are the molar masses of the test molecular sieve and the standard molecular sieve, respectively.

[0028] The test method of Db value is as follows: accurately take methyl indane, butyl benzene and benzene (100 ml, room temperature) respectively, then add a certain amount of molecular sieve material (5 g), seal and stir under inert gas (N2) protection, 1 atm, 360℃ constant temperature for 10 hours, then filter, reconstitute the filtrate, cool to room temperature, and then measure the solution volume again with a measuring cylinder to obtain the adsorption volume difference AV 测试分子筛_甲基茚满 , AV 测试分子筛_丁基苯 , AV 测试分子筛_苯 The calculation formula of Db value is as follows:

[0029] Db = AV 测试分子筛_丁基苯 2 / (AV 测试分子筛_甲基茚满 * AV 测试分子筛_苯 )

[0030] Wherein, AV 测试分子筛_甲基茚满 , AV 测试分子筛_苯 must be about 0.

[0031] The catalyst of the present disclosure can effectively control the diffusion and adsorption performance of polycyclic aromatic hydrocarbon molecules on the catalyst from the reaction time and space angle by improving the matching of the pore structure of the catalyst active component molecular sieve and the structure and size of the reactant molecules, reaction intermediates and product molecules in the polycyclic aromatic hydrocarbon hydrogenation ring-opening process, and precisely controlling the directional hydrogenation ring-opening process of polycyclic aromatic hydrocarbons. Specifically, the present disclosure realizes rational screening of the acid component molecular sieve of the catalyst through N value and Db value, strengthens the matching degree of the pore structure of the molecular sieve and the reactant, reaction intermediate and product molecules in the polycyclic aromatic hydrocarbon hydrogenation ring-opening process, realizes the directional hydrogenation ring-opening of polycyclic aromatic hydrocarbons, and can be used for the process of improving the cetane number of diesel oil, especially poor diesel oil rich in polycyclic aromatic hydrocarbons by hydro-upgrading.

[0032] In a preferred embodiment of the present disclosure, the Db value of the second molecular sieve is 1-10, and the N value is 1-10, further preferably, the Db value of the second molecular sieve is 1-8, and the N value is 1-5; optionally, the pore volume of the second molecular sieve is 0.4-0.8 cm 3 / g, and the acid density is 0.8-2.5 μmol / m 2 .

[0033] According to the present disclosure, the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve can be 1:9-9:1, preferably 1:1-9:1.

[0034] According to the present disclosure, the content of the composite molecular sieve in the carrier can be 5-60% by weight, and the content of the heat-resistant inorganic oxide matrix can be 40-95% by weight, based on the total weight of the carrier.

[0035] According to the present disclosure, the catalyst can contain 40 to 75 wt% of the carrier, 1.5 to 6 wt% of the Group VIII metal element, and 10 to 35 wt% of the Group VIB metal element, based on the catalyst as an oxide.

[0036] According to the present disclosure, the first molecular sieve can be selected from at least one of HY molecular sieve, rare earth Y molecular sieve REY, rare earth HY molecular sieve REHY, ultrastable Y molecular sieve USY, partially amorphous USY, rare earth ultrastable Y molecular sieve REUSY, titanium-containing Y molecular sieve, phosphorus-containing Y and ultrastable and HY type molecular sieve, and dealuminized Y type molecular sieve; preferably, the first molecular sieve can be selected from at least one of HY molecular sieve, rare earth Y molecular sieve, rare earth HY molecular sieve, ultrastable Y molecular sieve, rare earth ultrastable Y molecular sieve, partially amorphous Y molecular sieve, titanium-containing Y molecular sieve, and phosphorus-containing Y type molecular sieve; the second molecular sieve can be selected from at least one of ITQ-33 molecular sieve, UCR-20 molecular sieve, and ITQ-40 molecular sieve; the heat-resistant inorganic oxide matrix can be selected from at least one of alumina, silica, and silica-alumina.

[0037] The alumina is selected from one or more of transition phase alumina of γ, η, θ, δ and χ, and can also be one or more of transition phase alumina of γ, η, θ, δ and χ containing one or more of silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth additive components, preferably γ-alumina and γ-alumina containing one or more of silicon, phosphorus, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth additive components. They can be commercially available products or obtained by any one of the existing methods.

[0038] The silica-alumina has preferably silica-alumina with pseudoboehmite structure, and can also be commercially available products or prepared by any one of the existing technologies. For example, the Siral series of commercially available silica-alumina with pseudoboehmite structure produced by Condea Company in Germany can be used in the present disclosure.

[0039] The catalyst provided according to the present disclosure can be carried out in any reactor sufficient to make the raw oil react with the catalyst under the hydrogenation reaction conditions, for example, the reaction is carried out in a fixed bed reactor, a moving bed reactor or a boiling bed reactor. Other various types of hydrocarbon oil raw materials can also be directly processed for hydroprocessing. The hydrocarbon oil raw material can also be various heavy mineral oils or synthetic oils or mixed distillate oils, such as one or more selected from crude oil, distillate oil, solvent refined oil, wax paste, wax oil, Fischer-Tropsch synthetic oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil. Diesel oil, especially poor diesel oil rich in polycyclic aromatic hydrocarbons, is particularly suitable for hydro-upgrading or hydrocracking processes.

[0040] The second aspect of the present disclosure provides a method for preparing a catalyst, which comprises:

[0041] S1, mixing the first molecular sieve, the second molecular sieve, the heat-resistant inorganic oxide matrix and the auxiliary agent, then kneading and extruding to obtain extruded strips; performing first drying and first calcination on the extruded strips to obtain a carrier; the auxiliary agent is selected from at least one of inorganic binders and extrusion aids;

[0042] S2, impregnating the carrier with an aqueous solution containing a Group VIII metal-containing compound and a Group VIB metal-containing compound to obtain an impregnated carrier; performing second drying and activation treatment on the impregnated carrier.

[0043] Optionally, the weight ratio of the first molecular sieve, the second molecular sieve and the heat-resistant inorganic oxide matrix can be 1-20:4-40:40-95.

[0044] Optionally, in step S1, the conditions of the first drying treatment include: a drying temperature of 80-300°C, preferably 100-200°C; a drying time of 1-12 hours, preferably 2-8 hours; the conditions of the first calcination include: a calcination temperature of 350-850°C, preferably 450-650°C; a calcination time of 1-12 hours, preferably 2-6 hours; in step S2, the conditions of the impregnation include: an impregnation temperature of room temperature-150°C, an impregnation time of 1-6 hours; the conditions of the second drying include: a temperature of 100-300°C, preferably 100-150°C; a time of 2-8 hours; the conditions of the activation treatment include: a temperature of 100-350°C, preferably 120-250°C; a time of 1-12 hours, preferably 2-6 hours.

[0045] The third aspect of the present disclosure provides a method for diesel hydro-upgrading, which comprises: contacting diesel and hydrogen with the hydrocracking catalyst described above to perform a hydrocracking reaction. The catalyst of the present disclosure can effectively improve the quality of diesel when applied to diesel hydro-upgrading. The hydrocracking reaction in the present disclosure is performed by a fixed bed single-stage series process. In a preferred embodiment of the present disclosure, the single-stage series process comprises a hydrofining reaction zone and a hydrocracking reaction zone; further preferably, the temperature of the hydrofining reaction zone can be 250-450°C, the reaction pressure can be 4.0-16.0 MPa, the hydrogen oil volume ratio can be 200-1500, and the volume space velocity can be 0.5-2.5 h -1 -1; the temperature of the hydrocracking reaction can be 300-450°C, the reaction pressure can be 4.0-16.0 MPa, the hydrogen oil volume ratio can be 200-1500, and the volume space velocity can be 0.5-2.5 h -1 -1.

[0046] The present disclosure will be further illustrated by the following examples, but the present disclosure is not limited in any way by the examples.

[0047] Example 1

[0048] Take 200.0 grams of pseudoboehmite (Catalyst Changling Branch) with a dry basis of 70%, 42.4 grams of Y-type molecular sieve with a dry basis of 85%, and 29.3 grams of ITQ-33 molecular sieve with a dry basis of 82%, and add an appropriate amount of additives containing inorganic binders and extrusion aids, etc., mix uniformly, extrude into butterfly-shaped carrier strips with an inscribed circle diameter of 1.6 mm on an extruder, dry at 120°C for 3 hours, and calcine at 600°C for 4 hours to obtain carrier Z1.

[0049] Take 100 grams of carrier Z1, impregnate with 79 ml of mixed solution containing WO3 278.5 g / L, NiO 25.3 g / L, and P2O5 12.7 g / L of ammonium metatungstate, basic nickel carbonate, and phosphoric acid, respectively, for 3 hours, dry at 120°C for 3 hours, and then activate at 200°C for 3 hours to obtain catalyst C1. The composition is shown in Table 2, with the catalyst as the basis.

[0050] Example 2

[0051] Take 200.0 grams of pseudoboehmite (Catalyst Changling Branch) with a dry basis of 70%, 28.2 grams of Y-type molecular sieve with a dry basis of 85%, and 43.9 grams of ITQ-33 molecular sieve with a dry basis of 82%, and add an appropriate amount of additives containing inorganic binders and extrusion aids, etc., mix uniformly, extrude into butterfly-shaped carrier strips with an inscribed circle diameter of 1.6 mm on an extruder, dry at 120°C for 3 hours, and calcine at 600°C for 4 hours to obtain carrier Z2.

[0052] Take 100 grams of carrier Z2, impregnate with 79 ml of mixed solution containing WO3 278.5 g / L, NiO 25.3 g / L, and P2O5 12.7 g / L of ammonium metatungstate, basic nickel carbonate, and phosphoric acid, respectively, for 3 hours, dry at 120°C for 3 hours, and then activate at 200°C for 3 hours to obtain catalyst C2. The composition is shown in Table 2, with the catalyst as the basis.

[0053] Example 3

[0054] Take 200.0 grams of pseudoboehmite (Catalyst Changling Branch) with a dry basis of 70%, 28.2 grams of Y-type molecular sieve with a dry basis of 85%, and 43.9 grams of ITQ-33 molecular sieve with a dry basis of 82%, and add an appropriate amount of additives containing inorganic binders and extrusion aids, etc., mix uniformly, extrude into butterfly-shaped carrier strips with an inscribed circle diameter of 1.6 mm on an extruder, dry at 120°C for 3 hours, and calcine at 600°C for 4 hours to obtain carrier Z3.

[0055] Take 100 grams of carrier Z3, and immerse in 91 milliliters of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid with WO3 241.8 grams / liter, NiO 22.0 grams / liter and P2O5 11.0 grams / liter respectively for 3 hours, dry at 120°C for 3 hours and activate at 200°C for 3 hours to obtain catalyst C3. The composition is shown in Table 2.

[0056] Example 4

[0057] Take 100 grams of carrier Z2, and immerse in 79 milliliters of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid with WO3 94.9 grams / liter, NiO 12.7 grams / liter and P2O5 6.3 grams / liter respectively for 3 hours, dry at 120°C for 3 hours and activate at 200°C for 3 hours to obtain catalyst C4. The composition is shown in Table 2.

[0058] Example 5

[0059] Take 100 grams of carrier Z2, and immerse in 79 milliliters of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid with WO3 94.9 grams / liter, NiO 12.7 grams / liter and P2O5 6.3 grams / liter respectively for 3 hours, dry at 120°C for 3 hours and activate at 200°C for 3 hours to obtain catalyst C4. The composition is shown in Table 2.

[0060] Example 6

[0061] Take 100 grams of carrier Z2, and immerse in 79 milliliters of mixed solution containing molybdenum trioxide, basic nickel carbonate and phosphoric acid with MoO3 189.9 grams / liter, NiO 25.3 grams / liter and P2O5 12.7 grams / liter respectively for 3 hours, dry at 120°C for 3 hours and activate at 200°C for 3 hours to obtain catalyst C6. The composition is shown in Table 2.

[0062] Example 7

[0063] Take 200.0 grams of pseudo-boehmite with dry basis of 70% (Catalyst Changling Branch), 28.2 grams of Y-type molecular sieve with dry basis of 85% and 44.4 grams of UCR-20 molecular sieve with dry basis of 81%, and add appropriate amount of auxiliary agent containing inorganic binder and auxiliary extruding agent, etc. to mix uniformly, extrude into butterfly-shaped carrier strips with outer circle diameter of 1.6 millimeters on the extruding machine, dry at 120°C for 3 hours and calcine at 600°C for 4 hours to obtain carrier Z7.

[0064] Take 100 grams of carrier Z7, and immerse in 81 ml of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid respectively with WO3 271.6 g / L, NiO 24.7 g / L, P2O5 12.3 g / L for 3 hours, dry at 120°C for 3 hours, and then activate at 200°C for 3 hours to obtain catalyst C7. The composition is shown in Table 2.

[0065] Example 8

[0066] Take 114.3 grams of pseudo-boehmite (Catalyst Changling Branch) with dry basis of 70%, 28.2 grams of Y-type molecular sieve with dry basis of 85%, 44.4 grams of UCR-20 molecular sieve with dry basis of 81%, and 78.9 grams of amorphous silica-alumina material (Siral 40 of Condea Company, Germany) with dry basis of 76%, and add appropriate amount of additives containing inorganic binder and extrusion aid, etc., mix uniformly, extrude into butterfly-shaped carrier strips with outer diameter of 1.6 mm on the extruder, dry at 120°C for 3 hours, and then calcine at 600°C for 4 hours to obtain carrier Z8.

[0067] Take 100 grams of carrier Z8, and immerse in 83 ml of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid respectively with WO3 265.1 g / L, NiO 24.1 g / L, P2O5 12.0 g / L for 3 hours, dry at 120°C for 3 hours, and then activate at 200°C for 3 hours to obtain catalyst C8. The composition is shown in Table 2.

[0068] Example 9

[0069] Take 257.1 grams of pseudo-boehmite (Catalyst Changling Branch) with dry basis of 70%, 9.4 grams of Y-type molecular sieve with dry basis of 85%, and 14.8 grams of UCR-20 molecular sieve with dry basis of 81%, and add appropriate amount of additives containing inorganic binder and extrusion aid, etc., mix uniformly, extrude into butterfly-shaped carrier strips with outer diameter of 1.6 mm on the extruder, dry at 120°C for 3 hours, and then calcine at 600°C for 4 hours to obtain carrier Z9.

[0070] Take 100 grams of carrier Z9, and immerse in 78 ml of mixed solution containing ammonium metatungstate, basic nickel carbonate and phosphoric acid respectively with WO3 282.1 g / L, NiO 25.6 g / L, P2O5 12.8 g / L for 3 hours, dry at 120°C for 3 hours, and then activate at 200°C for 3 hours to obtain catalyst C9. The composition is shown in Table 2.

[0071] Example 10

[0072] Take 142.9 grams of pseudo-boehmite (Catalyst Changling Branch) with a dry basis of 70%, 47.1 grams of Y-type molecular sieve with a dry basis of 85%, and 74.1 grams of UCR-20 molecular sieve with a dry basis of 81%, and add an appropriate amount of auxiliary agents containing inorganic binder and extrusion aid, etc. to mix uniformly, extrude into butterfly-shaped carrier strips with an inscribed circle diameter of 1.6 mm on an extruder, dry at 120°C for 3 hours, and calcine at 600°C for 4 hours to obtain carrier Z10.

[0073] Take 100 grams of carrier Z10, and immerse in 85 ml of mixed solution containing WO3 258.8 g / L, NiO 23.5 g / L, and P2O5 11.8 g / L of ammonium metatungstate, nickel carbonate, and phosphoric acid respectively for 3 hours, dry at 120°C for 3 hours, and activate at 200°C for 3 hours to obtain catalyst C10. The composition is shown in Table 2.

[0074] Comparative Example 1

[0075] Take 200.0 grams of pseudo-boehmite (Catalyst Changling Branch) with a dry basis of 70% and 70.6 grams of Y-type molecular sieve with a dry basis of 85%, and add an appropriate amount of auxiliary agents containing inorganic binder and extrusion aid, etc. to mix uniformly, extrude into butterfly-shaped carrier strips with an inscribed circle diameter of 1.6 mm on an extruder, dry at 120°C for 3 hours, and calcine at 600°C for 4 hours to obtain carrier DZ.

[0076] Take 100 grams of carrier DZ, and immerse in 78 ml of mixed solution containing WO3 282.1 g / L, NiO 25.6 g / L, and P2O5 12.8 g / L of ammonium metatungstate, nickel carbonate, and phosphoric acid respectively for 3 hours, dry at 120°C for 3 hours, and activate at 200°C for 3 hours to obtain catalyst DC. The composition is shown in Table 2.

[0077] Table 1

[0078] Molecular sieve number Pore volume / (cm 3 / g) Acid density / (mmol / m 2 ] N value Db value ITQ-33 0.497 1.723 0.97 2.33 UCR-20 0.399 2.291 2.20 2.10 Y 0.412 3.121 1.00 0.65

[0079] Table 2

[0080]

[0081] Test Example

[0082] The density is 0.9561 g / cm3 3The performance of catalysts C1, C2, C3, C7 and DC was evaluated using catalytically cracked diesel oil with a sulfur content of 9800 ppm, a nitrogen content of 743 ppm and a total aromatic hydrocarbon content of 85.7% as raw material in a 30-ml fixed bed device. The specific method was as follows: an industrial refining catalyst was loaded on the upper part of the bed, and a catalyst was loaded on the lower part, and the loading amount of the catalyst was 15 ml. The catalyst was pre-sulfided before the raw oil was fed, and the sulfiding conditions were as follows: sulfiding at 110°C for 2 hours and sulfiding at 300°C for 4 hours, and the sulfiding oil was kerosene containing 6% by weight of carbon disulfide. The reaction conditions of the hydrofining reaction zone were as follows: a reaction temperature of 350°C, a hydrogen partial pressure of 6.5 MPa, a liquid hourly space velocity of 1.5 h -1 , a hydrogen to oil volume ratio of 800, the reaction conditions of the hydrotreating reaction zone were as follows: a reaction temperature of 370°C, a hydrogen partial pressure of 6.5 MPa, a liquid hourly space velocity of 1.2 h -1 , and a hydrogen to oil volume ratio of 800.

[0083] The test results are listed in Table 3.

[0084] Table 3

[0085] Catalyst C1 C2 C3 C7 D1 Cetane improvement value Benchmark + 1.2 Benchmark + 0.9 Benchmark + 0.4 Benchmark + 0.7 Benchmark Density reduction value Benchmark + 0.001 Benchmark + 0.005 Benchmark + 0.002 Benchmark + 0.003 Benchmark

[0086] The test results in Table 3 show that the catalyst provided by the present disclosure has higher hydrodearomatization performance, the content of polycyclic aromatic hydrocarbons in the diesel product is lower, and the cetane number increase value is higher.

[0087] The preferred embodiments of the present disclosure are described in detail above, but the present disclosure is not limited to the specific details in the above-described embodiments, and various simple modifications can be made to the technical solutions of the present disclosure within the technical concept of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0088] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present disclosure will not further describe various possible combination manners.

[0089] In addition, various different embodiments of the present disclosure can also be combined in any manner, as long as it does not deviate from the idea of the present disclosure, and it should also be considered as disclosed by the present disclosure.

Claims

1. A diesel hydro-upgrading catalyst, characterized by, The catalyst comprises a carrier and an active metal component supported on the carrier; the active metal component comprises a Group VIII metal element and a Group VIB metal element; the carrier comprises a composite molecular sieve and a heat-resistant inorganic oxide matrix, the composite molecular sieve comprises a first molecular sieve and a second molecular sieve, the first molecular sieve is a Y molecular sieve, the second molecular sieve has a Db value of 1-10, and the Db value is not 1, and an N value of 1-10; Wherein, the N value of a certain to-be-tested molecular sieve is defined as the ratio of the adsorption amount of the to-be-tested molecular sieve to bicyclic aromatic hydrocarbons and derivatives thereof to the adsorption amount of a standard molecular sieve to bicyclic aromatic hydrocarbons and derivatives thereof, the standard molecular sieve is a HY molecular sieve, the molar ratio of SiO2 and Al2O3 in the standard molecular sieve is 5.4, and the cell constant is 24.60 angstroms; the Db value of a certain to-be-tested molecular sieve is defined as the ratio of the square of the adsorption amount of the to-be-tested molecular sieve to butylbenzene to the product of the adsorption amount of the to-be-tested molecular sieve to methylindane and the adsorption amount of the to-be-tested molecular sieve to benzene; the second molecular sieve has a pore volume of 0.4-0.8 cm 3 / g, and an acid density of 0.8-2.5 μmol / m 2 ; the weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve is 1:9-9:1; and the second molecular sieve is selected from at least one of an ITQ-33 molecular sieve, a UCR-20 molecular sieve, and an ITQ-40 molecular sieve. The catalyst contains 40-75 wt% of the carrier, 1.5-6 wt% of the Group VIII metal element, and 10-35 wt% of the Group VIB metal element, based on the total weight of the catalyst in terms of oxides; the content of the composite molecular sieve in the carrier is 5-60 wt%, and the content of the heat-resistant inorganic oxide matrix is 40-95 wt%, based on the total weight of the carrier.

2. The catalyst of claim 1, wherein, The second molecular sieve has a Db value of 1-8 and an N value of 1-5.

3. The catalyst of claim 1, wherein, The weight ratio of the first molecular sieve to the second molecular sieve in the composite molecular sieve is 1:1-9:

1.

4. The catalyst of claim 1, wherein, The first molecular sieve is selected from at least one of a HY molecular sieve, a rare earth Y molecular sieve REY, a rare earth HY molecular sieve REHY, a USY molecular sieve, a partially amorphous USY, a rare earth USY molecular sieve REUSY, a titanium-containing Y molecular sieve, a phosphorus-containing Y molecular sieve, and a dealuminized Y molecular sieve; The heat-resistant inorganic oxide matrix is selected from at least one of alumina, silica, and silica-alumina.

5. The catalyst of claim 4, wherein, The first molecular sieve is selected from at least one of a HY molecular sieve, a rare earth Y molecular sieve REY, a rare earth HY molecular sieve REHY, a USY molecular sieve, a rare earth USY molecular sieve REUSY, a partially amorphous USY, a titanium-containing Y molecular sieve, and a phosphorus-containing Y molecular sieve.

6. A process for the preparation of a catalyst according to any one of claims 1 to 5, characterized in that The method comprises: S1, mixing the first molecular sieve, the second molecular sieve, the heat-resistant inorganic oxide matrix, and an auxiliary agent, then performing kneading and extrusion to obtain an extruded strip; performing first drying and first calcination on the extruded strip to obtain a carrier; the auxiliary agent is selected from at least one of an inorganic binder and an extrusion aid; S2, impregnating the carrier with an aqueous solution containing a Group VIII metal compound and a Group VIB metal compound to obtain an impregnated carrier; performing second drying and activation treatment on the impregnated carrier.

7. The method of claim 6, wherein, The weight ratio of the first molecular sieve, the second molecular sieve, and the heat-resistant inorganic oxide matrix is 1-20:4-40:40-95.

8. The method of claim 6, wherein, In step S1, the first drying treatment conditions include: drying temperature of 80-300℃; drying time of 1-12 hours; the first calcination conditions include: calcination temperature of 350-850℃; calcination time of 1-12 hours; In step S2, the impregnation conditions include: impregnation temperature of room temperature-150℃, impregnation time of 1-6 hours; the second drying conditions include: temperature of 100-300℃; time of 2-8 hours; the activation treatment conditions include: temperature of 100-350℃; time of 1-12 hours.

9. The method of claim 8, wherein, In step S1, the first drying treatment conditions include: drying temperature of 100-200℃; drying time of 2-8 hours; the first calcination conditions include: calcination temperature of 450-650℃; calcination time of 2-6 hours; In step S2, the second drying conditions include: temperature of 100-150℃; the activation treatment conditions include: temperature of 120-250℃; time of 2-6 hours.

10. A process for the hydro-upgrading of diesel oil, characterized in that, The method includes: contacting diesel and hydrogen with the hydro-upgrading catalyst according to any one of claims 1-5 to perform a hydrocracking reaction.

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