Catalyst with hydrogenation catalysis effect, preparation method and application of catalyst and hydrocracking method

[0027] In the catalyst obtained according to the preparation method of the present invention, the content of the VIB group metal element, the group VIII metal element and the element as an auxiliary agent can be appropriately selected according to the specific application of the catalyst. Generally, the introduction amount of the VIB group metal element, the group VIII metal element and the element as an auxiliary agent on the shaped porous support is such that, based on the total amount of the catalyst, the shaped The content of the porous carrier may be 30-88.5 wt%, preferably 43-88.5 wt%, more preferably 52-85% by weight; based on oxide, the content of group VIB metal elements may be 10-50 wt%, Preferably it is 10-45% by weight, more preferably 12-40% by weight; based on the oxide, the content of the group VIII metal element may be 1-10% by weight, preferably 1-7% by weight, more preferably 2- 5 wt%; based on the element, the content of the element as the auxiliary agent may be 0.5-10 wt%, preferably 0.5-5 wt%, more preferably 1-3 wt%.

[0028] According to the preparation method of the present invention, the group VIB metal element and the group VIII metal element can be conventionally selected in the art. Generally, the group VIB metal element is preferably molybdenum element and/or tungsten element, and the group VIII metal element is preferably cobalt element and/or nickel element.

[0029] According to the preparation method of the present invention, the element used as the auxiliary agent can be various elements commonly used in the art that can improve the performance of the catalyst with hydrogenation catalysis, and can be selected from metal elements and non-metal elements. Specifically, the metal element as the auxiliary agent may be selected from the group IIB metal element, the group IA metal element, the IIA group metal element and the rare earth metal element; preferably, it is selected from the zinc element, sodium element, potassium element, magnesium element, calcium Element, lanthanum element and cerium element; more preferably selected from zinc element, magnesium element and lanthanum element. The non-metallic element as the auxiliary agent can be selected from phosphorus, boron and fluorine; preferably, it is selected from boron and fluorine.

[0030] According to the preparation method of the present invention, the method of introducing at least one group VIB metal element and at least one group VIII metal element on the shaped porous carrier includes the following steps:

[0031] (1) Impregnating the shaped porous carrier with an aqueous solution, wherein the aqueous solution contains at least one compound containing a group VIB metal element and at least one compound containing a group VIII metal element, with or without auxiliary Solvent

[0032] (2) The mixture obtained by immersion is subjected to hydrothermal treatment in a closed reactor, and the hydrothermal treatment is performed at a pressure of P 0 +ΔP; and

[0033] (3) The mixture obtained by the hydrothermal treatment is subjected to solid-liquid separation, and the obtained solid phase is dried.

[0034] According to the preparation method of the present invention, in the aqueous solution of step (1), the concentration of the compound containing the group VIB metal element and the compound containing the group VIII metal element is such that the concentration of the group VIB metal in the finally prepared catalyst The content of elements and group VIII metal elements meets the specific usage requirements (such as the content requirements mentioned above).

[0035] According to the present invention, the aqueous solution can be prepared by dissolving at least one compound containing a group VIB metal element and at least one compound containing a group VIII metal element commonly used in the art.

[0036] The compound containing group VIB metal element can be selected from water-soluble compounds containing group VIB metal elements commonly used in the art, and group VIB metal element-containing compounds that can form water-soluble compounds in water in the presence of a cosolvent. Compound; The compound containing Group VIII metal element may be selected from the group VIII metal element-containing water-soluble compounds commonly used in the art, and the Group VIII metal-containing compound that can form water-soluble compounds in water in the presence of a cosolvent Compounds of the elements.

[0037] Specifically, the compound containing a group VIB metal element may be selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.

[0038] The compound containing group VIII metal elements may be selected from the group consisting of nitrates of group VIII metals, chlorides of group VIII metals, sulfates of group VIII metals, formates of group VIII metals, and group VIII metals Group VIII metal phosphate, Group VIII metal citrate, Group VIII metal oxalate, Group VIII metal carbonate, Group VIII metal alkali carbonate , Group VIII metal hydroxide, Group VIII metal phosphate, Group VIII metal phosphide, Group VIII metal sulfide, Group VIII metal aluminate, Group VIII metal molybdate Salts, tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.

[0039] Preferably, the group VIII metal element-containing compound is selected from the group consisting of oxalate of group VIII metal, nitrate of group VIII metal, sulfate of group VIII metal, acetate of group VIII metal, and Chloride of group VIII metal, carbonate of group VIII metal, alkali carbonate of group VIII metal, hydroxide of group VIII metal, phosphate of group VIII metal, molybdenum of group VIII metal Salts, tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.

[0040] Specifically, the group VIII metal element-containing compound may be selected from but not limited to: nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, chlorinated Cobalt and nickel chloride.

[0041] According to the preparation method of the present invention, the aqueous solution described in step (1) may also contain various co-solvents commonly used in the art to improve the compound containing the group VIB metal element and the compound containing the group VIII metal element The solubility of the compound in water; or stabilizing the aqueous solution to prevent precipitation. The co-solvent may be various substances commonly used in the field that can achieve the above functions, and is not particularly limited. For example, the co-solvent may be one or more of phosphoric acid, citric acid and ammonia. The present invention has no particular limitation on the concentration of the ammonia water, which can be conventionally selected in the field. The amount of the co-solvent can be conventionally selected in the art. Generally, the content of the co-solvent in the aqueous solution can be 1-10% by weight.

[0042] According to the preparation method of the present invention, various methods commonly used in the art can be used to introduce at least one element as an auxiliary agent on the shaped porous carrier. For example: the element as the auxiliary agent can be introduced on the shaped porous support before the introduction of the VIB group metal element and the group VIII metal element; it can also be introduced on the shaped porous carrier at the same time At least one element as an auxiliary agent, at least one metal element from group VIB and at least one metal element from group VIII; and it can also be introduced during the preparation of the shaped porous carrier Elements of additives.

[0043] In the first embodiment of the present invention, the method of introducing at least one element as an auxiliary agent on the shaped porous carrier includes: in step (1), impregnating the shaped porous carrier with the aqueous solution Previously, at least one element as an auxiliary agent was supported on the shaped porous carrier. Various methods commonly used in the art can be used to load the element as an auxiliary agent on the shaped porous carrier. For example, an aqueous solution containing at least one compound containing an element as an auxiliary agent can be contacted with the shaped porous carrier, and the shaped porous carrier loaded with the compound can be dried and calcined successively, thereby serving as an auxiliary agent. The elements of the agent are supported on the shaped porous carrier. The contact method can be conventionally selected in the field, such as dipping and spraying.

[0044] In the second embodiment of the present invention, the method of introducing at least one element as an auxiliary agent on the shaped porous carrier includes: dissolving at least one compound containing the element as an auxiliary agent in the step (1). The aqueous solution (that is, contains at least one compound containing a group VIII metal element and at least one compound containing a group VIB metal element, and the aqueous solution with or without a co-solvent also contains at least one containing as a co-solvent Compound), and impregnating the porous support with the aqueous solution, thereby simultaneously introducing the element as the auxiliary agent, the VIB group metal element, and the group VIII metal element on the shaped porous support. In this embodiment, P 0 Is the shaped porous support, the compound containing the group VIII metal element, the compound containing the group VIB metal element, the cosolvent with or without, the compound containing the element as an auxiliary agent , And the pressure generated by the water in the aqueous solution during the hydrothermal treatment.

[0045] In the third embodiment of the present invention, the method of introducing at least one element as an auxiliary agent on the shaped porous support includes: combining at least one compound containing the element as an auxiliary agent with The raw materials of the shaped porous carrier are mixed, and the resulting mixture is shaped.

[0046] According to the preparation method of the present invention, the above three embodiments can be used alone or in combination, and there is no particular limitation, as long as the content of the element as the auxiliary agent in the finally obtained catalyst can meet the specific use requirements (for example, the above-mentioned The content range mentioned above). From the viewpoint of process simplicity, the method according to the present invention preferably adopts the second embodiment to introduce an element as an auxiliary agent on the shaped porous carrier.

[0047] According to the present invention, the compound containing the element as an auxiliary agent can be various water-soluble compounds containing the element as an auxiliary agent commonly used in the art. For example, the compound containing the element as an auxiliary agent can be selected from the group IIB metal water-soluble compounds. Nitrates, water-soluble nitrates of group IA metals, water-soluble nitrates of group IIA metals, water-soluble nitrates of rare earth metals, water-soluble chlorides of group IIB metals, and water-soluble chlorine of group IA metals Compounds, water-soluble chlorides of group IIA metals, water-soluble chlorides of rare earth metals, water-soluble hydroxides of group IIB metals, water-soluble hydroxides of group IA metals, water-soluble hydrogen of group IIA metals Oxides, water-soluble hydroxides of rare earth metals, hydrofluoric acid, hydrofluorates, fluorosilicic acid, fluorosilicates, ammonium fluoride, boric acid, ammonium borate, ammonium metaborate, and ammonium tetraborate. Preferably, the compound containing the element as an auxiliary is selected from the group consisting of magnesium nitrate, sodium nitrate, zinc nitrate, cerium nitrate, lanthanum nitrate, magnesium chloride, sodium chloride, zinc chloride, cerium chloride, lanthanum chloride, ammonium fluoride, Ammonium fluorosilicate, boric acid, and ammonium tetraborate.

[0048] According to the method of the present invention, the porous support contains a heat-resistant inorganic oxide and a macroporous molecular sieve. In the present invention, the content of the heat-resistant inorganic oxide and the macroporous molecular sieve in the porous carrier can be appropriately selected according to the application of the final prepared catalyst. When the catalyst prepared according to the method of the present invention is used for the hydrocracking of hydrocarbon oil, based on the total amount of the porous carrier, the content of the macroporous molecular sieve may be 2 to 75% by weight, preferably 5 to 60 % By weight, more preferably 5-40% by weight, further preferably 5-30% by weight; the content of the heat-resistant inorganic oxide may be 25-98% by weight, preferably 40-95% by weight, more preferably 60 -95% by weight, more preferably 70-95% by weight.

[0049] According to the present invention, the term "heat-resistant inorganic oxide" refers to an inorganic oxygen-containing compound with a decomposition temperature of not less than 300°C (for example, a decomposition temperature of 300-1000°C) under oxygen or an oxygen-containing atmosphere.

[0050] According to the present invention, the heat-resistant inorganic oxide may be various heat-resistant inorganic oxides commonly used in the field. Generally, the heat-resistant inorganic oxide can be selected from alumina, silica, titania, magnesia, alumina-silica, silica-magnesia, silica-zirconia, silica-thorium, oxide Silicon-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium oxide, titanium oxide-zirconium oxide, silicon oxide-aluminum oxide-thorium oxide, silicon oxide-aluminum oxide-titanium oxide, silicon oxide-aluminum oxide-magnesium oxide, And silica-alumina-zirconia.

[0051] Preferably, the heat-resistant inorganic oxide is alumina.

[0052] In the present invention, the macroporous molecular sieve refers to a zeolite molecular sieve with a twelve-membered ring pore structure. For example, the macroporous molecular sieve may be selected from a zeolite molecular sieve having a faujasite structure, a zeolite molecular sieve having a Beta zeolite structure, and a zeolite molecular sieve having a mordenite structure.

[0053] Preferably, the macroporous molecular sieve is Y-type zeolite.

[0054] More preferably, the macroporous molecular sieve is HY zeolite, rare earth Y zeolite (ie REY zeolite), rare earth HY zeolite (ie REHY zeolite), ultra stable Y zeolite (ie, USY zeolite), rare earth ultra stable One or more of Y zeolite (ie, REUSY zeolite), phosphorus-containing Y-type zeolite, phosphorus-containing ultra-stable Y zeolite, phosphorus-containing HY-type zeolite, and dealuminated Y-type zeolite.

[0055] Further preferably, the macroporous molecular sieve has B acid and L acid, the molar ratio of the B acid to the L acid is greater than 0.9, and the zeolite molecular sieve is between 3685-3760 cm -1 At least one characteristic peak corresponding to silanol appears.

[0056] More preferably, the molar ratio of the B acid to the L acid is 1-10, and the macroporous molecular sieve is 3685-3760 cm -1 Two characteristic peaks corresponding to silanol groups appear.

[0057] The B acid and L acid of the macroporous molecular sieve can be determined by methods commonly used in the art, for example, infrared spectroscopy can be used to determine the specific test method: the macroporous molecular sieve is ground and pressed to about 10 mg/cm 2 The self-supporting sheet is placed in the in-situ cell of the infrared spectrometer at 350℃, 10 -3 Purify the surface under Pa vacuum for 2 hours, then lower the temperature to room temperature, introduce saturated vapor of pyridine, and after adsorption equilibrium for 15 minutes, vacuum desorption at 200°C for 30 minutes, then lower the temperature to room temperature and perform infrared scanning , The scanning range is 1400cm -1 -1700cm -1 , Will 1540cm -1 ±5cm -1 The ratio of the absorbance at the infrared absorption peak to the weight and area of ​​the sample piece is defined as the amount of B acid (expressed as: A B ·(Cm 2 ·G) -1 ); will be 1450cm -1 ±5cm -1 The ratio of the absorbance at the infrared absorption peak to the weight and area of ​​the sample piece is defined as the amount of L acid (expressed as: A L ·(Cm 2 ·G) -1 ), will A B /A L The value of is defined as the ratio of B acid to L acid of the macroporous molecular sieve.

[0058] According to the present invention, methods commonly used in the art can be used to determine the silanol groups of the macroporous molecular sieve, such as infrared spectroscopy. Specifically, the method of using infrared spectroscopy to determine the silanol groups of the macroporous molecular sieve can be as follows: grinding the zeolite molecular sieve sample and pressing it to about 10 mg/cm 2 The self-supporting sheet is placed in the in-situ cell of the infrared spectrometer at 350℃, 10 -3 Surface purification treatment under Pa vacuum for 2 hours, the temperature is lowered to room temperature for infrared scanning, the scanning range is 3400cm -1 -4000cm -1.

[0059] According to the method of the present invention, various methods commonly used in the art can be used to prepare the shaped porous carrier. For example, a heat-resistant inorganic oxide and/or a precursor capable of forming a heat-resistant inorganic oxide under calcination conditions can be mixed with a macroporous molecular sieve, and the obtained mixture can be formed by drying and calcination successively. Various methods commonly used in the art can be used to shape the mixture, for example, extrusion, spraying, spheronization, tableting or a combination thereof. Specifically, the heat-resistant inorganic oxide and/or the precursor capable of forming the heat-resistant inorganic oxide under calcination conditions can be mixed with a macroporous molecular sieve, and the resulting mixture can be extruded and molded in an extruder.

[0060] In a preferred embodiment of the present invention, the precursor capable of forming alumina under calcination conditions is mixed with a macroporous molecular sieve, the resulting mixture is extruded and molded, and then the extruded molded body is dried and calcined, thereby The porous support is obtained.

[0061] In the present invention, the precursor capable of forming the heat-resistant inorganic oxide under firing conditions may be appropriately selected according to the type of the expected heat-resistant inorganic oxide, so that the heat-resistant inorganic oxide can be formed by firing Prevail. For example, when the heat-resistant inorganic oxide is alumina, the precursor that can form the heat-resistant inorganic oxide under the calcination conditions may be various substances commonly used in the art that can form alumina under the calcination conditions, For example: hydrated alumina (such as pseudo-boehmite), aluminum sol.

[0062] According to the present invention, when the extrusion method is used for molding, the mixture may also contain an extrusion aid and/or an adhesive. The types and amounts of the extrusion aids and adhesives are well known to those skilled in the art, and will not be repeated here.

[0063] According to the present invention, the conditions for firing the molded body can be conventionally selected in the field. For example, the calcination temperature may be 350-650°C, preferably 400-600°C; the calcination time may be 2-6 hours, preferably 3-5 hours.

[0064] According to the present invention, the porous carrier may have various shapes according to specific applications, such as spherical, sheet-shaped, strip-shaped or clover-shaped.

[0065] According to the preparation method of the present invention, in step (1), the impregnation method is not particularly limited, and can be conventionally selected in the art, such as: pore saturation impregnation method and excessive impregnation method (ie, supersaturation impregnation method). Preferably, according to the method of the present invention, the impregnation is excessive impregnation. The pore saturation impregnation method and the excess impregnation method are well-known in the art and will not be repeated here. According to the preparation method of the present invention, the number of impregnations in step (1) is not particularly limited. It may be one impregnation or multiple impregnations, so that in the finally obtained catalyst, the group VIII metal elements and the group VIB The content of the metal element can meet the use requirements (for example, the content range mentioned above) shall prevail.

[0066] According to the preparation method of the present invention, in step (2), the hydrothermal treatment has a pressure of P 0 +ΔP conditions.

[0067] In the present invention, P 0 Is the shaped porous carrier, the compound containing the metal element of group VIII, the compound containing the metal element of group VIB, the cosolvent with or without, and the one with or without containing as an auxiliary agent The compound of the element and the pressure generated by the water in the aqueous solution during the hydrothermal treatment.

[0068] According to the method of the present invention, during the hydrothermal treatment process, the pressure in the closed container used for the hydrothermal treatment is divided by P 0 In addition, it also includes ΔP, where ΔP is 0.05-15 MPa. From the perspective of balancing the catalytic activity of the finally prepared catalyst and the internal pressure borne by the closed container, ΔP is preferably 0.1-10 MPa, more preferably 0.2-8 MPa, and still more preferably 0.2-5 MPa.

[0069] In the present invention, all pressures are measured by gauge pressure.

[0070] Various methods commonly used in the art can be used to make the hydrothermal treatment at a pressure of P 0 +ΔP conditions.

[0071] In an embodiment of the present invention, the hydrothermal treatment is made at a pressure of P 0 The method of performing under the condition of +ΔP includes: performing the hydrothermal treatment in the presence of at least one volatile organic compound, and the added amount of the volatile organic compound makes the pressure generated by the volatile organic compound in the hydrothermal treatment ΔP.

[0072] Various methods can be used to make the hydrothermal treatment performed in the presence of the volatile organic compound (that is, the volatile organic compound is contained in the closed container for the hydrothermal treatment). For example, the volatile organic compound may be added to the aqueous solution used for impregnating the porous support or the mixture obtained by impregnation, so that the hydrothermal treatment is performed in the presence of the volatile organic compound. From the perspective of further improving the catalytic activity of the prepared catalyst, the method according to the present invention preferably adds volatile organic compounds to the mixture obtained by impregnation, so that the hydrothermal treatment is performed in the presence of volatile organic compounds.

[0073] In this embodiment, various commonly used volatile organic compounds can be added to the closed container, as long as the volatile organic compounds can increase the pressure in the closed container for the hydrothermal treatment under the hydrothermal treatment conditions, so that the closed container The pressure within is within the range described above.

[0074] In the present invention, the volatile organic compounds may be various substances that can transform from a liquid state to a gaseous state under hydrothermal treatment conditions and/or substances that can generate gas under hydrothermal treatment conditions. For example, the volatile organic compounds may be selected from alcohols, acids, amines, and polyethylene glycols with a number average molecular weight of 200-1500. Preferably, the volatile organic compounds are selected from C 1 -C 30 Fatty alcohol, C 2 -C 30 Fatty acids, C 2 -C 30 Fatty amine, C 6 -C 30 Alkanes and polyethylene glycols with a number average molecular weight of 200-1500. More preferably, the volatile organic compounds are selected from C 1 -C 12 Fatty alcohol, C 2 -C 10 Fatty acids, C 2 -C 12 Fatty amine, C 6 -C 12 Alkanes and polyethylene glycols with a number average molecular weight of 200-1500. Further preferably, the volatile organic compounds are selected from C 1 -C 8 Fatty alcohol, C 2 -C 5 Fatty acids, C 2 -C 7 Fatty amine and C 6 -C 11 The alkanes.

[0075] Specifically, the volatile organic compounds can be selected from but not limited to: ethanol, n-propanol, isopropanol, ethylene glycol, glycerol, triethylene glycol, polyethylene glycol with a number average molecular weight of 200-1500, Diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, tartaric acid, malic acid, ethylenediamine, hexane and its isomers, Heptane and its isomers, octane and its isomers, and decane and its isomers.

[0076] According to the method of the present invention, the amount of the volatile organic compound is not particularly limited, and can be appropriately selected according to the expected ΔP value and the type of volatile organic compound used, which will not be repeated here.

[0077] In another embodiment of the present invention, the hydrothermal treatment is made at a pressure of P 0 The method of performing under the condition of +ΔP includes: performing the hydrothermal treatment in the presence of at least one inert gas, and the added amount of the inert gas makes the pressure generated by the inert gas in the hydrothermal treatment ΔP.

[0078] In the present invention, the inert gas refers to a porous carrier, a compound containing a group VIB metal element, a compound containing a group VIII metal element, a co-solvent, or a compound containing an element as an auxiliary agent during the hydrothermal treatment process. The gas that chemically interacts with water can be various inert gases commonly used in the field. Preferably, the inert gas is selected from nitrogen, group zero element gas (for example: argon), carbon dioxide, sulfur hexafluoride and C 1 -C 5 Of hydrocarbons. Further preferably, the inert gas is selected from nitrogen and group zero element gas.

[0079] According to this embodiment, in the process of hydrothermal treatment, an inert gas can be passed into the closed container for hydrothermal treatment, so that the pressure in the closed container is P 0 +ΔP; it is also possible to pass the inert gas into the closed container for the hydrothermal treatment before the hydrothermal treatment, and then close the container for the hydrothermal treatment.

[0080] According to another embodiment of the present invention, the post-treatment is made at a pressure of P 0 The method of performing under the condition of +ΔP includes: performing the hydrothermal treatment in the presence of at least one volatile organic compound and at least one inert gas, and the total added amount of the volatile organic compound and the inert gas makes the volatilization The total pressure of organic matter and inert gas produced in hydrothermal treatment is ΔP.

[0081] In this embodiment, the types and usage methods of the volatile organic compounds and the inert gas are as described above, and will not be repeated here.

[0082] According to the method of the present invention, although the above three methods can be used to achieve the purpose of improving the catalytic activity of the finally obtained catalyst, from the perspective of further improving the activity of the catalyst obtained by the preparation method of the present invention and the ease of operation, according to the present invention The preparation method of the invention preferably performs the hydrothermal treatment in the presence of an inert gas, or performs the hydrothermal treatment in the presence of volatile organic compounds and inert gases, so that the hydrothermal treatment is performed at a pressure of P 0 +ΔP conditions. More preferably, the hydrothermal treatment is performed in the presence of an inert gas.

[0083] According to the preparation method of the present invention, the time and temperature of the hydrothermal treatment can be conventionally selected in the art, as long as the pressure of the hydrothermal treatment meets the aforementioned requirements. Preferably, the temperature of the hydrothermal treatment may be 100-200°C; the time of the hydrothermal treatment may be 0.5-36 hours, preferably 1-24 hours.

[0084] The preparation method according to the present invention further includes step (3): solid-liquid separation of the mixture obtained by the hydrothermal treatment, and drying the obtained solid phase. The preparation method of the present invention is not particularly limited to the method of solid-liquid separation, which can be conventionally selected in the field, for example, it can be filtration, static separation or centrifugal separation. The present invention also has no particular limitation on the drying conditions, which can be conventionally selected in the field. Generally, the drying conditions include: temperature may be 100-300°C, preferably 100-280°C, more preferably 120-250°C; time may be 1-12 hours, preferably 2-8 hours.

[0085] The preparation method according to the present invention may further include roasting the solid material obtained by drying. The firing conditions can be conventionally selected in the field. Generally, the baking conditions include: the temperature can be 350-550°C, preferably 400-500°C; the time can be 1-8 hours, preferably 2-6 hours.

[0086] The second aspect of the present invention provides a catalyst prepared by the method of the present invention.

[0087] The catalyst according to the present invention has higher catalytic activity when used in the hydrocracking of hydrocarbon oil. The catalyst according to the present invention is particularly suitable as a hydrocracking catalyst for heavy distillate oil and inferior distillate oil to produce middle distillate oil with a distillation range of 149-371°C, especially a distillation range of 180-370°C.

[0088] Thus, the third aspect of the present invention provides an application of the catalyst according to the present invention in the hydrocracking of hydrocarbon oil.

[0089] The fourth aspect of the present invention provides a hydrocracking method, which includes contacting a hydrocarbon oil with the catalyst provided by the present invention under hydrocracking conditions.

[0090] According to the hydrocracking method of the present invention, the hydrocarbon oil may be various heavy mineral oils, synthetic oils or their mixtures. Specifically, examples of the hydrocarbon oil may include, but are not limited to: vacuum gas oil, demetalized oil, atmospheric residue, deasphalted vacuum residue, vacuum residue, coking distillate, shale oil, Tar sand oil and coal liquefied oil.

[0091] The present invention improves the activity of the catalyst in hydrocracking by using the catalyst according to the present invention. The remaining conditions of hydrocracking are not particularly limited, and may be conventional conditions in the field. Preferably, the hydrocracking conditions include: the temperature may be 200-650°C, preferably 300-510°C; in gauge pressure, the pressure may be 3-24 MPa, preferably 4-15 MPa; the volume ratio of hydrogen to oil may be 100-5000, preferably 200-1000; the liquid hourly volumetric space velocity of hydrocarbon oil can be 0.1-10 hours -1 , Preferably 0.2-5 hours -1.

[0092] According to the hydrocracking method of the present invention, the catalyst is preferably presulfided before use. The pre-vulcanization conditions can be conventional conditions in the field. For example, the pre-sulfurization conditions may include: in the presence of hydrogen, at a temperature of 360-400°C, using one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide Pre-vulcanized. According to the hydrocracking method of the present invention, the presulfurization can be carried out outside the reactor, or can be sulfided in-situ in the reactor.

[0096] Preparation Example 1

[0097] (1) Take 200g of dry-base NaY molecular sieve (commercially purchased from the catalyst plant of Sinopec Changling Refining and Chemical Company, the unit cell constant is Relative crystallinity is 100%, specific surface area is 720m 2 /g, sodium oxide content of 13.1% by weight) was placed in the reactor, 200g of ammonium sulfate and 2000mL of water were added, the temperature was raised to 90°C with stirring, and the temperature was maintained for 2 hours. After the reaction, the reaction product was filtered, and the filter cake was washed three times with water to obtain molecular sieve NY-1.

[0098] (2) Take 100 grams of the molecular sieve NY-1 prepared in step (1), put it in a muffle furnace, and add water vapor while raising the temperature to raise the temperature to 550°C, keep it at a constant temperature for 2 hours, and then cool it out. The obtained product is placed in a reaction kettle, and 1000 mL of an aqueous solution containing sulfuric acid and ammonium sulfate is added, wherein the concentration of sulfuric acid is 0.1% by weight and the content of ammonium sulfate is 100 grams. With stirring, the temperature was increased to 90°C and kept at a constant temperature for 2 hours. The reaction product is filtered, and the obtained filter cake is repeated step (2) twice.

[0099] (3) Place the filter cake obtained in step (2) in a reaction kettle, and add 500 mL of an aqueous solution containing ammonium fluorosilicate and ammonium sulfate, wherein in the aqueous solution, ammonium fluorosilicate (commercially purchased from Yunnan Fluorine Chemical Industry Co., Ltd.) content is 2 grams, the content of ammonium sulfate is 100 grams, with stirring, the temperature is increased to 90 ℃, constant temperature for 2 hours and then filtered, the obtained filter cake is dried at 120 ℃ to constant weight, to obtain macropores Molecular sieve CZ-1. Measured by infrared spectroscopy, the macroporous molecular sieve is at 3685-3760cm -1 Two hydroxyl peaks appear, the absorption peak positions are 3740cm respectively -1 And 3710cm -1 , B acid/L acid = 8.3 (molar ratio).

[0100] (4) 150 grams of the macroporous molecular sieve CZ-1 prepared in step (3) and 850 grams (on a dry basis) pseudo-boehmite (commercially purchased from Shandong Aluminum Factory, trade name SD powder, dry basis content: 69% by weight) was mixed with 30 g of Sesbania powder, and extruded into a trilobal strip with a circumscribed circle diameter of 1.6 mm using an extruder. The extruded molded body was dried at 120°C for 5 hours, and then calcined at 550°C for 3 hours to prepare carrier S1. In the carrier S1, the content of the macroporous molecular sieve is 15.0% by weight, and the content of alumina is 85.0% by weight.

[0101] Preparation Example 2

[0102] 50 grams of REY molecular sieve (commercially purchased from the catalyst plant of Sinopec Changling Refining and Chemical Company, the trade name is REHY, and the unit cell constant is Rare earth element content is 3% by weight), 950 grams (on a dry basis) pseudo-boehmite (commercially purchased from Shandong Aluminum Factory, trade name SD powder, dry basis content 69% by weight), and 30 grams of Sesbania powder Mix and extrude into a trilobal strip with a circumscribed circle diameter of 1.6 mm with an extruder. The extruded molded body was dried at 120°C for 5 hours, and then calcined at 550°C for 3 hours to prepare carrier S2. In the carrier S2, the content of the macroporous molecular sieve is 5.0% by weight, and the content of alumina is 95.0% by weight.