[0026] In the catalyst obtained by the preparation method of the present invention, the content of the metal element of Group VIB, the metal element of Group VIII and the element as auxiliary agent can be appropriately selected according to the specific application of the catalyst. Generally, the amount of the Group VIB metal element, the Group VIII metal element and the element as an auxiliary agent is introduced on the shaped porous support such that, based on the total amount of the catalyst, the shaped porous support is The content of the porous support can be 30-88.5% by weight, preferably 43-88.5% by weight, more preferably 52-85% by weight; in terms of oxides, the content of Group VIB metal elements can be 10-50% by weight, It is preferably 10-45 wt %, more preferably 12-40 wt %; in terms of oxides, the content of Group VIII metal elements may be 1-10 wt %, preferably 1-7 wt %, more preferably 2- 5% by weight; based on the element, the content of the element as an auxiliary agent may be 0.5-10% by weight, preferably 0.5-5% by weight, more preferably 1-3% by weight.
[0027] According to the preparation method of the present invention, the metal element of Group VIB and the metal element of Group VIII may be conventionally selected in the field. Generally, the metal element of group VIB is preferably molybdenum element and/or tungsten element, and the metal element of group VIII is preferably cobalt element and/or nickel element.
[0028] According to the preparation method of the present invention, the elements used as auxiliary agents 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 can be selected from the group IIB metal element, the group IA metal element, the group IIA metal element and the rare earth metal element; preferably selected from the group consisting of zinc element, sodium element, potassium element, magnesium element, calcium element element, lanthanum and cerium; more preferably selected from zinc, magnesium and lanthanum. The non-metallic element as an auxiliary agent may be selected from phosphorus, boron and fluorine; preferably, it is selected from boron and fluorine.
[0029] According to the preparation method of the present invention, the method for introducing at least one metal element of Group VIB and at least one metal element of Group VIII on the shaped porous support comprises the following steps:
[0030] (1) Impregnating the shaped porous support 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 and with or without auxiliary solvent;
[0031] (2) The mixture obtained by impregnation is subjected to hydrothermal treatment in a closed reactor, and the hydrothermal treatment is carried out at a pressure of P 0 +ΔP; and
[0032] (3) The mixture obtained by the hydrothermal treatment is subjected to solid-liquid separation, and the obtained solid phase is dried.
[0033] 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 element in the finally prepared catalyst is The content of the elements and Group VIII metal elements shall meet the specific use requirements (such as the content requirements described above).
[0034] According to the present invention, the aqueous solution can be prepared by dissolving in water 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.
[0035] The VIB group metal element-containing compound may be selected from the group VIB metal element-containing water-soluble compounds commonly used in the art, and the VIB group metal element-containing compound capable of forming a water-soluble compound in water in the presence of a cosolvent. compound. Specifically, the compound containing the Group VIB metal element may be selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
[0036]The Group VIII metal element-containing compound may be selected from the group VIII metal element-containing water-soluble compounds commonly used in the art, and the Group VIII metal element-containing compounds capable of forming a water-soluble compound in water in the presence of a cosolvent. compound. Specifically, the compound containing a metal element of Group VIII may be selected from the group consisting of nitrates of metals of Group VIII, chlorides of metals of Group VIII, sulfates of metals of Group VIII, formates of metals of Group VIII, Group VIII metal acetate, Group VIII metal phosphate, Group VIII metal citrate, Group VIII metal oxalate, Group VIII metal carbonate, Group VIII metal base Carbonates, Hydroxides of Group VIII Metals, Phosphates of Group VIII Metals, Phosphides of Group VIII Metals, Sulfides of Group VIII Metals, Aluminates of Group VIII Metals, Group VIII Metals molybdates, tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.
[0037] Preferably, the compound containing a metal element of Group VIII is selected from the group consisting of oxalate of metal of Group VIII, nitrate of metal of Group VIII, sulfate of metal of Group VIII, acetate of metal of Group VIII, Group VIII metal chloride, Group VIII metal carbonate, Group VIII metal hydroxycarbonate, Group VIII metal hydroxide, Group VIII metal phosphate, Group VIII metal molybdenum Acid salts, tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.
[0038] Specifically, the compound containing the metal element of Group VIII 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, Cobalt and Nickel Chloride.
[0039] According to the preparation method of the present invention, the aqueous solution described in step (1) may also contain various cosolvents commonly used in the art, so as to improve the compounds containing Group VIB metal elements and the compounds containing Group VIII metal elements. Solubility of a compound in water; or stabilization of the aqueous solution against precipitation. The co-solvent can be various substances commonly used in the art that can realize the above-mentioned functions, and is not particularly limited. For example, the co-solvent may be one or more of phosphoric acid, citric acid, and aqueous ammonia. In the present invention, the concentration of the ammonia water is not particularly limited, and can be a conventional choice in the field. The amount of the co-solvent can be selected conventionally in the art. Generally, in the aqueous solution, the content of the co-solvent can be 1-10% by weight.
[0040] 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 an auxiliary agent can be introduced on the shaped porous carrier before the introduction of the Group VIB 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 of said elements as adjuvants, at least one of said Group VIB metal elements and at least one of said Group VIII metal elements; it is also possible to introduce said elements as Auxiliary elements.
[0041] 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 Before, at least one element as an auxiliary agent is supported on the shaped porous carrier. Elements as adjuvants can be supported on the shaped porous carrier by various methods commonly used in the art. For example, by contacting the shaped porous carrier with an aqueous solution containing at least one compound containing an element as an adjuvant, and successively drying and calcining the shaped porous carrier loaded with the compound, the adjuvant can be used as an adjuvant. The elements of the agent are supported on the shaped porous carrier. The contacting method can be conventionally selected in the field, such as dipping and spraying.
[0042] 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 an auxiliary agent element in the step (1). The aqueous solution described (that is, the aqueous solution containing at least one compound containing a Group VIII metal element and at least one compound containing a Group VIB metal element and with or without a cosolvent also contains at least one compound containing as a cosolvent. A compound of an element as an agent), and impregnating the porous carrier with the aqueous solution, thereby simultaneously introducing the element as an auxiliary agent, the Group VIB metal element and the Group VIII metal element on the shaped porous carrier. In this embodiment, P 0 is the shaped porous support, the compound containing a metal element of Group VIII, the compound containing a metal element of Group VIB, the cosolvent with or without, the compound containing an element as a coagent , and the pressure generated by the water in the aqueous solution in the hydrothermal treatment.
[0043] In the third embodiment of the present invention, the manner of introducing at least one element as an auxiliary agent on the shaped porous support comprises: combining at least one compound containing an element as an auxiliary agent with a compound used for preparing the The raw materials for the shaped porous carrier are mixed and the resulting mixture is shaped.
[0044] According to the preparation method of the present invention, the above three embodiments can be used alone or in combination, without particular limitation, as long as it can ensure that the content of the element as an auxiliary agent in the finally obtained catalyst can meet the specific use requirements (for example, the aforementioned the stated content range). From the viewpoint of process simplicity, the method according to the present invention preferably adopts the second embodiment to introduce elements as auxiliary agents on the shaped porous carrier.
[0045] According to the present invention, the compound containing the element as the auxiliary agent can be various water-soluble compounds containing the element as the auxiliary agent commonly used in the art, for example: the compound containing the element as the auxiliary agent can be selected from the water-soluble compounds of the Group IIB metals Natural 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, water-soluble chlorides 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 hydrogens of group IIA metals Oxides, water-soluble hydroxides of rare earth metals, hydrofluoric acid, hydrofluoric acid salts, fluorosilicic acid, fluorosilicates, ammonium fluoride, boric acid, ammonium borate, ammonium metaborate, and ammonium tetraborate. Preferably, the compound containing the element as 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.
[0046] According to the method of the present invention, the shaped porous support contains silica, alumina and at least one mesoporous molecular sieve. In the present invention, the content of silica, alumina and mesoporous molecular sieve in the shaped porous carrier can be appropriately selected according to the application occasion of the finally prepared catalyst. When the catalyst prepared according to the method of the present invention is used for the hydroisomerization of hydrocarbon oil, based on the total amount of the shaped porous support, the content of the silicon oxide may be 2-45% by weight, preferably 5-40% by weight, more preferably 10-30% by weight, further preferably 15-20% by weight; the content of the mesoporous molecular sieve can be 2-75% by weight, preferably 5-60% by weight, more preferably 2-30% by weight, more preferably 5-20% by weight; the alumina content can be 23-96% by weight, preferably 35-90% by weight, more preferably 40-88% by weight, further preferably 60% by weight -80% by weight.
[0047] In the present invention, the mesoporous molecular sieve refers to a molecular sieve with a ten-membered ring pore structure, which may be an aluminum silicate zeolite molecular sieve or a non-zeolite molecular sieve. For example, the mesoporous molecular sieve can be selected from ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-12 molecular sieve, ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-35 molecular sieve, ZSM-38 molecular sieve, ZSM-48 molecular sieve , one or more of TMA chabazite, SAPO-11 molecular sieve, SAPO-31 molecular sieve and SAPO-41 molecular sieve. The above-mentioned mesoporous molecular sieves and their preparation methods can be referred to US3,702,886, US3,709,979, US4,481,177, US3,832,449, US4,076,842, US4,016,245, US4,046,859, US4,397,827, US4,440,871 and US4,689,138. This article will not repeat them.
[0048] When the catalyst prepared by the method of the present invention is used for the hydroisomerization of hydrocarbon oil, the mesoporous molecular sieve is more preferably one or more of SAPO-11 molecular sieve, ZSM-5 molecular sieve and ZSM-22 molecular sieve.
[0049] According to the method of the present invention, the shaped porous carrier can be prepared by various methods commonly used in the art. For example: Alumina and/or a precursor capable of forming alumina under calcination conditions, silicon oxide and/or a precursor capable of forming silica under calcination conditions can be mixed with mesoporous molecular sieves, and the resulting mixture will be extruded into molding, The extruded shaped body is then dried and calcined to obtain the shaped porous support.
[0050] The precursor capable of forming alumina under calcination conditions can be selected from, for example, hydrated alumina (such as pseudoboehmite) and alumina sol. The precursors that can form silicon oxide under calcination conditions can be, for example, water-soluble silicon-containing compounds, and silicon-containing compounds that can be hydrolyzed to form silica gel or silica sol in an aqueous medium. Specific examples of the precursors capable of forming silicon oxide under firing conditions may include, but are not limited to, water glass, silica sol, and silicate esters.
[0051] According to the present invention, the mixture may also contain extrusion aids and/or adhesives when forming by extrusion. The types and amounts of the extrusion aid and the adhesive are well known to those skilled in the art, and will not be repeated here.
[0052] According to the present invention, the conditions for calcining the shaped body can be selected conventionally in the field. For example, the roasting temperature may be 350-650°C, preferably 400-600°C; the roasting time may be 2-6 hours, preferably 3-5 hours.
[0053] According to the present invention, the porous carrier can have various shapes, such as spherical, sheet, bar or clover shape, according to specific application occasions.
[0054] According to the preparation method of the present invention, in step (1), the impregnation method is not particularly limited, and can be a conventional choice in the field, such as: pore saturation impregnation method and excess impregnation method (ie, supersaturation impregnation method). Preferably, according to the method of the present invention, the impregnation is an excess impregnation. The pore saturation impregnation method and the excess impregnation method are well known in the art and will not be repeated herein. According to the preparation method of the present invention, in step (1), the number of impregnations is not particularly limited, and may be one impregnation or multiple impregnations, so that in the finally obtained catalyst, the metal elements of Group VIII and Group VIB The content of metal elements can meet the requirements of use (such as the content range described above).
[0055] According to the preparation method of the present invention, in step (2), the hydrothermal treatment is performed at a pressure of P 0 performed under the conditions of +ΔP.
[0056] In the present invention, P 0 are the shaped porous support, the compound containing a metal element of Group VIII, the compound containing a metal element of Group VIB, the co-solvent with or without, the co-solvent with or without as a co-agent The compound of the element, and the pressure of the water in the aqueous solution in the hydrothermal treatment.
[0057] According to the method of the present invention, during the hydrothermal treatment, the pressure in the airtight container used for the hydrothermal treatment is reduced by P 0In addition, ΔP is also included, wherein ΔP is 0.05-15MPa. From the viewpoint of balancing the catalytic activity of the finally prepared catalyst and the internal pressure of the airtight container, ΔP is preferably 0.1-10 MPa, more preferably 0.2-8 MPa, and even more preferably 0.2-5 MPa.
[0058] In the present invention, all pressures are gauge pressures.
[0059] Various methods commonly used in the art can be used to make the hydrothermal treatment at a pressure of P 0 performed under the conditions of +ΔP.
[0060] In one embodiment of the present invention, the hydrothermal treatment is carried out at a pressure of P 0 The manner of performing under the condition of +ΔP includes: performing the hydrothermal treatment in the presence of at least one volatile organic compound, and the amount of the volatile organic compound added is such that the pressure generated by the volatile organic compound in the hydrothermal treatment is ΔP.
[0061] The hydrothermal treatment can be carried out in the presence of the volatile organics in various ways (ie, the volatile organics are in a closed vessel in which the hydrothermal treatment is carried out). For example, the volatile organic compounds can be added to the aqueous solution used to impregnate the porous support or the resulting mixture, so that the hydrothermal treatment is performed in the presence of the volatile organic compounds. From the viewpoint 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 carried out in the presence of volatile organic compounds.
[0062] In this embodiment, various commonly used volatile organic compounds can be added to the airtight container, as long as the volatile organic compounds can increase the pressure in the airtight container in which the hydrothermal treatment is performed under the conditions of hydrothermal treatment, so that the airtight container can The internal pressure may be within the range described above.
[0063] In the present invention, the volatile organic compounds may be various substances that can be converted from liquid to 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 having a number average molecular weight of 200-1500. Preferably, the volatile organic compounds are selected from C 1 -C 3 0 fatty alcohols, C 2 -C 30 fatty acids, C 2 -C 30 of fatty amines, C 6 -C 30 of 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 alcohols, C 2 -C 10 fatty acids, C 2 -C 12 of fatty amines, C 6 -C 12 of 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 alcohols, C 2 -C 5 fatty acids, C 2 -C 7 of fatty amines and C 6 -C 11 alkanes.
[0064] 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.
[0065] 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 the volatile organic compound used, which will not be repeated herein.
[0066] In another embodiment of the present invention, the hydrothermal treatment is performed at a pressure of P 0 The manner of performing under the condition of +ΔP includes: performing the hydrothermal treatment in the presence of at least one inert gas, and the inert gas is added in an amount such that the pressure generated by the inert gas in the hydrothermal treatment is ΔP.
[0067] In the present invention, the inert gas refers to a gas that does not interact with the porous carrier, the compound containing the metal element of Group VIB, the compound containing the metal element of Group VIII, the cosolvent, or the element containing the auxiliary agent during the hydrothermal treatment. The gas that chemically interacts with water can be various inactive gases commonly used in the field. Preferably, the inert gas is selected from nitrogen, group zero element gases (eg: argon), carbon dioxide, sulfur hexafluoride and C 1 -C 5 of hydrocarbons. Further preferably, the inert gas is selected from nitrogen gas and group zero element gas.
[0068] According to this embodiment, in the process of hydrothermal treatment, inert gas can be introduced into the airtight container for hydrothermal treatment, so that the pressure in the airtight container is P 0 +ΔP; It is also possible to pass the inert gas into the airtight container for the hydrothermal treatment before the hydrothermal treatment, and then close the container to carry out the hydrothermal treatment.
[0069] According to yet another embodiment of the present invention, the post-treatment is made at a pressure of P 0 The manner 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 amount of the volatile organic compound and the inert gas added makes the volatilization The total pressure generated by the organics and inactive gases in the hydrothermal treatment is ΔP.
[0070] In this embodiment, the types and use methods of the volatile organic compounds and the inert gas are as described above, and will not be repeated here.
[0071] According to the method of the present invention, although the purpose of improving the catalytic activity of the catalyst finally obtained can be achieved by adopting the above three methods, from the viewpoint 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 a volatile organic compound and an inert gas, so that the hydrothermal treatment is performed at a pressure of P. 0 performed under the conditions of +ΔP. More preferably, the hydrothermal treatment is carried out in the presence of an inert gas.
[0072] According to the preparation method of the present invention, the time and temperature of the hydrothermal treatment can be selected conventionally in the field, as long as the pressure of the hydrothermal treatment meets the requirements described above. 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.
[0073] The preparation method according to the present invention further comprises step (3): performing solid-liquid separation on the mixture obtained by the hydrothermal treatment, and drying the obtained solid phase. The preparation method of the present invention is not particularly limited for the method of solid-liquid separation, and can be a conventional choice in the field, for example, it can be filtration, static separation or centrifugal separation. In the present invention, the drying conditions are not particularly limited, and can be conventionally selected in the field. Generally, the drying conditions include: the temperature can be 100-300°C, preferably 100-280°C, more preferably 100-250°C; the time can be 1-12 hours, preferably 2-8 hours.
[0074] The preparation method according to the present invention may further comprise calcining the solid substance obtained by drying. The calcination conditions can be conventionally selected in the art. Generally, the calcination conditions include: the temperature can be 350-550°C, preferably 400-500°C; the time can be 1-8 hours, preferably 2-6 hours.
[0075] A second aspect of the present invention provides a catalyst prepared by the method of the present invention.
[0076] The catalyst according to the present invention has higher catalytic activity when used in the hydroisomerization of hydrocarbon oil. The catalysts according to the invention are particularly suitable as catalysts for isomeric degassing of lube base oils, as catalysts for isomeric dewaxing of hydrocracking tails, and as catalysts for the restoration of gasoline octane number.
[0077] Thus, a third aspect of the present invention provides a use of a catalyst according to the present invention in the hydroisomerization of hydrocarbon oils.
[0078] A fourth aspect of the present invention provides a hydroisomerization method, the method comprising contacting a hydrocarbon oil with the catalyst provided by the present invention under hydroisomerization conditions.
[0079] According to the hydroisomerization method of the present invention, the hydrocarbon oil can be various feedstock oils that need to be isomerized, such as lubricating oil base oil, hydrocracking tail oil and gasoline.
[0080] The present invention is to improve the activity of the catalyst in hydroisomerization by using the catalyst according to the present invention, and the remaining conditions of hydroisomerization are not particularly limited, and can be conventional conditions in the art. Preferably, the hydroisomerization conditions include: the temperature may be 300-420° C., preferably 300-400° C.; in terms of gauge pressure, the pressure may be 0.5-15 MPa, preferably 1-10 MPa; Hourly volume space velocity can be 0.1-5 hours -1 , preferably 0.5-3 hours -1; The volume ratio of hydrogen oil can be 100-3000, preferably 100-2000.
[0081] According to the hydroisomerization process of the present invention, the catalyst is preferably pre-sulfided before use. The pre-vulcanization conditions can be conventional conditions in the field. For example, the pre-sulfiding conditions may include: in the presence of hydrogen, at a temperature of 360-400 ° C, with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide. 2-4 hours of pre-vulcanization. According to the hydroisomerization method of the present invention, the pre-sulfurization can be carried out outside the reactor or in-situ in the reactor.
