CN103285939B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrofinishing process - Google Patents

Abstract

The present invention relates to a catalyst with hydrogenation catalysis and its preparation method and application. The preparation method comprises the introduction of Group VIB metal elements, Group VIII metal elements and metal elements as auxiliary agents on a shaped porous carrier, wherein the introduction of the first The method for a Group VIB metal element and a Group VIII metal element comprises impregnating said shaped porous support with an aqueous solution containing at least one Group VIII metal element-containing compound and at least one Group VIB metal element-containing compound compound and with or without co-solvent; the mixture obtained by impregnation is subjected to hydrothermal treatment in a closed reactor under the condition of pressure P ₀ +ΔP; the mixture obtained by hydrothermal treatment is subjected to solid-liquid separation, and the obtained solid phase dry. The invention also relates to a hydrofinishing method. The catalyst of the present invention shows higher catalytic activity in the hydrofinishing of hydrocarbon oil.

Description

Catalyst with hydrogenation catalytic effect, preparation method and application thereof, and hydrogenation refining method

technical field

The invention relates to a catalyst with hydrogenation catalysis, a preparation method thereof, and the application of the catalyst in hydrocarbon oil hydrofinishing; the invention also relates to a hydrofinishing method using the catalyst.

Background technique

With the increasingly stringent environmental protection requirements worldwide, countries have increasingly stringent requirements on the quality of vehicle fuel. In addition, due to the reduction of oil resources, the nature of crude oil has become heavier and worse, and refineries have to process lower-quality crude oil. Therefore, greatly reducing the content of impurities and polycyclic aromatic hydrocarbons in diesel oil and significantly improving the quality of diesel oil has become an urgent problem for oil refining companies to solve. Hydrogenation technology is one of the main technologies to reduce the impurity content in oil and improve the quality of oil, and its core is hydrogenation catalyst.

Therefore, the development of catalysts with higher hydrogenation activity has become a research hotspot.

CN101298043B discloses a hydrothermal deposition preparation method of a supported single metal hydrodesulfurization catalyst, the method comprising:

(1) add a kind of metal salt solution that is selected from the VIB group active metal in the autoclave that has alumina, take mineral acid as precipitating agent, take organic acid as dispersant, the temperature of controlling hydrothermal reaction is 100- 200°C for 6-48 hours, wherein the molar ratio of the dispersant to the active metal is 0.5-3:1, and the dispersant is a dibasic or tribasic carboxylic acid with 2-12 carbon atoms;

(2) After the hydrothermal reaction is completed, the suspension is filtered, washed with water, dried and roasted to obtain a hydrodesulfurization catalyst.

CN101298047A discloses a method for preparing a hydrogenation catalyst, the carrier of the hydrogenation catalyst is loaded with Group VIB metal and Group VIII metal active components, and the preparation method comprises:

(1) Add the carrier and the salt solution containing Group VIB metals into the autoclave, use inorganic acid as precipitant, cationic surfactant as dispersant, control the temperature of hydrothermal reaction to be 100-200°C, and the time is 12 -36 hours;

(2) After the hydrothermal reaction is completed, the suspension is filtered, washed with water, dried and roasted to obtain a monometallic catalyst;

(3) Place the obtained monometallic catalyst in an autoclave, add the salt solution of Group VIII metal, use urea as a precipitating agent, react at a temperature of 50-90° C. for 4-12 hours, then raise the temperature to 90-137°C, then react for 4-12 hours;

(4) After the reaction product is filtered and washed with water, it is dried and calcined to obtain a hydrogenation catalyst with a bimetallic component.

When adopting the disclosed hydrothermal deposition method of CN101298043B and CN101298047A to prepare the hydrogenation catalyst, because the solubility of the compound containing the VIB group metal element is different from the solubility of the compound containing the VIII group metal element, it is necessary to carry out two hydrothermal deposition reactions. The preparation of hydrogenation catalysts with bimetallic components is cumbersome and difficult to meet the needs of large-scale production.

Li Juncheng et al. (Effect of hydrothermal modification on the structure and performance of NiMO/γ-Al ₂ O ₃ hydrodenitrogenation catalyst, Journal of Inorganic Chemistry, 20(6): 739-742, 2004) disclosed a hydrogenation catalyst A preparation method, which comprises loading (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O and Ni(NO ₃ ) ₂ ·6H ₂ O on γ-Al ₂ O ₃ by a stepwise impregnation method, and after impregnation The product was hydrothermally modified at a temperature of 140-180 °C for 2 hours. However, it was found during the research that the hydrogenation activity of the catalyst prepared by this method still needs to be further improved.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a catalyst with hydrogenation catalysis, the catalyst prepared by the method has high hydrogenation catalysis activity, and the method is easy to operate, and can be prepared by one-step impregnation. and Group VIII metal elements as catalysts.

The inventors of the present invention have found in the course of research that the porous carrier is impregnated with an aqueous solution containing at least one compound containing a Group VIB metal element and at least one compound containing a Group VIII metal element, and the impregnated mixture is subjected to water During the heat treatment, increasing the pressure of the hydrothermal treatment can significantly improve the catalytic activity of the final prepared catalyst. The present invention has thus been accomplished.

A first aspect of the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the preparation method comprising:

introducing at least one metal element of group VIB, at least one metal element of group VIII and at least one metal element as an auxiliary agent on the shaped porous carrier;

Wherein, 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 carrier comprises the following steps:

(1) impregnating the formed porous support with an 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;

(2) The impregnated mixture is subjected to hydrothermal treatment in a closed reactor, and the hydrothermal treatment is carried out under the condition of pressure P ₀ +ΔP, wherein P ₀ is the formed porous carrier, the VIII-containing The compound of the group metal element, the compound containing the group VIB metal element, the co-solvent with or without the co-solvent, and the pressure generated by the water in the aqueous solution during the hydrothermal treatment, ΔP is 0.05-15MPa; and

(3) Separating the mixture obtained by hydrothermal treatment into solid and liquid, and drying the obtained solid phase.

A second aspect of the present invention provides a catalyst obtained by the preparation method of the present invention.

A third aspect of the present invention provides the use of the catalyst according to the present invention in hydrorefining of hydrocarbon oils.

A fourth aspect of the present invention provides a hydrofinishing process comprising contacting a hydrocarbon oil with a catalyst according to the present invention under hydrofinishing conditions.

According to the method of the present invention, when the mixture obtained after impregnating the shaped porous carrier with the impregnating liquid is subjected to hydrothermal treatment, in addition to the shaped porous carrier, the compound containing the metal element of Group VIII, the compound containing the metal element of Group VIB, containing or not In addition to the pressure P0 generated by the co-solvent and water in the aqueous solution, the pressure _ΔP is additionally applied, and the catalyst thus prepared shows higher catalytic activity in the hydrofinishing of hydrocarbon oil.

Detailed ways

The first aspect of the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the preparation method comprising introducing at least one metal element of Group VIB, at least one metal element of Group VIII and at least one metal element as an auxiliary agent.

In the present invention, the term "at least one" means one or two or more.

In the catalyst obtained according to the preparation method of the present invention, the contents of the Group VIB metal element, the Group VIII metal element and the metal element as a promoter can be properly selected according to the specific application of the catalyst. Generally, the introduction amount of the metal element of the VIB group, the metal element of the VIII group and the metal element as an auxiliary agent on the shaped porous support is such that, based on the total amount of the catalyst, Based on oxides, the content of Group VIB metal elements may be 10-50% by weight, preferably 15-45% by weight; the content of Group VIII metal elements may be 1-10% by weight, preferably 1-7% by weight The content of the metal element as an auxiliary agent can be 0.5-10% by weight, preferably 0.5-5% by weight; the content of the shaped porous carrier can be 30-88.5% by weight, preferably 43-83.5% by weight .

According to the preparation method of the present invention, the metal elements of Group VIB and the metal elements of Group VIII may be conventional choices in the art. Generally, the Group VIB metal element is preferably molybdenum and/or tungsten, and the Group VIII metal element is preferably cobalt and/or nickel.

According to the preparation method of the present invention, the metal elements used as promoters can be various metal elements commonly used in the art that can improve the performance of catalysts with hydrogenation catalysis, and can be selected according to the application of the catalyst. Preferably, the metal element used as an auxiliary agent may be selected from Group IIB metal elements, Group IA metal elements, Group IIA metal elements and rare earth metal elements. More preferably, the metal element used as an auxiliary agent is selected from zinc, sodium, potassium, magnesium, calcium, lanthanum and cerium.

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 carrier comprises the following steps:

(1) The shaped porous support is impregnated with an aqueous solution containing 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 solvent;

(2) subjecting the mixture obtained by impregnation to hydrothermal treatment in a closed reactor, and the hydrothermal treatment is carried out under the condition that the pressure is P ₀ +ΔP; and

(3) Separating the mixture obtained by hydrothermal treatment into solid and liquid, and drying the obtained solid phase.

According to the preparation method of the present invention, in the aqueous solution described in step (1), the concentration of the compound containing the VIB group metal element and the compound containing the VIII group metal element can make the VIB group metal in the final prepared catalyst The content of the element and the Group VIII metal element shall meet the specific use requirements (such as the content requirements mentioned above).

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 in water.

For example, the compound containing the Group VIB metal element can be a water-soluble compound containing the Group VIB metal element commonly used in the art, and the compound containing the Group VIII metal element can be a commonly used compound containing the Group VIII metal element in the art. Water-soluble compounds of elements.

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

The compound containing the metal element of Group VIII may be selected from the group consisting of nitrates of metal elements of Group VIII, chlorides of metal elements of Group VIII, sulfates of metal elements of Group VIII, formates of metal elements of Group VIII, Acetates of Group VIII metal elements, phosphates of Group VIII metal elements, citrates of Group VIII metal elements, oxalates of Group VIII metal elements, carbonates of Group VIII metal elements, Hydroxides of Group VIII metal elements, Hydroxides of Group VIII metal elements, Phosphates of Group VIII metal elements, Phosphides of Group VIII metal elements, Sulfides of Group VIII metal elements, Group VIII Aluminates of group metal elements, molybdates of group VIII metal elements, tungstates of group VIII metal elements and water-soluble oxides of group VIII metal elements.

Preferably, the compound containing the metal element of Group VIII is selected from the group consisting of oxalates of metal elements of Group VIII, nitrates of metal elements of Group VIII, sulfates of metal elements of Group VIII, esters of metal elements of Group VIII acid salt, chloride of Group VIII metal element, carbonate of Group VIII metal element, basic carbonate of Group VIII metal element, hydroxide of Group VIII metal element, Phosphates, molybdates of Group VIII metals, tungstates of Group VIII metals and water-soluble oxides of Group VIII metals.

Specifically, the compound containing the Group VIII metal element 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, chloride Cobalt and Nickel Chloride.

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 reaction between the compound containing the VIB group metal element and the compound containing the VIII group metal element. Solubility in water; or stabilization of said aqueous solution against precipitation. The co-solvent can be various substances commonly used in the art that can achieve the above functions, without any particular limitation. For example, the co-solvent may be one or more of phosphoric acid, citric acid and ammonia water. The present invention has no particular limitation on the concentration of the ammonia water, which may be a conventional choice in the art. The amount of the co-solvent can be conventionally selected in the art, and generally, the content of the co-solvent in the aqueous solution can be 1-10% by weight.

According to the preparation method of the present invention, various methods commonly used in the art can be used to introduce at least one metal element as an auxiliary agent on the shaped porous carrier. For example: before introducing the VIB group metal element and the VIII group metal element, the metal element as an auxiliary agent can be introduced on the shaped porous carrier; it can also be simultaneously introduced on the shaped porous carrier Introducing at least one metal element as an auxiliary agent, at least one metal element of Group VIB and at least one metal element of Group VIII; it is also possible to introduce the Describe the metal elements used as additives.

In the first embodiment of the present invention, the method of introducing at least one metal element as an auxiliary agent on the shaped porous carrier includes: in step (1), impregnating the shaped porous carrier with the aqueous solution Before the carrier, at least one metal element as an auxiliary agent is supported on the shaped porous carrier. Various methods commonly used in the art can be used to load the metal element as an auxiliary agent on the shaped porous carrier. For example: by contacting the shaped porous carrier with an aqueous solution containing at least one compound containing a metal element as an auxiliary agent, and successively drying and calcining the shaped porous carrier loaded with the compound, the The metal element of the additive is supported on the shaped porous carrier. The contacting method can be a conventional choice in this field, for example: dipping and spraying.

In the second embodiment of the present invention, the method of introducing at least one metal element as an auxiliary agent on the shaped porous support includes: dissolving at least one compound containing the metal element as an auxiliary agent in In the aqueous solution described in step (1) (that is, containing at least one compound containing the VIII metal element and at least one compound containing the VIB group metal element and containing or not containing a cosolvent, the aqueous solution also contains at least a compound containing the metal element as an auxiliary agent), and impregnate the porous carrier with the aqueous solution, thereby simultaneously introducing the metal element as an auxiliary agent, the Group VIB metal element, and The Group VIII metal element. In this embodiment, 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 co-solvent with or without, the The compound containing the metal element as an auxiliary agent, and the pressure generated by the water in the aqueous solution during the hydrothermal treatment.

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

According to the preparation method of the present invention, the above-mentioned three embodiments can be used alone or in combination, without special limitation, as long as it can be ensured that in the finally obtained catalyst, the content of the metal element as a promoter can meet the specific requirements for use (such as the above-mentioned The stated content range) can be. From the viewpoint of process simplicity, the method according to the present invention preferably adopts the second embodiment to introduce the metal element as an auxiliary agent on the shaped porous carrier.

According to the present invention, the compound containing the metal element as an auxiliary agent can be various water-soluble compounds containing the metal element as an auxiliary agent commonly used in the art, for example: water-soluble nitric acid that can be selected from the metals of Group IIB Salts, water-soluble nitrates of Group IA metals, water-soluble nitrates of Group IIA metals and water-soluble nitrates of rare earth metals, water-soluble chlorides of Group IIB metals, water-soluble chlorides of Group IA metals, 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 hydroxides of Group IIA metals and water-soluble hydroxides of rare earth metals. Specifically, the compound containing the metal element as an auxiliary agent may be selected from magnesium nitrate, sodium nitrate, zinc nitrate, cerium nitrate, lanthanum nitrate, magnesium chloride, sodium chloride, zinc chloride, cerium chloride and lanthanum chloride.

According to the preparation method of the present invention, the shaped porous carrier may be various shaped porous carriers commonly used in the art, without any particular limitation. Preferably, the shaped porous support is a shaped refractory inorganic oxide. In the present invention, the term "heat-resistant inorganic oxide" refers to an inorganic oxygen-containing compound whose decomposition temperature is not lower than 300°C (for example, the decomposition temperature is 300-1000°C) in oxygen or an oxygen-containing atmosphere. In the present invention, the shaped porous carrier can be formed of one kind of heat-resistant inorganic oxide, or can be formed of more than two kinds of heat-resistant inorganic oxide.

According to the present invention, the heat-resistant inorganic oxide may be various heat-resistant inorganic oxides commonly used in the field that can be used as a catalyst carrier. Generally, the heat-resistant inorganic oxide can be aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silicon oxide-magnesia, silicon oxide-zirconia, silicon oxide-thorium oxide, silicon oxide-beryllium oxide, silicon oxide - titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-oxide One or more of zirconium.

Preferably, the heat-resistant inorganic oxide is alumina.

According to the preparation method of the present invention, the shaped porous carrier can be prepared by methods commonly used in the art. For example, it can be obtained by molding at least one heat-resistant inorganic oxide and/or at least one precursor capable of forming a heat-resistant inorganic oxide under firing conditions, and firing the obtained shaped body. The molding method can be a conventional choice in the field, for example: at least one heat-resistant inorganic oxide and/or at least one precursor capable of forming a heat-resistant inorganic oxide under calcination conditions can be placed in an extruder Extrusion.

In the present invention, the precursor capable of forming a heat-resistant inorganic oxide under calcination conditions can be properly selected according to the type of the expected heat-resistant inorganic oxide, whichever can form the heat-resistant inorganic oxide by calcination .

For example, when the heat-resistant inorganic oxide is alumina, the precursor capable of forming heat-resistant inorganic oxide under calcination conditions can be various substances commonly used in the art that can form alumina under calcination conditions, For example: hydrated alumina (such as pseudoboehmite), aluminum sol.

In a preferred embodiment of the present invention, the precursor capable of forming alumina under calcination conditions is extruded, and then the extruded molded body is dried and calcined to obtain the porous carrier.

According to the present invention, extrusion aids and/or adhesives may also be added to the heat-resistant inorganic oxide and/or the precursor capable of forming the heat-resistant inorganic oxide under firing conditions when extrusion is used for molding . The type and amount of the extrusion aid and peptizing agent are well known to those skilled in the art, and will not be repeated here.

According to the present invention, the conditions for firing the extruded shaped body can be selected conventionally in the art. 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.

According to the present invention, the porous carrier can have various shapes according to the specific use occasions, for example: spherical, sheet or strip.

According to the preparation method of the present invention, in step (1), there is no particular limitation on the method of impregnation, which can be a conventional choice in this field, for example: pore saturated impregnation method and excess impregnation method (ie, supersaturated impregnation method). Preferably, according to the method of the present invention, said impregnation is over-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 times of impregnation is not particularly limited, it can be one impregnation, or multiple impregnations, so that in the catalyst finally obtained, the metal elements of Group VIII and Group VIB The content of the metal element can meet the use requirements (for example, the content range mentioned above) shall prevail.

According to the preparation method of the present invention, in step (2), the hydrothermal treatment is carried out under the condition that the pressure is P ₀ +ΔP.

In the present invention, _P0 is the shaped porous carrier, the compound containing the metal element of Group VIII, the compound containing the metal element of Group VIB, the co-solvent containing or not containing, containing or not containing The compound containing the metal element as an auxiliary agent, and the pressure generated by the water in the aqueous solution in the hydrothermal treatment.

According to the method of the present invention, in the hydrothermal treatment process, the pressure in the airtight container used for hydrothermal treatment includes, in addition to P ₀ , ΔP, wherein ΔP is 0.05-15 MPa. Preferably, ΔP is 0.1-10 MPa. From the perspective of balancing the catalytic activity of the final prepared catalyst and the internal pressure of the closed container, ΔP is more preferably 0.2-7 MPa, and ΔP is more preferably 0.2-5 MPa.

In the present invention, the pressure is all measured by gauge pressure.

Various methods commonly used in the art can be used to carry out the hydrothermal treatment under the condition of pressure P ₀ +ΔP.

In one embodiment of the present invention, the method of performing the hydrothermal treatment under the condition of pressure P ₀ +ΔP includes: performing the hydrothermal treatment in the presence of at least one volatile organic compound, the volatile The amount of organic matter added is such that the pressure generated by the volatile organic matter in the hydrothermal treatment is ΔP.

Various ways can be employed to allow the hydrothermal treatment to be performed in the presence of the volatile organic compounds (ie, the volatile organic compounds are present in a closed container for hydrothermal treatment). For example, the volatile organic compounds may be added to the aqueous solution used to impregnate the porous support or the impregnated mixture such that the hydrothermal treatment is performed in the presence of volatile organic compounds. From the perspective of further improving the catalytic activity of the prepared catalyst, according to the method of the present invention, volatile organic compounds are preferably added to the impregnated mixture, so that the hydrothermal treatment is performed in the presence of volatile organic compounds.

In this embodiment, various commonly used volatile organic compounds can be added into the airtight container, as long as the volatile organic compounds can increase the pressure in the airtight container for the hydrothermal treatment under the hydrothermal treatment conditions, so that the airtight container It is sufficient that the internal pressure is within the range mentioned above.

In the present invention, the volatile organic compounds may be various substances that can change from liquid to gas under hydrothermal treatment conditions and/or substances that can generate gas under hydrothermal treatment conditions. For example, the volatile organic compound 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 alcohols, C ₂ -C ₃₀ fatty acids, C ₂ -C ₃₀ fatty amines, C ₆ -C ₃₀ alkanes and number average molecular weights of 200- 1500 polyethylene glycol. More preferably, the volatile organic compound is selected from the group consisting of C ₁ -C ₁₂ fatty alcohols, C ₂ -C ₁₀ fatty acids, C ₂ -C ₁₂ fatty amines, C ₆ -C ₁₂ alkanes and a number average molecular weight of 200 -1500 polyethylene glycol. Further preferably, the volatile organic compound is selected from C ₁ -C ₈ fatty alcohols, C ₂ -C ₅ fatty acids, C ₂ -C ₇ fatty amines and C ₆ -C ₁₁ alkanes.

Specifically, the volatile organic compound can be selected from but not limited to: n-propanol, isopropanol, ethylene glycol, glycerol, triethylene glycol, polyethylene glycol with a number average molecular weight of 200-1500, diethylene glycol Diol, 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.

According to the method of the present invention, the amount of the volatile organic compound is not particularly limited, and can be properly selected according to the expected ΔP value and the type of the volatile organic compound used, and will not be described herein again.

In another embodiment of the present invention, the method of performing the hydrothermal treatment under the condition of pressure P ₀ +ΔP includes: performing the hydrothermal treatment in the presence of at least one inert gas, the non-reactive gas The amount of active gas added is such that the pressure generated by the inert gas during the hydrothermal treatment is ΔP.

In the present invention, the inert gas refers to the inert gas that will not interact with the porous carrier, the compound containing the metal of Group VIB, the compound containing the metal of Group VIII, the cosolvent, the metal element containing the metal element as the auxiliary agent during the hydrothermal treatment process. The gas that chemically interacts with the compound and water can be various inert gases commonly used in this 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 hydrocarbons. Further preferably, the inert gas is selected from nitrogen and group zero element gases.

According to this embodiment, in the process of hydrothermal treatment, an inert gas can be introduced into the airtight container for hydrothermal treatment, so that the pressure in the airtight container is P ₀ +ΔP; The inert gas is introduced into the airtight container for the hydrothermal treatment, and then the container is closed for hydrothermal treatment.

According to yet another embodiment of the present invention, the way of performing the post-treatment under the condition of pressure P ₀ +ΔP includes: performing the post-treatment in the presence of at least one volatile organic compound and at least one inert gas In the hydrothermal treatment, the total addition amount of the volatile organic compound and the inert gas makes the total pressure generated by the volatile organic compound and the inactive gas in the hydrothermal treatment be ΔP.

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

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 catalyst finally obtained, but from the perspective of further improving the activity and ease of operation of the catalyst obtained by the preparation method of the present invention, according to this method In the preparation method of the invention, the hydrothermal treatment is preferably carried out in the presence of an inert gas, or the hydrothermal treatment is carried out in the presence of volatile organic compounds and an inert gas, so that the hydrothermal treatment can be performed at a pressure of P ₀ +ΔP under conditions. More preferably, the hydrothermal treatment is performed in the presence of an inert gas.

According to the preparation method of the present invention, the time and temperature of the hydrothermal treatment can be conventionally selected in the field, as long as the pressure of the hydrothermal treatment meets the above-mentioned 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.

The preparation method according to the present invention further includes step (3): separating the solid and liquid from the mixture obtained by the hydrothermal treatment, and drying the obtained solid phase. The preparation method of the present invention has no special limitation on the method of solid-liquid separation, which can be a conventional choice in this field, for example, it can be filtration, static separation or centrifugation. In the present invention, the drying conditions are not particularly limited, and may be conventional choices in the art. Generally, the drying conditions include: the temperature may be 100-300°C, preferably 100-280°C, more preferably 100-250°C; the time may be 1-12 hours, preferably 2-8 hours.

The preparation method according to the present invention may also include roasting the dried solid matter. The conditions of the calcination can be conventionally selected in the art. Generally, the calcination conditions include: the temperature may be 350-550° C., preferably 400-500° C.; the time may be 1-8 hours, preferably 2-6 hours.

A second aspect of the present invention provides a catalyst obtained by the preparation method of the present invention. The catalyst according to the invention has a higher catalytic activity when used for hydrofinishing of hydrocarbon oils.

Thus, a third aspect of the present invention provides a use of the catalyst according to the present invention in the hydrorefining of hydrocarbon oils.

The fourth aspect of the present invention provides a hydrofinishing method, which comprises contacting hydrocarbon oil with the catalyst provided by the present invention under hydrofinishing conditions.

The hydrorefining method according to the present invention is suitable for refining processes such as hydrodesulfurization and hydrodenitrogenation of various hydrocarbon oil raw materials. The hydrocarbon oil raw material can be one or more of gasoline, diesel oil, lubricating oil, kerosene and naphtha, for example; one or more.

The present invention improves the activity of the catalyst in the hydrofinishing process by using the catalyst of the present invention, and there is no special limitation on the remaining conditions of the hydrofinishing method, which can be conventional choices in the field. Generally, the conditions of the hydrofinishing include: the temperature can be 300-400° C.; the pressure can be 1.0-8.0 MPa in terms of gauge pressure; the liquid hourly volume space velocity of the hydrocarbon oil can be 0.5-3.0 hours ⁻¹ ; The volume ratio of hydrogen to oil can be 100-700.

According to the hydrofinishing method of the present invention, the catalyst is preferably presulfurized by conventional methods in the art before use. Generally, the presulfurization 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 Carry out 2-4 hours of pre-vulcanization. According to the hydrofinishing method of the present invention, the presulfurization can be carried out outside the hydrogenation reactor, or in-situ in the hydrogenation reactor.

The present invention will be described in detail below in conjunction with the examples.

In the following examples and comparative examples, a 3271E X-ray fluorescence spectrometer commercially available from Rigaku Electric Industries Co., Ltd. was used to analyze and measure the content of each element in the catalyst.

In the following examples and comparative examples, gas chromatography was used to measure the sulfur content and nitrogen content in the hydrodesulfurization raw materials and the obtained products.

In the following examples and comparative examples, the relative hydrodesulfurization activity is used to evaluate the hydrodesulfurization activity of the catalyst. The calculation method is to treat the hydrodesulfurization reaction as a 1.65-order reaction, and calculate the reaction rate constant k (X ) _HDS :

In the formula, LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrofining reaction,

Based on the hydrodesulfurization activity of catalyst D-3 (denoted as k(D-3) _HDS ), the relative hydrodesulfurization activity of catalyst X is calculated by the following formula:

In the following examples and comparative examples, the relative hydrodenitrogenation activity is used to evaluate the hydrodenitrogenation activity of the catalyst. The calculation method is to treat the hydrodenitrogenation reaction as a first-order reaction, and calculate the reaction rate constant of catalyst X according to the following formula k(X) _HDN :

In the formula, LHSV is the liquid hourly volume space velocity of the hydrocarbon oil during the hydrofining reaction,

Based on the hydrodenitrogenation activity of catalyst D-3 (denoted as k(D-3) _HDN ), the relative hydrodenitrogenation activity of catalyst X is calculated by the following formula:

Examples 1-7 are used to illustrate the catalyst with hydrogenation catalysis and its preparation method of the present invention.

Example 1

(1) 1000 grams of aluminum hydroxide powder (purchased from Sinopec Changling Branch Catalyst Factory, dry basis content is 72% by weight) is extruded into a butterfly bar with a circumscribed circle diameter of 1.3 mm with an extruder, and the extruded The wet strip was dried at 120° C. for 4 hours, and then fired at 600° C. for 3 hours to obtain carrier S1.

(2) 50 grams of ammonium molybdate is added to 120 milliliters of water, under heating and stirring, dropwise add ammoniacal liquor with a concentration of 25% by weight until the ammonium molybdate dissolves, then add 30 grams of cobalt nitrate and 15 grams of zinc nitrate, after stirring and dissolving, add 20ml of ethanol, then add water to make up to 200ml. 100 g of carrier S1 was impregnated with the above aqueous solution by the excess impregnation method, and the impregnation time was 0.1 hour. The impregnated mixture was placed in a high-pressure reactor for hydrothermal treatment. The conditions of hydrothermal treatment include: temperature 150°C, time 4 hours; pressure 0.7MPa, where P ₀ =0.5MPa, ΔP=0.2MPa. The mixture obtained by hydrothermal treatment was cooled to room temperature, and after filtration, the obtained solid was dried at 120° C. for 2 hours, and then calcined at 450° C. for 3 hours to obtain catalyst B-1 according to the present invention. The composition of catalyst B-1 is shown in Table 1.

Example 2

Add 15 grams of basic cobalt carbonate and 30 grams of molybdenum trioxide into 120 milliliters of water, add 10 grams of phosphoric acid and 25 grams of magnesium nitrate with stirring, heat and stir to dissolve, add 15 milliliters of isopropanol, and then add water to make up to 200 milliliters. 100 g of carrier S1 was impregnated with the above aqueous solution by the method of excessive impregnation, and the impregnation time was 0.2 hours. The impregnated mixture was placed in an autoclave for hydrothermal treatment. The hydrothermal treatment conditions included: temperature 200°C; time 10 hours; pressure 2.1MPa, where P ₀ =1.5MPa, ΔP=0.6MPa. The mixture obtained by the hydrothermal treatment was cooled to room temperature, and after filtration, the solid obtained was dried at 120° C. for 2 hours, followed by further drying at 250° C. for 3 hours, thereby obtaining catalyst B-2 according to the present invention. The composition of catalyst B-2 is shown in Table 1.

Example 3

Add 20 grams of basic nickel carbonate to 150 milliliters of water, add 8 grams of phosphoric acid with stirring, heat and stir to dissolve, add 12 grams of ammonium molybdate, 110 grams of ammonium metatungstate and 9 grams of lanthanum nitrate respectively with stirring, add water after dissolution Make up to 200ml. 100 g of carrier S1 was impregnated with the above aqueous solution by the method of excessive impregnation, and the impregnation time was 0.5 hour. The mixture obtained by impregnation is placed in a high-pressure reactor for hydrothermal treatment. The conditions of the hydrothermal treatment include: the temperature is 100° C.; the time is 24 hours; nitrogen gas is introduced into the high-pressure reactor during the hydrothermal treatment to make the The pressure is 5.2MPa, where P ₀ =0.2MPa, ΔP=5.0MPa. The mixture obtained by hydrothermal treatment was cooled to room temperature, and after filtration, the obtained solid was dried at 120° C. for 2 hours, and then dried at 200° C. for 3 hours to obtain catalyst B-3 according to the present invention. For the composition of catalyst B-3, see Table 1.

Example 4

Adopt the same method as Example 3 to prepare the catalyst, the difference is that in the hydrothermal treatment process, the feed rate of nitrogen makes the pressure in the autoclave be 10.2MPa, wherein, P ₀ =0.2MPa, ΔP=10.0MPa, obtain According to the catalyst B-4 of the present invention, the composition of the catalyst B-4 is shown in Table 1.

Comparative example 1

Adopt the same method as Example 3 to prepare the catalyst, the difference is that nitrogen is not passed into the autoclave in the hydrothermal treatment process, and the pressure in the autoclave is 0.2MPa (that is, ΔP=0), and the catalyst D- 1, whose composition is shown in Table 1.

Example 5

Add 30 grams of ammonium molybdate to 70 milliliters of water, add ammonia water with a concentration of 25% by weight dropwise under heating and stirring until the ammonium molybdate dissolves, then add 20 grams of cobalt nitrate and 15 grams of zinc nitrate, stir and dissolve, then add water to set the volume to 85 ml. 100 g of the S1 carrier was impregnated with the above aqueous solution by a saturated impregnation method, and the impregnation time was 2 hours. The mixture obtained by impregnating is placed in a high-pressure reactor for hydrothermal treatment. The conditions of the hydrothermal treatment include: the temperature is 100 ° C, and the time is 12 hours. During the hydrothermal treatment, nitrogen is introduced into the high-pressure reactor to make the pressure in the high-pressure reactor is 3.2MPa, where P ₀ =0.2MPa, ΔP=3.0MPa. The mixture obtained by hydrothermal treatment was cooled to room temperature, and after filtration, the obtained solid was dried at 120° C. for 2 hours, and then dried at 200° C. for 3 hours to obtain catalyst B-5 according to the present invention. The composition of catalyst B-5 was shown in Table 1.

Comparative example 2

Adopt the same method as Example 5 to prepare the catalyst, the difference is that in the hydrothermal treatment process, nitrogen is not passed into the autoclave, and the pressure in the autoclave is 0.2MPa (that is, ΔP=0), and catalyst D is obtained. -2, the composition of the catalyst is shown in Table 1.

Example 6

(1) 1000 grams of aluminum hydroxide powder (purchased from the Catalyst Factory of Sinopec Changling Branch Company, dry basis content is 72% by weight) is mixed with 40 grams of magnesium nitrate, and after mixing evenly, it is extruded into a circumscribed circle with a diameter of 1.3 mm butterfly strips, the extruded wet strips were dried at 120° C. for 4 hours, and then fired at 600° C. for 3 hours to obtain carrier S2.

(2) 50 grams of ammonium molybdate is added to 120 milliliters of water, under heating and stirring, dripping concentration is the ammoniacal liquor of 25% by weight to ammonium molybdate dissolving, then adds 30 grams of cobalt nitrate, after stirring and dissolving, add 20 milliliters of ethanol, then Add water to make up to 200 ml. 100 g of carrier S2 was impregnated with the above aqueous solution by the excess impregnation method, and the impregnation time was 0.1 hour. Place the impregnated mixture in a high-pressure reactor for hydrothermal treatment. The conditions of the hydrothermal treatment include: the temperature is 150°C, and the time is 4 hours. During the hydrothermal treatment, argon gas is introduced into the high-pressure reactor to make The pressure is 2.5MPa, wherein, P ₀ =0.5MPa, ΔP=2.0MPa (the pressure generated by ethanol is 0.2MPa, and the pressure generated by argon is 1.8MPa). The mixture obtained by hydrothermal treatment was cooled to room temperature, and after filtration, the obtained solid was dried at 120° C. for 2 hours, followed by calcining at 450° C. for 3 hours to obtain catalyst B-6 according to the present invention. The composition of Catalyst B-6 is shown in Table 1.

Example 7

The catalyst was prepared in the same manner as in Example 1, except that instead of adding 20 milliliters of ethanol to the aqueous solution, 20 milliliters of ethanol was added to the autoclave with the mixture obtained by impregnation, thereby obtaining the catalyst according to the present invention Catalyst B-7. The composition of Catalyst B-7 is shown in Table 1.

Comparative example 3

The catalyst is prepared in the same manner as in Example 1, except that ethanol and zinc nitrate are not added to the autoclave. During the hydrothermal treatment, the pressure in the autoclave is 0.5 MPa (wherein, ΔP=0), and Catalyst D-3, the composition of which is shown in Table 1.

Table 1

Examples 8-14 are used to illustrate the application of the catalyst according to the present invention and the hydrofinishing method.

Examples 8-14

The catalysts prepared in Examples 1-7 were respectively evaluated on a 30 ml diesel hydrogenation unit.

The raw materials used are as follows:

Raw material: Middle East Straight Run Diesel

S content: 9700wppm

N content: 97wppm

Density (20°C): 0.8321g/cm ³

Refractive index (20°C): 1.4658

The following process operating conditions were used:

Liquid hourly volumetric space velocity: 2.0h ^-1

Hydrogen oil volume ratio: 300

Pressure: 3.2MPa

Reaction temperature: 330°C

Among them, the relative hydrodesulfurization activity and relative hydrodenitrogenation activity of the catalysts are shown in Table 2.

Comparative example 4-6

The same method as in Examples 8-14 is used for hydrofining, except that the catalyst is the catalyst prepared in Comparative Examples 1-3, wherein the relative hydrodesulfurization activity and relative hydrodenitrogenation activity of the catalyst are listed in Table 2 Shows.

Table 2

The results in Table 2 show that the catalyst prepared according to the method of the present invention exhibits higher catalytic activity in the hydrorefining of hydrocarbon oil.

Claims (22)

1. A preparation method of a catalyst with hydrogenation catalysis, the preparation method comprising: introducing at least one metal element of group VIB, at least one metal element of group VIII and at least one metal element as an auxiliary agent on the shaped porous carrier; It is characterized in that 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 carrier comprises the following steps: (1) impregnating the formed porous support with an aqueous solution, the aqueous solution consisting of at least one compound containing a Group VIII metal element, at least one compound containing a Group VIB metal element, a co-solvent with or without , containing or not containing volatile organic compounds, containing or not containing at least one compound containing the metal element as an auxiliary agent, and water; (2) The impregnated mixture is subjected to hydrothermal treatment in a closed reactor, and the hydrothermal treatment is carried out under the condition of pressure P ₀ +ΔP, wherein P ₀ is the formed porous carrier, the VIII-containing The compound of group metal element, the compound containing VIB group metal element, the co-solvent containing or not containing, the compound containing the metal element as auxiliary agent containing or not, and the compound in the aqueous solution The pressure generated by the water in the hydrothermal treatment, ΔP is 0.05-15MPa; and (3) performing solid-liquid separation on the mixture obtained by the hydrothermal treatment, and drying the obtained solid phase; The hydrothermal treatment is carried out under the condition that the pressure is P ₀ +ΔP in one of the following ways: The hydrothermal treatment is carried out in the presence of at least one first volatile organic compound, the added amount of the first volatile organic compound is such that the pressure generated by the first volatile organic compound in the hydrothermal treatment is ΔP, and the first volatile organic compound is Volatile organic compounds are selected from C ₁ -C ₁₂ fatty alcohols, C ₂ -C ₁₂ fatty amines, C ₆ -C ₁₂ alkanes and polyethylene glycol with a number average molecular weight of 200-1500; The hydrothermal treatment is carried out in the presence of at least one inert gas in an amount such that the pressure generated by the inert gas during the hydrothermal treatment is ΔP; The hydrothermal treatment is carried out in the presence of at least one second volatile organic compound and at least one inert gas, the total amount of the second volatile organic compound and the inert gas being added so that the second volatile organic compound and the inert gas The total pressure generated by the reactive gas in the hydrothermal treatment is ΔP. 2. The preparation method according to claim 1, wherein the introduction amount of the metal element of the VIB group, the metal element of the VIII group and the metal element as an auxiliary agent on the porous carrier of the molding is such that , based on the total amount of the catalyst, in terms of oxides, the content of the VIB group metal element is 10-50% by weight, the content of the VIII group metal element is 1-10% by weight, and the metal element as the auxiliary agent The content of the molded porous carrier is 0.5-10% by weight, and the content of the shaped porous carrier is 30-88.5% by weight. 3. The preparation method according to claim 1, wherein the second volatile organic compound is selected from C ₁ -C ₁₂ fatty alcohol, C ₂ -C ₁₀ fatty acid, C ₂ -C ₁₂ fatty amine, C ₆ -C ₁₂ alkanes and polyethylene glycol with a number average molecular weight of 200-1500. 4. The preparation method according to claim 3, wherein the second volatile organic compound is selected from C ₁ -C ₈ fatty alcohol, C ₂ -C ₅ fatty acid, C ₂ -C ₇ fatty amine and C ₆ -C ₁₁ alkanes. 5. The preparation method according to claim 1, wherein the first volatile organic compound is selected from C ₁ -C ₈ fatty alcohols, C ₂ -C ₇ fatty amines and C ₆ -C ₁₁ alkanes. 6. The preparation method according to claim 1, wherein ΔP is 0.1-10 MPa. 7. The preparation method according to claim 6, wherein ΔP is 0.2-7 MPa. 8. The preparation method according to claim 1, wherein the manner of introducing at least one metal element as an auxiliary agent on the porous carrier of the molding comprises: In step (1), at least one compound containing the metal element as an auxiliary agent is dissolved in the aqueous solution used to impregnate the shaped porous carrier, P ₀ is the shaped porous carrier, the The compound containing the metal element of Group VIII, the compound containing the metal element of Group VIB, the co-solvent containing or not, the compound containing the metal element as an auxiliary agent, and the water in the aqueous solution Pressure generated during hydrothermal treatment; In step (1), before impregnating the shaped porous carrier with the aqueous solution, at least one metal element as an auxiliary agent is loaded on the shaped porous carrier; and/or mixing at least one compound containing the metal element as an auxiliary agent with the raw materials used to prepare the shaped porous carrier, and shaping the resulting mixture so that the shaped porous carrier contains at least one the metal elements. 9. The preparation method according to claim 1 or 8, wherein the impregnation is excessive impregnation. 10. The preparation method according to any one of claims 1, 2 and 8, wherein the VIB group metal element is molybdenum and/or tungsten, and the VIII group metal element is cobalt and/or or nickel. 11. according to the preparation method described in any one in claim 1,2 and 8, wherein, described metal element as auxiliary agent is selected from the group IIB metal element, the IA group metal element, the IIA group metal element and rare earth metal elements. 12 . The preparation method according to claim 11 , wherein the metal element used as an auxiliary agent is selected from the group consisting of zinc, sodium, potassium, magnesium, calcium, lanthanum and cerium. 13. The preparation method according to any one of claims 1, 2 and 8, wherein the shaped porous carrier is a shaped heat-resistant inorganic oxide. 14. The preparation method according to claim 13, wherein the heat-resistant inorganic oxide is selected from alumina, silicon oxide, titanium oxide, magnesium oxide, silicon oxide-magnesia, silicon oxide-zirconia, silicon oxide - thorium oxide, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-oxide One or more of aluminum-magnesia, and silicon oxide-alumina-zirconia. 15. The preparation method according to claim 1, wherein the temperature of the hydrothermal treatment is 100-200° C., and the time of the hydrothermal treatment is 0.5-36 hours. 16. The preparation method according to claim 1, wherein the preparation method further comprises roasting the dried solid phase. 17. The preparation method according to claim 16, wherein the conditions of the calcination include: the temperature is 350-550°C, and the time is 1-8 hours. 18. The preparation method according to claim 1 or 16, wherein the drying conditions include: a temperature of 100-300° C. and a time of 1-12 hours. 19. The catalyst obtained by the preparation method according to any one of claims 1-18. 20. The application of the catalyst according to claim 19 in hydrocarbon oil hydrotreating. 21. A hydrofinishing process comprising contacting a hydrocarbon oil with the catalyst of claim 19 under hydrofinishing conditions. 22. The method according to claim 21, wherein the hydrofining conditions include: a temperature of 300-400° C.; a gauge pressure of 1.0-8.0 MPa; a liquid hourly volume space velocity of hydrocarbon oil of 0.5 -3.0 hours ^-1 ; the volume ratio of hydrogen to oil is 100-700.