CN105772012A - Hydrofining catalyst, preparation method and application thereof, and hydrofining method - Google Patents

Abstract

The present invention relates to a hydrofinishing catalyst, a preparation method, an application and a hydrofinishing method using the catalyst. The catalyst includes an alumina carrier and an active metal component, based on the weight of the alumina carrier, including 10-35 weight % of a metal component of Group VIB of the Periodic Table of the Elements and 1-9% by weight of a metal component of Group VIII of the Periodic Table of the Elements, each based on the oxide of its corresponding metal element; the preparation method of the catalyst comprises The active metal components are supported on the alumina carrier, treated with organic additives and hydrothermally treated under closed conditions without further treatment. The catalysts of the invention have improved catalytic activity.

Description

Hydrofining catalyst, preparation method and application and hydrofining methods

technical field

The invention relates to a hydrorefining catalyst, and also relates to a preparation method and application of the catalyst, and a hydrorefining method.

Background technique

With the increasingly stringent environmental protection around the world, countries have increasingly stringent requirements on the quality of petroleum fuels. In addition, due to the rapid growth of the market demand for light oil products (that is, petroleum products), especially high-quality clean light oil products, and the world's crude oil is gradually becoming heavier and worse, it is necessary to greatly reduce the impurities in diesel oil and many Remarkably improve the quality of diesel oil by reducing the content of ring aromatics, which has become an urgent problem to be solved by various refineries.

As we all know, hydrogenation technology is one of the important means to reduce the impurity content of oil products and improve the quality of oil products, and its core is hydrogenation catalyst.

At present, the most widely used hydrofining catalyst is based on VIB group (such as Mo or W) metal as the main agent, VIII group (such as Ni or Co) metal as the auxiliary agent, and refractory oxide (such as alumina) as the carrier. type catalyst. The addition of organic additives in the catalyst preparation process has a great impact on the hydrogenation activity. Organic additives can be introduced in different forms at different stages in the catalyst preparation process, and a certain additive will vary depending on the catalyst preparation method. The difference has a greater impact on the structure and activity of the catalyst.

When the catalyst contains organic matter, the method of introducing the organic matter may be to prepare a mixed solution of the organic matter and other components and then impregnate the carrier and dry it, or prepare the organic matter separately into a solution and then impregnate the carrier and dry it.

JP 04-166231 describes a catalyst preparation method, which is characterized in that the carrier is impregnated with a solution containing metal salts of Group VIII and VIB, the impregnated carrier is dried at a temperature not higher than 200°C, and the dried impregnated carrier is contacted with a polyol Finally, it is dried at a temperature not higher than 200°C to make a catalyst.

US 6280610B1 proposes a new hydrogenation catalyst activation method, that is, after impregnation, drying and roasting, impregnate with a solution of an additive (containing at least two hydroxyl groups and 2-10 carbon atoms), and then Carry out drying, the drying condition should make the additive retain more than 50%, preferably can retain 90%, no longer roasting.

EP 0601722 describes a catalyst preparation method, which is characterized in that a γ-alumina carrier is impregnated with an aqueous solution containing VIII and VIB metals, phosphoric acid and glycol, and the impregnated carrier is dried at 100°C to make a catalyst .

CN 101279289A relates to a preparation method of a hydrogenation treatment catalyst. The catalyst carrier is first impregnated with an organic compound solution, and then the active metal is introduced by the impregnation method. During and/or after the introduction of the active metal, the organic compound additive is impregnated again. After the impregnation is completed, it is directly dried, but the roasting process is not carried out. Proprietary organic compounds include alcohols, ethers or sugars. However, it is found through experiments that different preparation processes have a great influence on the activity of the catalyst, and the activity of the catalyst prepared by the above method still needs to be further improved.

The above patents all involve the method of introducing organic matter, which can be prepared as a mixed solution of organic matter and compounds containing other components and then impregnated with the carrier and dried, or after the organic matter is prepared into a solution alone and then impregnated with the carrier and dried The catalyst was introduced by solution impregnation and then dried directly.

Li Juncheng et al. (The 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 A method for preparing the catalyst, 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 The impregnated product was subjected to hydrothermal modification at a temperature of 140-180° C. for 2 hours.

CN201110328381.2 discloses a catalyst and its preparation method and application. The method includes impregnating a formed porous carrier with an aqueous solution, and performing hydrothermal treatment of the impregnated mixture in a closed reactor by adding volatile organic compounds. and inert gas to increase the pressure of the hydrothermal treatment, the pressure of the hydrothermal treatment is P0+ΔP, wherein, P0 is a porous carrier, a compound of a metal of Group VIB, a compound containing a metal of Group VIII, an auxiliary compound with or without Solvents, and water are under pressure during hydrothermal treatment. The total added amount of the volatile organic compound and the inert gas makes the total pressure generated by the volatile organic compound and the inert gas in the hydrothermal treatment be ΔP, and ΔP is 0.05-15 MPa.

The above two literatures and patents both deal with impregnating the mixture of active metals and are methods of loading metals. CN 103071508A increases the pressure of hydrothermal treatment by adding volatile organic compounds and inert gases. Since most of the impregnation solutions of active metals are acidic, such as molybdenum and nickel/or cobalt solutions, phosphoric acid is usually added to form a stable solution. Its pH value is less than 2; the pH value of nickel nitrate and ammonium metatungstate solutions commonly used in nickel-tungsten catalysts is also around 2, and the carrier will be eroded under the action of acid and hydrothermal. For related discussions, see the literature Chemical treatment ofγ- Al ₂ O ₃ and its influence on the properties of Co-based catalysts for Fischer–Tropsch synthesis, Applied Catalysis A: General 243 (2003) 121–133.

Therefore, it is necessary to develop a catalyst with higher activity.

Contents of the invention

The inventor found through a large number of experiments: in the oil refining process, impregnating the dried catalyst precursor with a solution of organic additives, and then carrying out hydrothermal treatment to the mixture of impregnated organic additives under airtight conditions can improve the catalytic performance of the catalyst. active.

In view of this, the object of the present invention is to provide a hydrofinishing catalyst with higher catalytic activity, the preparation and use of the catalyst, and a hydrofinishing method.

According to a first aspect of the present invention, there is provided a hydrorefining catalyst comprising an alumina support and an active metal component, based on the weight of the alumina support, comprising

10-35% by weight of a metal component of Group VIB of the Periodic Table of the Elements and 1-9% by weight of a metal component of Group VIII of the Periodic Table of the Elements, each based on the oxide of the highest valence state of the metal of its corresponding metal element count;

Wherein, described catalyst is made by following method:

(1) The porous catalyst carrier is loaded with an active metal component, and the catalyst precursor is obtained after drying;

(2) impregnating the dried catalyst precursor obtained in step (1) with an organic auxiliary agent selected from organic polyols, sugars, ethers or any mixture thereof to obtain an impregnation mixture;

(3) The impregnated mixture obtained in step (2) is subjected to hydrothermal treatment under airtight conditions without further treatment, and the catalyst is obtained after drying (ie without roasting).

In a preferred embodiment of the hydrofinishing catalyst of the present invention, the catalyst has a specific surface area of 140 to 210 m ² /g, preferably 150 to 200 m ² /g, more preferably 160 to 190 m ² /g, most preferably 170 to 180 m ² /g; the pore volume is 0.25 to 0.55 ml/g, preferably 0.30 to 0.50 ml/g, most preferably 0.35 to 0.45 ml/g.

In a preferred embodiment of the hydrotreating catalyst of the present invention, the pore volume distribution of the catalyst is: the pore volume with a pore diameter of <4 nm accounts for 5% to 20% of the total pore volume, preferably 6% to 18%, more preferably Preferably 8% to 12%, most preferably 10% to 12%; the pore volume with a pore diameter of 4 to 10 nm accounts for 45% to 90% of the total pore volume, preferably 55% to 85%, most preferably 65% to 80%; the pore volume with a pore diameter of 10 to 80 nm accounts for 5% to 35% of the total pore volume, preferably 10% to 30%, more preferably 10% to 25%, most preferably 12% to 25%.

In a preferred embodiment of the hydrorefining catalyst of the present invention, the Group VIB metal is selected from molybdenum, tungsten or mixtures thereof and the Group VIII metal is selected from cobalt, nickel or mixtures thereof.

In a preferred embodiment of the hydrofinishing catalyst of the present invention, said catalyst further comprises 0-5% by weight of phosphorus, fluorine, titanium, boron or mixtures thereof, based on the weight of the alumina support.

According to a second aspect of the present invention, there is also provided a method for preparing a hydrotreating catalyst, the method comprising the following steps:

(1) The porous catalyst support is loaded with 10-35% by weight of a metal component of Group VIB of the Periodic Table of the Elements and 1-9% by weight of a metal component of Group VIII of the Periodic Table of the Elements, each based on its corresponding metal element In terms of oxides in the highest valence state of the metal, a catalyst precursor is obtained after drying;

(2) impregnating the dried catalyst precursor in step (1) with an organic auxiliary agent selected from organic polyols, sugars, ethers or any mixture thereof to obtain an impregnation mixture;

(3) The impregnated mixture obtained in step (2) is subjected to hydrothermal treatment under airtight conditions without further treatment, and the catalyst is obtained after drying (ie without roasting).

According to the third aspect of the present invention, there is provided the use of the above-mentioned catalyst for hydrotreating refined oil products.

According to a fourth aspect of the present invention, there is provided a method for hydrofinishing of oil (preferably Fischer-Tropsch oil, that is, the oil obtained by Fischer-Tropsch reaction), which comprises: sulfurizing the above-mentioned hydrofinishing catalyst; The sulfurized catalyst is contacted with Fischer-Tropsch oil in a fixed-bed reactor, wherein the reaction temperature for hydrofining is 150-300°C, preferably 200-250°C; the reaction pressure is 4-8.5MPa, preferably 5-7MPa; volume space velocity 0.5-3h ^-1 , preferably 1-2h ^-1 .

The organic compound used in the method of the present invention is the same as that of the prior art, but the prior method adopts solution impregnation to introduce the catalyst, and then directly dries, while the method of the present invention performs hydrothermal treatment on the mixture impregnated with organic matter under airtight conditions. The hydrothermal treatment of the present invention treats the catalyst in a neutral environment, which can effectively avoid the erosion of the catalyst. The experimental results show that the surface properties of the alumina carrier are further improved after the organic matter and hydrothermal treatment are carried out in a closed container with a certain temperature and pressure, so that the active components are evenly distributed on the carrier, and the organic additives are strengthened in the porous medium. loading, thereby improving the catalytic activity of the catalyst. The method of the invention does not need to greatly adjust the original preparation process, has simple operation process and is suitable for industrial application.

detailed description

In the present invention, unless otherwise stated, all operations are carried out at room temperature and normal pressure.

The invention provides a hydrorefining catalyst, comprising an alumina support and an active metal component, based on the weight of the alumina support, comprising

10-35% by weight of a metal component of Group VIB of the Periodic Table of the Elements and 1-9% by weight of a metal component of Group VIII of the Periodic Table of the Elements, each based on the oxide of the highest valence state of the metal of its corresponding metal element count;

It should be noted here that, before high-temperature calcination, the metal components in the catalyst can exist in any reasonable valence state. For convenience only, when defining the content of the metal component, it is converted into the content of the metal oxide in the highest valence state of the metal;

Wherein, described catalyst is made by following method:

(1) The porous catalyst carrier is loaded with an active metal component, and the catalyst precursor is obtained after drying;

(2) impregnating the dried catalyst precursor in step (1) with an organic auxiliary agent selected from organic polyols, sugars, ethers or any mixture thereof to obtain an impregnation mixture;

(3) The impregnated mixture obtained in step (2) is subjected to hydrothermal treatment under airtight conditions without further treatment, and the catalyst is obtained after drying (ie without roasting).

In actual operation, a high-temperature calcination step may also be included after step (3). In the calcined catalyst, its metal component is in a stable oxidation state, usually its highest valence state.

In a preferred embodiment of the present invention, the catalyst has a specific surface area of 140 to 210 m ² /g, preferably 150 to 200 m ² /g, more preferably 160 to 190 m ² /g, most preferably 170 to 180 m ² /g; The pore volume is 0.25 to 0.55 ml/g, preferably 0.30 to 0.50 ml/g, most preferably 0.35 to 0.45 ml/g.

In a preferred embodiment of the present invention, the pore volume distribution of the catalyst is: the pore volume with a pore diameter of <4 nm accounts for 5% to 20% of the total pore volume, preferably 6% to 18%, more preferably 8% to 12%, most preferably 10% to 12%; the pore volume with a pore diameter of 4 to 10 nm accounts for 45% to 90% of the total pore volume, preferably 55% to 85%, most preferably 65% to 80%; the pore diameter The pore volume of 10 to 80 nm accounts for 5% to 35% of the total pore volume, preferably 10% to 30%, more preferably 10% to 25%, most preferably 12% to 25%.

In a preferred embodiment of the present invention, the Group VIB metal is selected from molybdenum, tungsten or a mixture thereof; the Group VIII metal is selected from cobalt, nickel or a mixture thereof.

In a preferred embodiment of the present invention, the catalyst further comprises 0-5% by weight of phosphorus, fluorine, titanium, boron or mixtures thereof, based on the weight of the alumina support.

In a more preferred embodiment of the present invention, the catalyst further includes 0-5% by weight of elemental phosphorus, based on the weight of the catalyst support.

The present invention also provides a method for preparing a hydrorefining catalyst, which comprises the following steps:

(1) The porous catalyst carrier is loaded with 10-35% by weight of a metal of Group VIB of the Periodic Table of the Elements and 1-9% by weight of a metal of Group VIII of the Periodic Table of the Elements, each based on the highest metal valence of its corresponding metal element In terms of oxides in the state, the catalyst precursor is obtained after drying;

(2) impregnating the dried catalyst precursor in step (1) with an organic auxiliary agent selected from organic polyols, sugars, ethers or any mixture thereof to obtain an impregnation mixture;

(3) The impregnated mixture obtained in step (2) is subjected to hydrothermal treatment under airtight conditions without further treatment, and the catalyst is obtained after drying (ie without roasting).

In a preferred embodiment of the present invention, the porous carrier described in step (1) is determined by those skilled in the art based on common knowledge according to the needs of use. Generally prepared from refractory oxides, typically alumina, silica-alumina, silica, zeolite, titania, zirconia, boria and/or mixtures thereof for hydrotreating catalysts, preferably alumina.

In a preferred embodiment of the present invention, in step (1), the molding method of the carrier can be drop ball molding, extrusion molding, tablet molding, etc., preferably extrusion molding.

In a preferred embodiment of the present invention, in step (1), the shape of the carrier can be spherical, strip (including cylindrical or shaped strips such as clover), sheet and so on.

In a preferred embodiment of the present invention, in step (1), the shaped carrier is dried and calcined, the drying temperature is 40-180°C, preferably 100-150°C, and the drying time is 0.5-24 hours, preferably 1-8 hours; the calcination temperature is 400-700°C, preferably 450-650°C, and the calcination time is 0.5-24 hours, preferably 1-8 hours.

In one embodiment of the invention, the Group VIB metal is selected from molybdenum, tungsten or mixtures thereof and the Group VIII metal is selected from cobalt, nickel or mixtures thereof.

The method of adding the active metal component is well known to those skilled in the art, and may be impregnation, including saturation impregnation, spray impregnation and excess impregnation. The metal sources used are their suitable mineral or organic acid salts. Including but not limited to their nitrates, acetates, oxalates, chlorides and/or sulfates.

In a preferred embodiment of the present invention, in step (1), the carrier is loaded with active metal components and then dried at a drying temperature below 300°C, preferably 100-300°C, more preferably 100-200°C , drying time is 1-24 hours.

In a preferred embodiment of the present invention, the organic additives in step (2) include, for example, one or more of alcohols, ethers or sugars. For example, suitable alcohols may include one or more of ethylene glycol, propylene glycol, or glycerin; suitable ethers may include diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, or tetraethylene glycol; One or more; suitable sugars include one or more of monosaccharides or polysaccharides. Wherein, the monosaccharide may include one or more of glucose or fructose, and the polysaccharide may include one or more of lactose, maltose or sucrose.

In one embodiment of the present invention, in step (2), the weight ratio of the organic auxiliary agent to the weight of the catalyst as a whole is 3-20%, preferably 5-15%, more preferably 6-10%.

In one embodiment of the present invention, the amount of the organic additive introduced is such that the molar ratio of the organic additive to the active metal component calculated as oxide in the catalyst is 0.03-2, preferably 0.08-1.5.

In a preferred embodiment of the invention, the organic compound has a boiling point of 100-400°C, preferably 150-350°C. The organic compounds used in the present invention are commonly used substances in the field and are well known to those skilled in the art. The present invention enables the catalyst to have more outstanding performance through an optimized preparation process.

In a preferred embodiment of the present invention, the temperature for the treatment under airtight conditions described in step (3) is room temperature-250°C, preferably 40-250°C, more preferably 80-220°C, and very preferably 120-250°C. 200°C, most preferably 140-180°C; the hydrothermal treatment time is 0.03-24 hours, preferably 1-12 hours.

The solid phase treated under airtight conditions is dried, wherein the drying temperature can be below 300°C, preferably 100-300°C, more preferably 100-200°C, and the drying time is 1-24 hours.

In one embodiment of the present invention, in step (1) and (2) in the step of preparing carrier and catalyst precursor, add inorganic auxiliary agent, described inorganic auxiliary agent is selected from phosphorus, fluorine, titanium, boron, or its mixture.

The present invention also provides the use of the above-mentioned catalyst for hydrotreating refined oil products.

The present invention also provides a method for hydrofinishing of oil (preferably Fischer-Tropsch oil, i.e. the oil obtained by Fischer-Tropsch reaction), which comprises: sulfurizing the above-mentioned Fischer-Tropsch oil hydrotreating catalyst; The catalyst and Fischer-Tropsch oil are contacted in a fixed-bed reactor, wherein the reaction temperature for hydrofining is 150-300°C, preferably 200-250°C; the reaction pressure is 4-8.5MPa, preferably 5-7MPa; the volume space velocity is 0.5 -3h ^-1 , preferably 1-2h ^-1 .

Other conditions in catalyst preparation can be determined according to the conventional knowledge in the art.

Without being bound by any theory, it is believed that the improvement of the catalytic activity of the hydrocarbon oil hydrotreating catalyst of the present invention is based on the following reasons: the aluminum oxide of the loaded metal component is impregnated with an organic auxiliary agent after drying, and then in a closed room with a certain temperature The hydrothermal treatment of organic matter in a container with high pressure further improves the surface properties of the alumina carrier, makes the active components evenly distributed on the carrier, and strengthens the loading of organic additives in the porous medium, thereby improving the catalytic activity of the catalyst; In addition, the hydrothermal treatment is carried out in a neutral environment, which can effectively avoid the erosion of the catalyst.

The features of the present invention are further described below through examples, but these examples cannot limit the present invention.

Example

The following examples are only exemplary, and unless otherwise specified, the parts and ratios in the present invention refer to parts by weight and ratios by weight.

The raw materials used in the examples are described as follows:

Fischer-Tropsch oil: provided by Shenhua Ordos Coal-to-Liquid Plant, see Table 2 for properties;

Aluminum hydroxide powder: PURAL SB, purchased from Sasol company;

Molybdenum trioxide: purchased from Sinopharm Chemical Reagent Co., Ltd.;

Basic nickel carbonate: purchased from Sinopharm Chemical Reagent Co., Ltd.

The equipment used in the embodiment is described as follows:

Kneader: Model MZ05TWIN "Z" BLADED Mixer, purchased from Winkworth Company, UK;

Extrusion machine: the model is B-B Gun, purchased from BONNOT in the United States;

High-pressure reactor: the model is Parr 4568, purchased from U.S. Parr Company;

Specific surface area tester: the model is TriStar II 3020, purchased from Micromeritics, USA.

Analytical method:

The BET specific surface area and pore volume and pore size distribution were measured by a TriStar II 3020 nitrogen adsorption instrument produced by Micromeritics, USA. The BET equation was used to calculate the specific surface area of the sample, and the BJH model was used to calculate the pore volume and pore size distribution from the desorption isotherm.

Preparation Example

Example 1

(1) Knead 2000g of aluminum hydroxide powder (SB powder, purchased from Sasol Company), 40g of 65% nitric acid and an appropriate amount of water in a kneader. After mixing and kneading, use an extruder to extrude into a cylindrical φ3mm×6mm strip, and dry the extruded wet strip at 120°C for 4 hours, and then bake it at 550°C for 4 hours to obtain the carrier S1.

(2) Take 2.45g 85% phosphoric acid and add it to an appropriate amount of water, then add the phosphoric acid solution to 19.7g molybdenum trioxide and 5.5g basic nickel carbonate (NiCO ₃ 2Ni(OH) ₂ 4H ₂ O), heat Continue heating until the precipitate is completely dissolved, then impregnate 75.5g S-1 carrier, impregnate at room temperature for 2h, and dry at 120°C for 6h to obtain catalyst precursor Z-1.

(3) Add 5.6 g of ethylene glycol into an appropriate amount of water, impregnate catalyst precursor Z-1, impregnate at room temperature for 2 hours, place the impregnated mixture in a high-pressure reactor, and carry out hydrothermal treatment. The conditions for hydrothermal treatment include: temperature 120°C for 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature, and dried at 160° C. for 6 hours to obtain catalyst C-1.

Example 2

(1)-(2) are the same as steps (1)-(2) in Example 1.

(3) Add 5.6 g of ethylene glycol into an appropriate amount of water, impregnate catalyst precursor Z-1, impregnate at room temperature for 2 hours, place the impregnated mixture in a high-pressure reactor, and carry out hydrothermal treatment. The conditions for hydrothermal treatment include: temperature 140°C for 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature, and dried at 160° C. for 6 hours to prepare catalyst C-2.

Example 3

(1)-(2) are the same as steps (1)-(2) in Example 1.

(3) Add 5.6 g of ethylene glycol into an appropriate amount of water, impregnate catalyst precursor Z-1, impregnate at room temperature for 2 hours, place the impregnated mixture in a high-pressure reactor, and carry out hydrothermal treatment. The conditions for hydrothermal treatment include: temperature 180°C for 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature, and dried at 160° C. for 6 hours to prepare catalyst C-3.

Example 4

(1)-(2) are the same as steps (1)-(2) in Example 1.

(3) Add 5.6 g of ethylene glycol into an appropriate amount of water, impregnate catalyst precursor Z-1, impregnate at room temperature for 2 hours, place the impregnated mixture in a high-pressure reactor, and carry out hydrothermal treatment. The conditions for hydrothermal treatment include: temperature at 200°C for 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature and dried at 160° C. for 6 hours to obtain catalyst C-4.

Example 5

(1)-(2) are the same as steps (1)-(2) in Example 1.

(3) Take 13.6 g of triethylene glycol and add it to an appropriate amount of water, impregnate the catalyst precursor Z-1, and impregnate it at room temperature for 2 hours. The mixture obtained by impregnating is placed in a high-pressure reactor for hydrothermal treatment. The conditions for hydrothermal treatment include: temperature 150°C for 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature, and dried at 160° C. for 6 hours to prepare catalyst C-5.

Comparative Example 1

(1)-(2) are the same as steps (1)-(2) in Example 1.

(3) Add 5.6 g of ethylene glycol into an appropriate amount of water, impregnate catalyst precursor Z-1 for 2 hours at room temperature, and dry at 160° C. for 6 hours to prepare catalyst D-1.

Comparative Example 2

(1) is the same as step (1) in Example 1.

(2) Take 2.45g 85% phosphoric acid and add it to an appropriate amount of water, then add the phosphoric acid solution to 19.7g molybdenum trioxide and 5.5g basic nickel carbonate (NiCO ₃ 2Ni(OH) ₂ 4H ₂ O), heat Bring to a slight boil and continue heating until the precipitate is completely dissolved, then add 5.6g of ethylene glycol into the solution, then impregnate 75.5g of S-1 carrier, impregnate at room temperature for 2 hours, and place the impregnated mixture under high pressure reaction In the still, carry out hydrothermal treatment, the condition of hydrothermal treatment comprises: temperature is 140 ℃, time is 4 hours. The mixture obtained by hydrothermal treatment was cooled to room temperature, and dried at 160° C. for 6 hours to prepare catalyst D-2.

Catalysts C-2 and D-2 prepared in Example 2 and Comparative Example 2 were tested for BET specific surface area and pore size distribution, and the test results are listed in Table 1 below.

Table 1 BET specific surface area and pore size distribution test results

Table 1 shows the test results of the catalysts prepared under the same hydrothermal treatment conditions. Among them, in Comparative Example 2, the carrier is impregnated with an active metal impregnating solution in the presence of organic additives and then directly subjected to hydrothermal treatment, so the hydrothermal environment is strongly acidic, while the method of the present invention dries the carrier loaded with active metal Finally, the catalyst precursor is obtained, impregnated with an organic auxiliary agent, and then the mixture impregnated with the organic auxiliary agent is subjected to hydrothermal treatment under airtight conditions, so the hydrothermal treatment of the present invention is carried out in a neutral environment. As can be seen from Table 1, when the hydrothermal treatment conditions are the same, compared with the catalyst D-2 prepared by the method of Comparative Example 2, the catalyst C-2 prepared by the method of the present invention has larger specific surface area and pore volume, and the pore Volume distribution is better.

The following examples serve to illustrate the activity of the catalysts according to the invention and the hydrofinishing process.

Experimental example

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

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

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

Based on the hydrodeoxygenation activity of catalyst D-1 (denoted as k(D-1) _HDO ), the relative hydrodeoxygenation activity of catalyst X is calculated by the following formula:

Catalyst evaluation was carried out in a 30ml fixed-bed reactor, and the feedstock oil used was a Fischer-Tropsch synthetic light oil, whose properties are shown in Table 2. Before formal feeding, the catalyst is sulfurized with kerosene containing 2% carbon disulfide. After cutting the raw materials, the reaction temperature was 210°C, the reaction pressure was 6.4MPa, and the volume space velocity was 1.5h ^-1 . The results are listed in Table 3.

Table 2 LO properties of synthetic light oil

parameter analyze data Density at 20℃/(g/cm ³ ) 0.7695 Acid value/(mgKOH/g) 9.4

Bromine value/(gBr/100g) 10.5 Oxygen content/% 2.2 Sulfur content/(μg/g) 7.2 Nitrogen content/(μg/g) 4.8 Distillation range (D86)/℃ IBP/5% (initial boiling point) 92/111 10%/30% 130/187 50%/70% 239/273 90%/95% 324/350 FBP (final boiling point) 374

Table 3 Catalyst evaluation results

catalyst relative hydrodeoxygenation activity C-1 125 C-2 130 C-3 120 C-4 115 C-5 135 D-1 100 D-2 110

In table 3, through the contrast of embodiment and comparative example 1, it can be found that: compared with the method of directly drying after solution impregnation, the hydrothermal treatment of organic matter in a closed container with a certain temperature and pressure of the present invention is further improved. The surface performance of the alumina carrier is improved, the active components are evenly distributed on the carrier, and the loading of the organic auxiliary agent in the porous medium is strengthened, thereby improving the catalytic activity of the catalyst.

Through the comparison of Examples and Comparative Example 2, it can be found that: Comparative Example 2 uses the active metal impregnating solution to impregnate the carrier in the presence of organic additives and then directly conducts hydrothermal treatment, so the hydrothermal environment is strongly acidic, while this In the method of the invention, the catalyst precursor is obtained by drying the carrier loaded with active metals, impregnated with an organic auxiliary agent, and then performing hydrothermal treatment on the mixture impregnated with the organic auxiliary agent under airtight conditions, so the hydrothermal treatment of the present invention can be carried out in a neutral environment. It can effectively avoid the erosion of the catalyst and improve the activity of the catalyst.

The result of table 3 shows, when adopting hydrorefining catalyst C-1 to C-5 of the present invention to carry out hydrotreating to Fischer-Tropsch oil, its activity is obviously better than the activity of catalyst D-1 and D-2 of comparative example .

In summary, the catalyst of the present invention impregnates the dried catalyst precursor with an organic auxiliary agent, and then performs hydrothermal treatment on the mixture impregnated with the organic auxiliary agent under airtight conditions, which can improve the catalytic activity of the catalyst.

It should be understood that the above embodiments of the invention are only exemplary, and are not intended to limit the present invention in any form. Those skilled in the art can make changes to the above embodiments within the scope of the present invention without departing from the gist of the present invention. Or modification, all content that does not depart from the claims of the present invention all fall within the protection scope of the present invention.

Claims (16)

1. a Hydrobon catalyst, including alumina support and active metal component, based on The weight of alumina support, including

A kind of periodic table of elements vib metals component of 10-35 weight % and the one of 1-9 weight % Planting periodic table of elements group VIII metal component, the metal being each based on its respective metal element is the highest The oxide meter of valence state；

Wherein, described catalyst comprises the following steps:

(1) by porous catalyst carrier supported active metals component, before obtaining catalyst after drying Body；

(2) with having machine aided selected from organic polyhydric alcohol, sugar, ether or their a kind of any mixture The dried catalyst precarsor of agent impregnation steps (1), obtains dip compound；

(3) dip compound step (2) obtained is the most in confined conditions Carry out hydrothermal treatment consists, the most i.e. obtain catalyst.

2. the catalyst of claim 1, it is characterised in that the specific surface area of described catalyst is 140 to 210m²/ g, preferably 150 to 200m²/ g, more preferably 160 to 190m²/ g, most preferably 170 to 180m²/g；Pore volume is 0.25 to 0.55ml/g, preferably 0.30 to 0.50ml/g, optimum Select 0.35 to 0.45ml/g.

3. the catalyst of claim 1, it is characterised in that the pore volume distribution of described catalyst For: aperture be < pore volume of 4nm accounts for the 5% to 20% of total pore volume, preferably 6% to 18%, more preferably 8% to 12%, most preferably 10% to 12%；Aperture is 4 to 10nm Pore volume account for the 45% to 90% of total pore volume, preferably 55% to 85%, most preferably 65% to 80%；Aperture is that the pore volume of 10 to 80nm accounts for the 5% to 35% of total pore volume, excellent Elect 10% to 30% as, more preferably 10% to 25%, most preferably 12% to 25%.

4. the catalyst of claim 1, it is characterised in that vib metals selected from molybdenum, tungsten or Its mixture, group VIII metal is selected from cobalt, nickel or its mixture.

5. the catalyst of claim 1, it is characterised in that described catalyst also includes 0-5 weight The amount phosphorus of %, fluorine, titanium, boron or its mixture, weight meter based on alumina support.

6. the method preparing Hydrobon catalyst, it comprises the following steps:

(1) alumina catalyst carrier is loaded a kind of periodic table of elements of 10-35 weight % Group vib metal component and a kind of periodic table of elements group VIII metal component of 1-9 weight %, It is each based on the oxide meter of the metal highest price state of its respective metal element, is catalyzed after drying Agent precursor；

(2) with having machine aided selected from organic polyhydric alcohol, sugar, ether or their a kind of any mixture The dried catalyst precarsor that agent impregnation steps (1) obtains, obtains dip compound；

(3) dip compound step (2) obtained is the most in confined conditions Carry out hydrothermal treatment consists, the most i.e. obtain catalyst.

7. the method for claim 6, it is characterised in that described organic polyhydric alcohol can include second two One or more in alcohol, propylene glycol or glycerol；Ether includes diethylene glycol, dipropylene glycol, three sweet One or more in alcohol, three butanediols or tetraethylene glycol (TEG)；Sugar include monosaccharide or the one of polysaccharide or Multiple.

8. the method for claim 6 or 7, it is characterised in that described monosaccharide includes glucose or fruit One or more of sugar；Described polysaccharide can include one or more of lactose, maltose or sucrose.

9. the method for claim 6, it is characterised in that the introduction volume of organic additive makes in catalyst The mol ratio of organic additive and the active metal component counted with oxide, as 0.03-2, is preferably 0.08-1.5。

10. the method for claim 6, it is characterised in that described processes in confined conditions Temperature be room temperature-250 DEG C, preferably 40-250 DEG C, more preferably 80-220 DEG C, highly preferred be 120-200 DEG C, most preferably 140-180 DEG C；The time of hydrothermal treatment consists is 0.3-24 hour, preferably For 1-12 hour.

The method of 11. claim 6, it is characterised in that step (1) and the described of (3) do The baking temperature of dry step can be less than 300 DEG C, preferably 100-300 DEG C, more preferably 100-200 DEG C, drying time is 1-24 hour.

The method of 12. claim 6, it is characterised in that in step (2), the weight of organic additive It is 3-20%, preferably 5-15%, more preferably 6-10% that amount accounts for the ratio of the overall weight of catalyst.

The method of 13. claim 6, it is characterised in that prepare carrier and catalysis in step (1) Adding inorganic assistant in the step of agent precursor, described inorganic assistant is selected from phosphorus, fluorine, titanium, boron, Or its mixture.

Catalyst any one of 14. claim 1-5 is for the purposes of hydrofinishing oil product.

The method that 15. 1 kinds of oil hydrogenations are refined, comprising: urging any one of claim 1-5 Agent vulcanizes；Vulcanized catalyst is contacted in fixed bed reactors with Fischer-Tropsch oil, its In hydrorefined reaction temperature be 150-300 DEG C, preferably 200-250 DEG C；Reaction pressure is 4-8.5 MPa, preferably 5-7MPa；Volume space velocity is 0.5-3h^-1, preferably 1-2h^-1。

The method that the oil hydrogenation of 16. claim 15 is refined, it is characterised in that described oil product is Fischer-Tropsch oil.