WO2021110086A1

WO2021110086A1 - Method for removing dissolved oxygen in oil product

Info

Publication number: WO2021110086A1
Application number: PCT/CN2020/133551
Authority: WO
Inventors: 王玉; 刘冬; 蔡吉乡; 许正跃; 许艺; 凌正国; 周立群; 顾文忠; 曹晶; 耿祖豹; 施祖伟; 邱祥涛; 赵宏仪
Original assignee: 中国石化集团金陵石油化工有限责任公司; 中国石油化工股份有限公司
Priority date: 2019-12-03
Filing date: 2020-12-03
Publication date: 2021-06-10
Also published as: CN112899012A; CN114616310A; CN112899012B; KR20220106832A; CN114616310B

Abstract

A method for removing dissolved oxygen in an oil product, comprising the following steps: 1) enabling an oil product and hydrogen to mix, the volume ratio of the hydrogen and oil product preferably being 1.0-4.0; and 2) enabling the mixture from step 1) to make contact with an oxygen-removing catalyst to carry out a hydrogenation and deoxygenation reaction, the catalyst comprising a carrier, the carrier comprising a first carrier, a second carrier that is coated on an outer surface of the first carrier, and a catalytically active component that is loaded on the second carrier, the porosity of the first carrier being ≤35%, and the catalytically active component preferably comprising at least one IUPAC Group 8-14 metal. The method has good deoxygenation stability, a long operation cycle, and the removal rate of trace dissolved oxygen in oil can reach over 95%.

Description

Method for removing dissolved oxygen in oil

Cross-references to related applications

This application claims the priority of the patent application filed on December 3, 2019, with the application number 201911223397.X, titled "a method for removing dissolved oxygen in oil", the content of which is incorporated herein by reference in its entirety. .

Technical field

This application relates to a method for removing dissolved oxygen in a liquid, and specifically relates to a method for removing dissolved oxygen from oil products through a hydrogenation and deoxygenation reaction.

Background technique

Many industrial processes include deoxygenation processes, such as the treatment of boiler water and oil field water and the purification of high-purity gases, propylene, synthesis gas and other gases. The methods of deaeration mainly include physical deaeration and chemical deaeration. The physical methods include: vacuum deaeration, atmospheric thermal deaeration, rectification, adsorption, membrane separation, desorption and deaeration, etc., and chemical deaeration. It is divided into chemical absorption (adsorption) deoxygenation, the use of oxygen and activated carbon and other deoxidizers to generate carbon dioxide deoxygenation, the use of variable valence oxide reducing agents to deoxygenate, and catalytic hydrogenation and deoxygenation.

In the petrochemical industry, straight-run oils such as kerosene are often dissolved in trace oxygen during storage and transportation. Dissolved oxygen will react with unstable hydrocarbons in kerosene at high temperatures to form oxidized colloids, which can easily cause equipment blockage. Chinese patent CN102876375B discloses a catalytic cracking gasoline pretreatment method, which enters the oxygen-containing FCC gasoline into a gas stripping tower and uses hydrogen for gas stripping; the obtained gas enters a gas purification and deoxygenation reactor, and contacts with catalyst I to purify the gas to remove oxygen ; The obtained liquid is mixed with the purified hydrogen and then enters the reactor, contacts with the catalyst II, and removes the diolefins and remaining oxygen in the gasoline. The oxygen-containing FCC gasoline first enters the stripping tower for gas stripping to remove the dissolved oxygen in the gasoline; the deoxygenated FCC gasoline then hydrogenates the diolefins at a lower temperature to remove the oxygen dissolved in the gasoline The step-by-step removal of diolefins and diolefins can effectively prevent the recombination of diolefins and oxygen during the hydrogenation process. However, the deoxygenation efficiency of gasoline in this patent is still low.

Summary of the invention

The purpose of this application is to provide a catalytic hydrogenation and deoxygenation method for removing dissolved oxygen in oil products. By adopting a catalyst with a double-layer carrier structure, the deoxygenation efficiency can be improved and the operation period is long.

In order to achieve the above objective, this application provides a method for removing dissolved oxygen in oil, which includes the following steps:

1) Mixing oil and hydrogen, preferably the volume ratio of the mixing of hydrogen and oil is 1.0-4.0; and

2) The mixture from step 1) is contacted with a deoxygenation catalyst for hydrogenation and deoxygenation reaction,

Wherein, the catalyst includes a carrier, the carrier includes a first carrier, a second carrier coated on the outer surface of the first carrier, and a catalytically active component supported on the second carrier, wherein the first carrier The porosity is less than or equal to 35%.

Preferably, the catalytically active component of the oxygen scavenging catalyst contains at least one IUPAC Group 8-14 metal.

Preferably, the ratio of the thickness of the second carrier of the oxygen scavenging catalyst to the effective diameter of the first carrier is between 0.01 and 0.2.

Preferably, the pore distribution curve of the second carrier of the oxygen scavenging catalyst has two pore distribution peaks, wherein the pore diameter corresponding to the peak of the first pore distribution peak is in the range of 4-80 nm, preferably in the range of 8-50 nm, more It is preferably in the range of 10-50 nm, and the pore diameter corresponding to the peak of the second pore distribution peak is in the range of 100-8000 nm, preferably in the range of 200-3000 nm, more preferably in the range of 200-1000 nm.

The catalyst used in the present application is formed by selecting different substances to form a catalyst carrier which contains a first carrier and a second carrier coated on the outer surface of the first carrier with different internal and external properties. The catalytic reaction active centers are distributed on the second carrier in the outer layer. , Which greatly shortens the diffusion distance of reactants and products in the catalyst. In addition, by adjusting the pore structure of the second carrier, two different types of pores with different pore diameters are provided. The first type of pores provides the high specific surface area and active centers required for the reaction, thereby improving the reaction activity of the catalyst; The second-type hole is used as the diffusion channel of the reactant and the product, which greatly improves the diffusion process of the reactant and the product, makes the oxygen removal reaction more thorough, and greatly improves the oxygen removal efficiency. Especially for kerosene and other oils with a long carbon chain (number of carbon atoms ≥ 10), the presence of the second type of pores with large pore diameters enables the reactants and products to diffuse rapidly, and the residence time inside the catalyst is short, and the pores of the catalyst are not easily blocked. , The carbon deposit situation is improved, and the catalyst life is significantly prolonged.

The catalyst used in this application still has high activity at low temperature and pressure, and can maintain high reaction activity for a long time. It can effectively remove the dissolved trace oxygen in the oil, and it can prevent the trace oxygen in the oil. The removal rate can reach more than 95%, thereby significantly improving the coking and clogging of oil products in the subsequent production process, and achieving the goal of cleaner production. This application is simple to operate, and is particularly suitable for removing trace oxygen dissolved in straight-run kerosene oil products.

Description of the drawings

Fig. 1 is a pore distribution curve of the second carrier of the catalyst prepared in Example 1 of the present application.

Detailed ways

Hereinafter, the present invention will be further described in detail through specific embodiments. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, but do not limit the present invention in any way.

Any specific numerical value (including the end point of the numerical range) disclosed in this article is not limited to the precise value of the numerical value, but should be understood to also cover values close to the precise value, for example, within the range of ±5% of the precise value All possible values. Moreover, for the disclosed numerical range, between the endpoints of the range, between the endpoints and the specific point values in the range, and between the specific point values can be combined arbitrarily to obtain one or more new Numerical ranges, these new numerical ranges should also be regarded as specifically disclosed herein.

Unless otherwise specified, the terms used herein have the same meanings as commonly understood by those skilled in the art. If the terms are defined herein and their definitions differ from those commonly understood in the art, the definitions herein shall prevail.

In this application, the "pore distribution curve" refers to the use of mercury intrusion method (ISO 15901-1) to characterize porous materials, the obtained abscissa is the pore size, the coordinate scale is the logarithmic scale, and the ordinate is the pore volume vs. The differential curve of the logarithm of the pore size is, for example, the curve shown in FIG. 1.

In this application, the hole corresponding to the first hole distribution peak on the hole distribution curve is called the first type hole, and the hole corresponding to the second hole distribution peak on the hole distribution curve is called The second type of hole. Correspondingly, the specific pore volume of the pores corresponding to the first pore distribution peak may be referred to as the specific pore volume of the first type of pores, and the specific pore volume of the pores corresponding to the second pore distribution peak may be referred to as the second type of pore. The specific pore volume.

In this application, the "specific pore volume" is based on the quality of the corresponding carrier and can be measured by mercury intrusion method (ISO 15901-1).

In this application, the "maximum pore size distribution" refers to the pore size corresponding to the peak of the corresponding pore distribution peak. For example, the maximum pore size distribution of the first type of pores refers to the peak corresponding to the first pore distribution peak. The pore size, and the maximum value of the pore size distribution of the second type of pores refers to the pore size corresponding to the peak of the second pore distribution peak.

In this application, except for the content clearly stated, any matters or matters not mentioned are directly applicable to those known in the art without any changes. Moreover, any implementation described herein can be freely combined with one or more other implementations described herein, and the technical solutions or technical ideas formed thereby shall be regarded as part of the original disclosure or original record of the present invention, and shall not be It is regarded as new content that has not been disclosed or anticipated in this article, unless those skilled in the art think that the combination is obviously unreasonable.

All patent and non-patent documents mentioned in this article, including but not limited to textbooks and journal articles, etc., are incorporated into this article by reference in their entirety.

As mentioned above, this application provides a method for removing dissolved oxygen in oil, which includes the following steps:

The catalyst used in the present application comprises a first carrier with a relatively low porosity and a second carrier with a porous structure coated on the outer surface of the first carrier, and the catalytically active components are mainly supported on the porous second carrier. In a preferred embodiment, the porosity of the first carrier is ≤25%, more preferably ≤15%. According to this application, the porosity can be measured by mercury intrusion method (ISO 15901-1). In a further preferred embodiment, the specific pore volume of the first carrier is less than or equal to 0.3 ml/g, and the specific surface area of the mercury intrusion method is less than or equal to ^{5 m 2 /g.}

In the catalyst used in the present application, the material constituting the first carrier is a material with low porosity, and the first carrier with low porosity reduces the infiltration of catalytically active components. For catalysts containing platinum, palladium and other precious metals, in order to reduce costs, the precious metals loaded on the spent catalyst will be recycled after the catalyst is deactivated and replaced. The recycling process requires the use of acid or alkali to dissolve the spent catalyst to precipitate the loaded precious metals into the solution. Recycling. However, the substances constituting the first carrier often cannot be completely dissolved by acid and alkali. If the precious metal penetrates into the first carrier more, it is difficult to completely recover it through the chemical process. After the recovery treatment, there will still be more precious metals remaining in the first carrier, resulting in precious metals. The recovery rate is low. In the catalyst used in this application, the material constituting the second carrier can generally be completely dissolved by acid or alkali, and the precious metal components carried in the second carrier are easier to recover; at the same time, the porosity of the first carrier is low It reduces the infiltration of catalytically active components, minimizes the amount of precious metals contained in the first carrier, and thereby reduces the loss when recovering precious metals from the spent catalyst. At the same time, the lower porosity of the first carrier also reduces the inward diffusion of reactants and products, shortens the diffusion distance of reactants and products inside the catalyst, and reduces the occurrence of side reactions.

According to the present application, the pores corresponding to the first pore distribution peak of the second carrier, that is, the first type pores, generally have a pore diameter in the range of 4-200 nm, preferably in the range of 6-100 nm; The pores corresponding to the second pore distribution peak of the second carrier, that is, the second type pores, generally have a pore diameter in the range of 80-10000 nm, preferably in the range of 100-5000 nm.

In a preferred embodiment, the pore diameter corresponding to the peak of the first pore distribution peak of the second carrier is in the range of 8-50 nm, more preferably in the range of 10-50 nm, and the peak of the second pore distribution peak corresponds to the pore diameter It is in the range of 200-3000 nm, more preferably in the range of 200-1000 nm.

In a preferred embodiment, the total specific pore volume of the pores corresponding to the first pore distribution peak and the pores corresponding to the second pore distribution peak of the second carrier (also referred to as the total specific pore volume of the first type of pore and the second type of pore) The specific pore volume) is at least 0.5 ml/g, preferably at least 1.0 ml/g. Further preferably, the pore volume of the pores corresponding to the first pore distribution peak (also referred to as the pore volume of the first type of pore) and the pore volume of the pores corresponding to the second pore distribution peak (also referred to as the pore volume of the second type of pore) The ratio of pore volume) is 1:9 to 9:1, preferably 3:7 to 7:3.

According to the present application, the carrier of the catalyst is composed of a first carrier located inside and a second carrier located outside, respectively, composed of two substances with different properties, and combined. Examples of the constituent material of the first carrier include, but are not limited to, α-alumina, silicon carbide, mullite, cordierite, zirconia, titania, or a mixture thereof. The first carrier can be formed into different shapes as required, such as a spherical shape, a bar shape, a sheet shape, a ring shape, a gear shape, a cylindrical shape, etc., preferably a spherical shape. The effective diameter of the first carrier may be 0.5 mm to 10 mm, preferably 1.2 mm to 2.5 mm. When the first carrier is spherical, the effective diameter refers to the actual diameter of the first carrier; and when the first carrier is non-spherical, the effective diameter refers to when the first carrier is formed In the case of a spherical shape, the diameter of the resulting spherical shape.

According to the present application, examples of the constituent materials of the second support include, but are not limited to, γ-alumina, δ-alumina, η-alumina, θ-alumina, zeolite, non-zeolite molecular sieves, titania, zirconia, Cerium oxide or a mixture thereof, preferably γ-alumina, δ-alumina, zeolite, non-zeolite molecular sieve or a mixture thereof. The second carrier has two different types of pore structures (ie, different pore sizes), and the maximum value of the pore size distribution of the first type of pores is between 4-80 nm, preferably in the range of 8-50 nm, and more preferably in the range of 10-80 nm. In the range of 50 nm, the maximum value of the pore size distribution of the second type of pores is between 100-8000 nm, preferably in the range of 200-3000 nm, more preferably in the range of 200-1000 nm. In a preferred embodiment, the mercury intrusion specific surface area of the second carrier is at least 50 m ² /g, preferably at least 100 m ² /g.

In a preferred embodiment, the catalytically active component of the oxygen scavenging catalyst includes at least one IUPAC Group 8-14 metal. Further preferably, based on the mass of the catalyst, the catalyst contains 0.01%-2% of at least one IUPAC Group 8-14 metal.

In a further preferred embodiment, the catalyst contains palladium as the main catalytically active component, and contains a catalytically active component selected from silver, tin or lead. Particularly preferably, based on the mass of the catalyst, the catalyst contains 0.01% to 2% of palladium, and 0.01% to 2% of the catalytically active component.

In some preferred embodiments, the catalyst is prepared by a method including the following steps:

1) Shape the raw material of the first carrier into a predetermined shape, react for 5-24 hours in an air atmosphere at 40-90°C and a relative humidity of ≥80%, dry and calcinate to obtain a material selected from the group consisting of α-alumina, silicon carbide, A first carrier composed of mullite, cordierite, zirconium oxide, titanium oxide or a mixture thereof;

2) Combine porous materials selected from γ-alumina, δ-alumina, η-alumina, θ-alumina, zeolite, non-zeolite molecular sieves, titanium oxide, zirconium oxide, cerium oxide or mixtures thereof with optional manufacturing The porogen is made into slurry, and the resulting slurry is applied to the outer surface of the first carrier, dried and fired to obtain a carrier comprising a first carrier and a second carrier coated on the outer surface of the first carrier. The pore distribution curve of the porous material has one pore distribution peak, and the pore distribution peak corresponding to the pore size is in the range of 4-80 nm, or the pore distribution curve of the porous material has two pore distribution peaks, wherein the first pore distribution peak The pore diameter corresponding to the peak of the second pore distribution peak is in the range of 4-80nm, and the pore diameter corresponding to the peak of the second pore distribution peak is in the range of 100-8000nm;

3) Impregnating the carrier obtained in step 2) with a solution containing catalytically active components, drying and calcining, and optionally performing steam treatment to obtain a catalyst precursor; and

4) The catalyst precursor obtained in step 3) is reduced with hydrogen to obtain a catalyst product.

The molding of the first carrier can be based on the characteristics of the constituent materials using carrier molding methods known in the art, such as compression molding, extrusion molding, rolling ball molding, drop ball molding, pelletizing molding, melt molding, and the like. According to the difference of the first carrier material, molding generally requires adding 2-20% of the weight of the raw material powder to one or more of inorganic or organic acids such as nitric acid, hydrochloric acid, citric acid, and glacial acetic acid. And a small amount of water, fully mixed and molded. The molded first carrier needs to continue to react for 5 to 24 hours under the conditions of 40 to 90 ℃ and air relative humidity ≥ 80%, and maintain the humidity environment at a suitable temperature to promote the crystal structure Fully transform, and then dry at 100 to 150 ℃ for 2 to 8 hours. The first carrier after drying needs to be calcined at a certain temperature to form a low-porosity structure. The calcining temperature should be at least higher than the catalyst temperature, which is generally 350 to 1700°C according to the characteristics of different materials. The fired first carrier is a substance with a low porosity, specifically, a substance with a specific pore volume ≤ 0.3 ml/g, a mercury injection method specific surface area ^{≤ 5 m 2} /g, and a porosity ≤ 35%.

The raw materials used to prepare the first carrier are well known to those skilled in the art and can be selected according to the constituent materials of the first carrier. For example, when the first carrier is mullite, alumina and silica can be used as raw materials to synthesize by a sintering method; when the first carrier is α-alumina, aluminum hydroxide can be obtained by high-temperature sintering as a raw material.

The combination of the second carrier and the first carrier can be achieved by first forming a slurry of the second carrier material, and then applying the resulting slurry to the outer surface of the first carrier by conventional methods such as dipping, spraying, coating, etc. To achieve, but not limited to the above several coating methods. The preparation of the second carrier material slurry usually includes a peptizing process. The second carrier material with a porous structure and water are mixed and stirred in a certain ratio. Usually, a certain amount of peptizing agent, such as nitric acid, hydrochloric acid or organic acid, is added. The dosage accounts for 0.01% to 5% of the total slurry. The thickness of the second carrier can be controlled by the amount of the second carrier material slurry.

According to the present application, the thickness of the second carrier can be determined according to the effective diameter of the first carrier, thereby obtaining the best catalytic reaction performance. Generally, the thickness of the second carrier is equal to the effective diameter of the first carrier. The ratio is between 0.01-0.2.

The second carrier with two types of pores can be directly prepared from a porous material with a desired pore structure, or can be prepared from a porous material with a certain pore structure combined with a suitable amount of pore former. For example, the second carrier may be directly made of a porous material having two types of pores (for example, the maximum value of the pore size distribution is in the range of 4-80nm and 100-8000nm, respectively); it may also be made of only one type of pores. (For example, the maximum value of the pore size distribution is in the range of 4-80 nm). The porous material is made by combining a suitable amount of pore former. According to the required pore size, the pore former can be selected from sesame powder, methyl cellulose, polyvinyl alcohol, carbon black and other materials, but it is not limited to these, and the addition amount is controlled to form the second carrier 5%-50% of the mass of the porous material. The second carrier of the finally prepared catalyst has two types of pores. The maximum value of the pore size distribution of the first type of pores is between 4-80 nm, preferably in the range of 8-50 nm, more preferably in the range of 10-50 nm, The maximum value of the pore size distribution of the second type of pores is between 100-8000 nm, preferably in the range of 200-3000 nm, more preferably in the range of 200-1000 nm. The pore volume provided by the first type of hole accounts for 10%-90% of the total pore volume, preferably 30%-70%, and the pore volume provided by the second type of pores accounts for 90%-10% of the total pore volume, preferably 70%-30 %.

The combination of the second carrier and the first carrier needs to be calcined at a high temperature to complete. For example, the first carrier coated with the porous material slurry is dried at 60-200°C for 0.5-10 hours, and then calcined at 300-1000°C for a sufficient time, such as 2-15 hours, to obtain the first carrier and the package. The carrier of the second carrier covering the outer surface of the first carrier.

Each catalytically active component can be supported on the aforementioned support by means of impregnation. One method is to make each catalytically active component into a mixed solution and contact the mixed solution with the carrier; the other method is to contact the solution of each catalytically active component with the carrier one by one. Dry the carrier impregnated with catalytically active components at 100-200°C for 2-8 hours, then calcinate at 300-600°C for 2-8 hours, and pass water vapor at 200-700°C for further treatment for 0.5-4 hours; Then, it is reduced with hydrogen at room temperature to 300°C, preferably 60-150°C, for 0.5-10 hours, preferably 1-5 hours, to obtain the catalyst.

In a preferred embodiment, the method of the present application is to fully mix the oil with hydrogen before it enters the hydrogenation reactor, and then the mixed oil enters the reactor to contact with the deoxygenation catalyst.

In a preferred embodiment, in step 1), the oil and hydrogen are mixed through a mixer. The mixer includes a housing and a cylindrical filter arranged in the housing, and the cylindrical filter does not contact the inner wall of the housing. A channel is formed between the two.

In a further preferred embodiment, the cylindrical filter can adopt a common sintered stainless steel filter cartridge with a pore diameter of 1-10 microns, which can fully mix hydrogen and oil.

In a preferred embodiment, the volume ratio of hydrogen to oil mixed in step 1) is 1.0-4.0.

In a preferred embodiment, the hydrogenation and deoxygenation reaction of step 2) is carried out in a hydrogenation reactor. The reactor may be a common fixed-bed reactor, which is filled with the deoxygenation catalyst to form a catalyst bed. Floor.

In a preferred embodiment, the conditions for the hydrogenation and deoxygenation reaction in step 2) include: temperature 40-80°C, hydrogen-oil volume ratio 1.0-4.0, pressure 0.2-1.0 MPa, liquid hourly volumetric space velocity 10-20h ^-1 .

According to this application, the "hydrogen to oil volume ratio" used in step 1) and the "hydrogen to oil volume ratio" used in step 2) both refer to the hydrogen and the waiting time determined according to the reaction temperature and pressure conditions of step 2). The volume ratio of the oil that removes dissolved oxygen.

According to the present application, there are no special restrictions on the oil products suitable for removing dissolved oxygen by the method of the present application, and examples include but are not limited to kerosene, diesel and the like.

In some preferred embodiments, this application provides the following technical solutions:

1. A method for removing dissolved oxygen in oil, characterized in that the oil is fully mixed with hydrogen before entering the reactor, and then it enters the reactor to contact with a deoxygenation catalyst, the catalyst including a carrier And at least one catalytic component supported on the carrier, the carrier including at least a first layer carrier and a second layer carrier, the second layer carrier spatially covering the first layer carrier, At least one of the catalytic components is deposited on the second layer of support.

2. The method according to item 1, characterized in that the ratio of the thickness of the second layer carrier to the effective diameter of the first layer carrier is between 0.01 and 0.2.

3. The method according to item 1, characterized in that the second layer of carrier is distributed with first type pores and second type pores, and the maximum value of the pore size distribution of the first type pores is between 4-50 nm The maximum value of the pore size distribution of the second type of holes is between 100 nm and 1000 nm.

4. The method according to item 3, characterized in that the pore size distribution range of the first type pores is between 10-20 nm, and the pore size distribution range of the second type pores is between 150-500 nm.

5. The method according to item 1, wherein the method includes the step of depositing the at least one IUPAC Group 8-14 metal onto the second layer of support.

6. The method according to item 1, characterized in that the oil product is fully mixed with hydrogen before entering the reactor further comprises: the oil product and hydrogen are mixed through a mixer, the mixer consists of a shell and a cylindrical filter It is constructed that the cylindrical filter is not in contact with the inner wall of the housing, and an annular channel is formed between the two.

7. The method according to item 6, characterized in that the pore size of the cylindrical filter is 1-10 microns.

8. The method according to item 1, characterized in that the mixing volume ratio of hydrogen and oil is 1.0-4.0.

9. The method according to item 1, characterized in that the hydrogenation and deoxygenation reaction conditions are: temperature: 40～80℃, hydrogen-to-oil volume ratio: 1.0～4.0, pressure: 0.2～1.0MPa, space velocity: 10～20h ^-1 .

10. The catalyst according to item 1, characterized in that the pore volume of the first layer of support is ≤ 0.3 ml/g, and the BET specific surface area is ≤ ²⁰ m 2 /g.

Example

Hereinafter, the present application will be described in detail through examples, but they do not constitute any limitation to the present application.

In the following examples and comparative examples, the specific pore volume, porosity and specific surface area of the first and second carriers, as well as the pore distribution of the second carrier, adopt the mercury intrusion method (ISO 15901-1 Evaluation of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption). The instrument used was the Poremaster GT60 Mercury Porosimetry Analyzer from Quantachrome Instrument, and the test conditions were 140° contact angle and mercury surface tension at 25°C of 0.4842 N·m ^-1 . The post-processing software is Poremaster for Windows. The pore distribution curve of the second carrier is obtained by mapping the measured data with Origin software.

In the following examples and comparative examples, the catalytically active component content of the catalyst obtained was determined by X-ray fluorescence spectrometry, the instrument used was ADVANT'TP X-ray fluorescence spectrometer from ARL Company, and the test conditions were Rh target, 40kV/ 60mA.

In the following examples and comparative examples, the crystal form of the carrier material is determined by X-ray powder diffraction (XRD), the instrument used is ARL X'TRA X-ray diffractometer, the test conditions are Cu target, Kα rays (wavelength λ = 0.154nm), the tube voltage is 45kV, the tube current is 200mA, and the scanning speed is 10°(2θ)/min.

In the following examples and comparative examples, the thickness of the second carrier is measured by scanning electron microscopy (SEM), the instrument used is a Hitachi TM3000 desktop microscope, and the test condition is that the sample is fixed on the sample stage with conductive glue for observation, and the voltage is 15kV.

In the following examples and comparative examples, the alumina powder with two types of pores used to prepare the second carrier was prepared with reference to the method disclosed in Chinese Patent Application CN1120971A, and other alumina and aluminum hydroxide powders were purchased from Shandong Aluminum Industry Co., Ltd.

Unless otherwise specified, the reagents used in the following examples and comparative examples are all analytically pure, and all are commercially available.

Example 1 Preparation of Catalyst A

In this embodiment, alumina powder with two types of pores is used to prepare the second carrier, and mullite is used as the first carrier to effectively combine to obtain a carrier containing two layers of inner and outer layers, and to prepare a catalyst.

Take 500 grams of alumina powder (purity 98.6%), 196 grams of silica powder (purity 99.0%), 70 grams of water, 10 grams of 10% nitric acid, mix, knead for 1 hour, press into small balls, 70℃, ≥80% The reaction was continued under relative humidity for 10 hours, then dried at 150°C for 2 hours, and then calcined at 1450°C for 3 hours to obtain the first carrier pellets with a diameter of 2.0 mm. XRD analysis showed that it was mullite crystal form.

The prepared first carrier was characterized by mercury intrusion method, and the results showed that the specific pore volume of the first carrier was 0.09 ml/g, the specific surface was 0.21 m ² /g, and the porosity was 12%.

Take 50 grams of alumina powder (with two types of pores, the maximum value of the pore size distribution of the two types of pores is 27 nm and 375 nm, respectively), 20 grams of 20% nitric acid, and 600 grams of water are mixed and stirred for 2 hours to prepare an alumina slurry. The slurry was sprayed on the first carrier ball with a diameter of 2.0 mm with a spray gun. The pellets coated with the slurry were dried at 100°C for 6 hours, and then calcined at 500°C for 6 hours to obtain a carrier containing two layers of inner and outer layers. SEM analysis showed that the thickness of the second carrier was 150 μm, and the ratio to the diameter of the first carrier was 0.075.

The prepared carrier was impregnated with a 0.4 mol/l palladium chloride solution, dried at 120°C for 5 hours, calcined at 550°C for 4 hours, and treated with steam at 550°C for 1 hour. Then, it was reduced with hydrogen with a purity of greater than 99% at 120°C for 4 hours to prepare catalyst A. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

The second carrier coated on the outer surface of the first carrier is peeled off mechanically, and the second carrier is characterized by mercury intrusion method. The obtained pore distribution curve is shown in FIG. 1. It can be seen from Figure 1 that the pore distribution curve of the second carrier of the catalyst has two pore distribution peaks, indicating that there are two types of pores with different sizes in the second carrier, and the pore size distribution of the first type of pore The maximum value (ie the pore size value corresponding to the peak of the first pore distribution peak in the curve, the same below) is 22nm, and the maximum value of the pore size distribution of the second type of hole (ie the peak value of the second pore distribution peak in the curve corresponds to The aperture value, the same below) is 412nm. Based on the mass of the second carrier, the specific pore volume of the first type of pore is 0.98 ml/g, the specific pore volume of the second type of pore is 0.72 ml/g, and the total specific pore volume is 1.70 ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 152 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 2 Preparation of Catalyst B

In this embodiment, the alumina powder with one type of pores and the pore-forming agent methylcellulose are added to prepare the second carrier with two types of pores, and mullite is used as the first carrier to effectively combine the inside and outside. A two-layer carrier and a catalyst are prepared.

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with one type of pores, the maximum pore size distribution is 25 nm), 20 grams of 20% nitric acid, 12 grams of methyl cellulose, and 600 grams of water are mixed and stirred to prepare an alumina slurry. Refer to the method of Example 1 for molding, and appropriately adjust the amount of alumina slurry to obtain a carrier containing two layers of inner and outer layers. SEM analysis showed that the thickness of the second carrier was 120 μm, and the ratio to the diameter of the first carrier was 0.06.

The catalyst B was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

With reference to Example 1 for characterization by mercury intrusion method, it is found that there are two types of pores in the second support of the catalyst. The maximum value of the pore size distribution of the first type of pore is 19 nm, and the maximum value of the pore size distribution of the second type of pore is 252 nm. Based on the mass of the second carrier, the specific pore volume of the first type of pore is 0.9ml/g, the specific pore volume of the second type of pore is 0.6ml/g, and the total specific pore volume is 1.50ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 135 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 3 Preparation of Catalyst C

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with two types of pores, the maximum value of the pore size distribution of the two types of pores is 20 nm and 516 nm, respectively), 20 grams of 20% nitric acid, and 600 grams of water are mixed and stirred for 2 hours to prepare an alumina slurry. Refer to the method of Example 1 for molding, and appropriately adjust the amount of alumina slurry to obtain a carrier containing two layers of inner and outer layers. Analysis shows that the thickness of the second carrier is 220 μm, and the ratio to the diameter of the first carrier is 0.11.

The catalyst C was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

With reference to Example 1 for characterization by mercury intrusion method, it is found that there are two types of pores in the second support of the catalyst, the maximum value of the pore size distribution of the first type of pore is 15 nm, and the maximum value of the pore size distribution of the second type of pore is 652 nm. Based on the mass of the second carrier, the specific pore volume of the first type is 0.91ml/g, the specific pore volume of the second type is 0.69ml/g, and the total specific pore volume is 1.60ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 145 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 4 Preparation of Catalyst D

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with two types of pores, the maximum value of the pore size distribution of the two types of pores is 12 nm and 100 nm, respectively), 20 grams of 20% nitric acid, and 600 grams of water are mixed and stirred for 2 hours to prepare an alumina slurry. Refer to the method of Example 1 for molding, and appropriately adjust the amount of alumina slurry to obtain a carrier containing two layers of inner and outer layers. SEM analysis showed that the thickness of the second carrier was 70 μm, and the ratio to the diameter of the first carrier was 0.035.

The catalyst D was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

Refer to Example 1 for characterization by mercury intrusion method, and it is found that there are two types of pores in the second support of the catalyst. The maximum value of the pore size distribution of the first type of pore is 9 nm, and the maximum value of the pore size distribution of the second type of pore is 120 nm. Based on the mass of the second carrier, the specific pore volume of the first type is 0.58ml/g, the specific pore volume of the second type is 0.82ml/g, and the total specific pore volume is 1.40ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 122 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 5 Preparation of Catalyst E

Refer to the method of Example 3 to prepare a carrier containing two layers of inner and outer layers, and appropriately adjust the amount of alumina slurry. SEM analysis showed that the thickness of the second carrier was 180 μm, and the ratio to the diameter of the first carrier was 0.09.

The prepared carrier was first impregnated with 0.4mol/l palladium chloride solution, dried at 120°C for 5 hours, calcined at 550°C for 3 hours, treated with steam at 550°C for 1 hour, and then used 0.3mol /l tin chloride solution, dried at 120°C for 5 hours, roasted at 550°C for 4 hours, treated with steam for 1 hour, and then reduced with hydrogen with a purity greater than 99% at 120°C for 4 hours.成catalyst E. Measured by X-ray fluorescence spectroscopy, based on the mass of the catalyst, the content of each metal component of the catalyst is 0.2 wt% of palladium and 0.4 wt% of tin, respectively.

With reference to Example 1 for characterization by mercury intrusion method, it is found that there are two types of pores in the second support of the catalyst. The maximum value of the pore size distribution of the first type of pore is 16 nm, and the maximum value of the pore size distribution of the second type of pore is 630 nm. Based on the mass of the second carrier, the specific pore volume of the first type is 0.89ml/g, the specific pore volume of the second type is 0.68ml/g, and the total specific pore volume is 1.57ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 140 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 6 Preparation of Catalyst F

In this embodiment, alumina powder with two types of pores is used to prepare the second carrier, and α-alumina is used as the first carrier to effectively combine to obtain a carrier containing two layers of inner and outer layers, and prepare a catalyst.

Take 800 grams of aluminum hydroxide powder (purity 99%) and roll it into small balls. Place them at 70°C and ≥80% relative humidity and continue to react for 20 hours, then dry at 120°C for 2 hours, and then at 1100 It is calcined at ℃ for 5 hours to obtain a small ball with a diameter of 2.0 mm as the first carrier. XRD analysis showed that it was α-alumina crystal form.

Refer to the method of Example 1 to form a carrier containing two layers of inner and outer layers, and appropriately adjust the amount of alumina slurry. SEM analysis showed that the thickness of the second carrier was 150 μm, and the ratio to the diameter of the first carrier was 0.075.

The prepared carrier was first impregnated with 0.4mol/l palladium chloride solution, dried at 120°C for 5 hours, calcined at 550°C for 3 hours, treated with steam at 550°C for 1 hour, and then used 0.3mol /l lead nitrate solution, dried at 120°C for 5 hours, roasted at 550°C for 4 hours, and then reduced with hydrogen with a purity of more than 99% at 120°C for 4 hours to prepare catalyst F. Measured by X-ray fluorescence spectroscopy, based on the mass of the catalyst, the content of each metal component of the catalyst is 0.15 wt% of palladium and 0.05 wt% of lead.

With reference to Example 1 for characterization by mercury intrusion method, it was found that there are two types of pores in the second layer of the catalyst. The maximum value of the pore size distribution of the first type of pores is 20 nm, and the maximum value of the pore size distribution of the second type of pores is 410 nm. . Based on the quality of the second carrier, the specific pore volume of the first type is 0.96ml/g, the specific pore volume of the second type is 0.70ml/g, and the total specific pore volume is 1.66ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 148 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 7 Preparation of Catalyst G

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with one type of pores, the maximum pore size distribution is 28 nm), 18 grams of 20% nitric acid, 10 grams of methyl cellulose, and 600 grams of water are mixed and stirred to prepare an alumina slurry. The slurry was sprayed on the first carrier ball with a diameter of 2.0 mm with a spray gun. The pellets coated with the slurry were dried at 100°C for 6 hours, and then calcined at 900°C for 6 hours to obtain a carrier containing two layers of inner and outer layers. SEM analysis showed that the thickness of the second carrier was 110 μm, and the ratio to the diameter of the first carrier was 0.055.

The catalyst G was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

Refer to Example 1 for characterization by mercury intrusion method. It is found that there are two types of pores in the second layer of the catalyst. The maximum value of the pore size distribution of the first type of pore is 30 nm, and the maximum value of the pore size distribution of the second type of pore is 280 nm. . Based on the mass of the second carrier, the specific pore volume of the first type is 0.49ml/g, the specific pore volume of the second type is 0.57ml/g, and the total specific pore volume is 1.06ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 106 m ² /g. According to the XRD measurement in Example 1, the crystal form of the second support is δ-alumina.

Comparative Example 1 Preparation of Catalyst H

Take 500 grams of alumina powder (purity 98.6%), 196 grams of silica powder (purity 99.0%), 70 grams of water, 10 grams of 10% nitric acid, mix, knead for 1 hour, press into pellets, and then bake at 150 ℃ Dry for 2 hours, and then calcinate at 1450°C for 1 hour to obtain first carrier pellets with a diameter of 2.0 mm. XRD analysis showed that it was mullite crystal form.

The prepared first carrier was characterized by mercury intrusion method, and the result showed that the specific pore volume of the first carrier was 0.32 ml/g, the specific surface was 8.5 m ² /g, and the porosity was 38%.

The catalyst H was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

With reference to Example 1 for characterization by mercury intrusion method, it is found that there are two types of pores in the second support of the catalyst, the maximum value of the pore size distribution of the first type of pore is 22 nm, and the maximum value of the pore size distribution of the second type of pore is 420 nm. Based on the mass of the second carrier, the specific pore volume of the first type is 0.98ml/g, the specific pore volume of the second type is 0.71ml/g, and the total specific pore volume is 1.69ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 155 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Comparative Example 2 Preparation of Catalyst I

In this embodiment, alumina powder with one type of pores is used to prepare the second carrier, and mullite is used as the first carrier to effectively combine to obtain a carrier containing two layers of inner and outer layers, and to prepare a catalyst.

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with one type of pores, the maximum pore size distribution is 22 nm), 20 grams of 20% nitric acid, and 600 grams of water are mixed and stirred for 2 hours to prepare an alumina slurry. The slurry was sprayed on the first carrier ball with a diameter of 2.0 mm with a spray gun. The pellets coated with the slurry were dried at 100°C for 6 hours, and then calcined at 500°C for 6 hours to obtain a carrier containing two layers of inner and outer layers. Analysis shows that the thickness of the second carrier is 110 μm, and the ratio to the diameter of the first carrier is 0.055.

The catalyst I was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

With reference to Example 1, the mercury intrusion method was used for characterization, and it was found that only one type of pores existed in the second support of the catalyst, and the maximum pore size distribution was 16 nm. Based on the mass of the second carrier, the specific pore volume is 1.15ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 180 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Preparation of Catalyst J of Comparative Example 3

In this example, an alumina spherical support with two types of pores and a radially uniform composition was prepared, and a catalyst was prepared.

Take 50 grams of alumina powder (with two types of pores, and the maximum pore size distribution of the two types of pores are 15 nm and 250 nm, respectively), 20 grams of 20% nitric acid, and 200 grams of water are mixed and stirred to prepare an alumina slurry. The slurry is formed into pellets by a method of forming an oil column, dried at 100°C for 6 hours, and then calcined at 500°C for 6 hours to obtain a radially uniform carrier.

The catalyst J was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

The mercury intrusion method was used to characterize the catalyst J. It was found that there were two types of pores in the catalyst. The maximum pore size distribution of the first type of pores was 20nm, the specific pore volume of the first type was 0.93ml/g, and the second type of pores had a specific pore volume of 0.93ml/g. The maximum pore size distribution is 395nm, the specific pore volume of the second type is 0.76ml/g, and the total specific pore volume is 1.69ml/g. The specific surface area of the carrier measured by the mercury intrusion method is 165 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Comparative Example 4 Preparation of Catalyst K

The first carrier was prepared according to the method of Example 1.

Take 50 grams of alumina powder (with two types of pores, the maximum pore size distribution of the two types of pores is 26 nm and 384 nm respectively), 20 grams of 20% nitric acid, and 600 grams of water are mixed and stirred for 2 hours to prepare an alumina slurry. The slurry was sprayed on the first carrier pellet with a diameter of 1.3 mm with a spray gun. The pellets coated with the slurry were dried at 100°C for 6 hours, and then calcined at 500°C for 6 hours to obtain a carrier containing two layers of inner and outer layers. SEM analysis showed that the thickness of the second carrier was 350 μm, and the ratio to the diameter of the first carrier was 0.27.

The catalyst K was obtained according to the catalyst preparation method of Example 1. Measured by X-ray fluorescence spectrometry, based on the mass of the catalyst, the palladium content of the catalyst is 0.2 wt%.

With reference to Example 1 for characterization by mercury intrusion method, it is found that there are two types of pores in the second support of the catalyst, the maximum value of the pore size distribution of the first type of pore is 21 nm, and the maximum value of the pore size distribution of the second type of pore is 450 nm. Based on the mass of the second carrier, the specific pore volume of the first type is 0.96ml/g, the specific pore volume of the second type is 0.75ml/g, and the total specific pore volume is 1.71ml/g. The specific surface area of the second carrier measured by mercury intrusion method was 153 m ² /g. According to XRD measurement, the crystal form of the second carrier is γ-alumina.

Example 8 Analysis of Pd content in the first carrier of the catalyst

The catalyst A obtained in Example 1 was digested with 15 wt% hydrochloric acid to remove the second carrier, and the Pd content of the remaining first carrier was analyzed by X-ray fluorescence spectrometry. The results show that based on the mass of the first carrier, the Pd content in the first carrier is 0.0009wt%.

Analysis of Pd content in the first carrier of the comparative example 5

The catalyst H obtained in Comparative Example 1 was digested with hydrochloric acid with a concentration of 15 wt% to remove the second carrier, and the Pd content of the remaining first carrier was analyzed by X-ray fluorescence spectrometry. The results show that based on the mass of the first carrier, the Pd content in the first carrier is 0.015 wt%.

By comparing the data of Comparative Example 1 and Example 1, it can be seen that the specific pore volume of the first carrier prepared by the method of Example 1 is 0.09ml/g, the specific surface is 0.21m ² /g, the porosity is 12%, and the porosity is The specific pore volume of the first carrier prepared by the method of Comparative Example 1 is 0.32 ml/g, the specific surface area is 8.5 m ² /g, the porosity is 38%, and the porosity is relatively high. At the same time, by comparing the data of Comparative Example 5 and Example 8, it can be seen that after acid cooking, the content of Pd in the catalyst A with low porosity of the first carrier is 0.0009wt%, which is much smaller than the porosity of the first carrier. The residual Pd content in the high catalyst H is 0.015 wt%. The above results indicate that the low-porosity first carrier of catalyst A reduces the entry of Pd, so that catalyst A has a higher recovery rate of Pd, the use efficiency of precious metals is higher, and the use cost of the catalyst is lower.

Example 9 Comparison of deoxygenation effect

The catalysts prepared in the foregoing examples and comparative examples were respectively charged into a fixed bed reactor, and the reaction temperature was controlled to 70° C., the pressure to be 0.8 MPa, the LHSV to be 10 h ^-1 , and the H ₂ /oil volume ratio to be 1.0. The kerosene containing a small amount of dissolved oxygen was passed through the reactor, and the Orbisphere 3650 dissolved oxygen analyzer was used to analyze the oxygen content changes before and after the kerosene passed through the reactor. The results are shown in Table 1.

Table 1 Deaeration test results

It can be seen from the data in Table 1 that the seven catalysts A, B, C, D, E, F, and G prepared in Examples 1-7 of the present application with two-layer supports and two types of pore distribution are compared with those of the comparative catalyst I , J, the deoxygenation rate is significantly improved. The catalyst A with the first support with low porosity has a higher oxygen removal rate than the catalyst H with the first support with higher porosity. The ratio of the thickness of the second carrier to the effective diameter of the first carrier is between 0.01 and 0.2. The oxygen removal rate of catalysts A, B, C, D, E, F, G is higher than that of the thickness of the second carrier. The catalyst K in which the ratio of the effective diameter of the first carrier is not between 0.01 and 0.2.

Example 10 Catalyst service life

The catalyst E prepared in the above Example 5 was put into a fixed bed reactor, and the reaction temperature was controlled to be 55° C., the pressure was 0.8 MPa, the LHSV was 20 h ^-1 , and the H ₂ /oil volume ratio was 3.0. Pass kerosene containing a small amount of dissolved oxygen into the reactor, and use the Orbisphere 3650 dissolved oxygen analyzer to analyze the oxygen content changes before and after the kerosene passes through the reactor after a period of continuous operation. The results are shown in the table. 2.

Table 2 Catalyst life (use time) test results

It can be seen from the data in Table 2 that in the method of the present application, the catalyst still has a higher oxygen removal rate after 4000 hours of continuous operation.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the embodiments of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions recorded in the foregoing embodiments can still be modified, or some of the technical features can be equivalently replaced; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and spirit of the technical solutions of the embodiments of the present application. range.

Claims

The method for removing dissolved oxygen in oil includes the following steps:

1) Mixing oil and hydrogen, preferably the volume ratio of the mixing of hydrogen and oil is 1.0-4.0; and

2) The mixture from step 1) is contacted with a deoxygenation catalyst for hydrogenation and deoxygenation reaction,

Wherein, the catalyst includes a carrier, the carrier includes a first carrier, a second carrier coated on the outer surface of the first carrier, and a catalytically active component supported on the second carrier, wherein the first carrier The porosity of <35%, preferably the catalytically active component contains at least one IUPAC Group 8-14 metal.
The method according to claim 1, wherein the ratio of the thickness of the second support of the oxygen scavenging catalyst to the effective diameter of the first support is between 0.01 and 0.2.
The method according to any one of the preceding claims, wherein the pore distribution curve of the second carrier of the oxygen scavenging catalyst has two pore distribution peaks, wherein the peak of the first pore distribution peak corresponds to the pore diameter of 4-80 nm Within the range, preferably in the range of 8-50nm, more preferably in the range of 10-50nm, and the pore diameter corresponding to the peak of the second pore distribution peak is in the range of 100-8000nm, preferably in the range of 200-3000nm, more preferably in the range of 200 -1000nm range.
The method of any one of the preceding claims, wherein the oxygen scavenging catalyst has one or more of the following characteristics:

The total specific pore volume of the pores corresponding to the first pore distribution peak and the pores corresponding to the second pore distribution peak is at least 0.5 ml/g, preferably at least 1.0 ml/g;

The ratio of the pore volume of the pores corresponding to the first pore distribution peak to the pore volume of the pores corresponding to the second pore distribution peak is 1:9 to 9:1, preferably 3:7 to 7:3.
The catalyst according to any one of the preceding claims, wherein the oxygen scavenging catalyst has one or more of the following characteristics:

The second carrier is composed of a material selected from the group consisting of γ-alumina, δ-alumina, η-alumina, θ-alumina, zeolite, non-zeolite molecular sieve, titanium oxide, zirconia, cerium oxide or a mixture thereof; and

The mercury intrusion specific surface area of the second carrier is at least 50 m 2 /g, preferably at least 100 m 2 /g.
The catalyst according to any one of the preceding claims, wherein the oxygen scavenging catalyst has one or more of the following characteristics:

The specific pore volume of the first carrier is less than or equal to 0.3 ml/g, and the specific surface area of the mercury injection method is less than or equal to 5 m 2 /g;

The porosity of the first carrier is ≤25%, more preferably ≤15%;

The first carrier is made of a material selected from the group consisting of α-alumina, silicon carbide, mullite, cordierite, zirconia, titania or a mixture thereof;

The first carrier is spherical, bar-shaped, sheet-shaped, ring-shaped, gear-shaped or cylindrical, preferably spherical; and

The effective diameter of the first carrier is 0.5 mm to 10 mm, preferably 1.2 mm to 2.5 mm.
The method according to any one of the preceding claims, wherein the step 1) is performed in a mixer, the mixer comprising a housing and a cylindrical filter arranged in the housing, the cylindrical filter and the inner wall of the housing There is no contact, and a channel is formed between the two. Preferably, the pore size of the cylindrical filter is 1-10 microns.
The method according to any one of the preceding claims, wherein the conditions for the hydrogenation and deoxygenation reaction in step 2) include: temperature 40-80°C, hydrogen-oil volume ratio 1.0-4.0, pressure 0.2-1.0 MPa, liquid time The volumetric space velocity is 10-20h -1 .