Hydrodeoxygenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the field of catalysts, and discloses a hydrodeoxygenation catalyst and a preparation method and application thereof. The hydrodeoxygenation catalyst comprises oxygen-rich hole CeO2, a metal active component loaded on the oxygen-rich hole CeO2, and an optional auxiliary agent, the auxiliary agent is alkali metal oxide and / or alkaline earth metal oxide; the metal active component is selected from at least one of Pd oxide, Au oxide, Pt oxide, Ag oxide, Ru oxide and Rh oxide. The hydrodeoxygenation catalyst provided by the invention is simple in preparation method and strong in operability, has very high deoxygenation efficiency under a low-temperature treatment condition, and can reduce the energy consumption in a deoxygenation operation process.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to a hydrodeoxygenation catalyst, its preparation method, and its application. Background Technology

[0002] Epichlorohydrin can be processed to produce epoxy resins, which can then be used in coatings, electronics, composite materials, and other fields. The production of epichlorohydrin via hydrogen peroxide oxidation offers advantages such as high atom economy and low wastewater and waste residue emissions. However, in this process, hydrogen peroxide is prone to decomposition under the catalytic action of alkalis, metal ions, and high temperatures, producing oxygen. This oxygen, when mixed with methanol and allyl chloride vapors, forms an explosive mixture, posing a risk of combustion and explosion, and threatening the safe and stable operation of industrial plants.

[0003] To address the aforementioned issues, the risk of combustion and explosion in the system is typically eliminated by diluting it with inert gases such as nitrogen. However, this method involves significant energy and material consumption, impacting the profitability of the equipment. Catalytic deoxygenation, which reacts oxygen with a sacrificial agent to achieve deoxygenation, has promising applications in practical chemical production processes. However, this method involves the preparation of a deoxygenation catalyst, and the quality of the catalyst directly affects the deoxygenation effect.

[0004] Patent application CN115707508A discloses a method for reducing the risk of combustion and explosion of oxygen-containing organic gases. The stabilizing gas disclosed in this technology can be recycled, reducing deoxygenation costs. However, in the hydrogen peroxide process for producing epichlorohydrin, the oxygen-containing organic gas feedstock contains a high content of 3-chloropropene. The highly electronegative chlorine species means that the reaction performance of most deoxygenation catalysts cannot meet the requirements of the on-site operating conditions, necessitating further increases in reaction temperature to achieve high deoxygenation chlorination. Furthermore, in existing technologies, the preparation methods for resistant 3-chloropropene poisoning deoxygenation catalysts are complex or costly, and their performance reproducibility is often difficult to guarantee. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems existing in the prior art and provide a hydrodeoxygenation catalyst that has excellent oxygen adsorption capacity and good hydrodeoxygenation performance for gases containing high concentrations of 3-chloropropene species.

[0006] To achieve the above objectives, the present invention provides a hydrodeoxygenation catalyst, the hydrodeoxygenation catalyst comprising oxygen-rich hole CeO2 and a metal active component supported on the oxygen-rich hole CeO2, and optional additives.

[0007] The additive is an alkali metal oxide and / or an alkaline earth metal oxide;

[0008] The active metal component is selected from at least one of Pd oxide, Au oxide, Pt oxide, Ag oxide, Ru oxide, and Rh oxide.

[0009] Preferably, the hydrodeoxygenation catalyst has a porous structure.

[0010] Preferably, the diameter of the pore is 2-50 nm.

[0011] Preferably, the weight ratio of the metal active component to the oxygen-rich hole CeO2 is 0.01-5:100, wherein the metal active component is calculated as a metal element.

[0012] Preferably, the weight ratio of the additive to the oxygen-rich hole CeO2 is 0-5:100, wherein the additive is calculated as a metal element.

[0013] A second aspect of the present invention provides a method for preparing a hydrodeoxygenation catalyst, the method comprising the following steps:

[0014] (1) CeO2 is pretreated with gaseous materials under a protective atmosphere to obtain oxygen-rich vacancy CeO2;

[0015] (2) The precursor solution and the oxygen-rich vacancy CeO2 obtained in step (1) are mixed, and then solid-liquid separation, drying and calcination are performed.

[0016] In step (1), the gaseous material is selected from at least one of ammonia, organic amine vapor, and water vapor;

[0017] In step (2), the precursor solution contains a metal-active component precursor and an optional auxiliary agent precursor;

[0018] The metal active component precursor is selected from at least one of Pd precursor, Au precursor, Pt precursor, Ag precursor, Ru precursor and Rh precursor;

[0019] The precursor of the adjuvant is an alkali metal precursor and / or an alkaline earth metal precursor.

[0020] Preferably, in step (1), the volume ratio of the gaseous material to the weight of the CeO2 is 80-1000 mL: 1 g.

[0021] Preferably, in step (1), the pretreatment conditions include: a temperature of 300-800℃, a pressure of 0.1-0.5MPa, and a time of 1-10h.

[0022] Preferably, in step (2), the weight ratio of the metal active component precursor to the oxygen-rich hole CeO2 is 0.01-5:100, wherein the metal active component precursor is calculated as a metal element.

[0023] Preferably, in step (2), the weight ratio of the auxiliary precursor to the oxygen-rich hole CeO2 is 0-5:100, wherein the auxiliary precursor is calculated as a metal element.

[0024] Preferably, in step (2), the calcination conditions include: a temperature of 400-600℃ and a time of 3-10h.

[0025] A third aspect of the present invention provides a hydrodeoxygenation catalyst prepared by the above method.

[0026] The fourth aspect of the present invention provides the application of the above-mentioned hydrodeoxygenation catalyst in the treatment of oxygen-containing hydrocarbon gases.

[0027] The fifth aspect of the present invention provides a method for treating oxygen-containing hydrocarbon gases, wherein the oxygen-containing hydrocarbon gases are contacted with a catalyst;

[0028] The catalyst is the aforementioned hydrodeoxygenation catalyst.

[0029] Preferably, the contact conditions include an airspeed of 500-9000 h⁻¹. -1 The pressure is 0.1-1.5MPa and the temperature is 150-250℃.

[0030] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0031] (1) The preparation method of the hydrodeoxygenation catalyst of the present invention is simple and highly operable;

[0032] (2) The hydrodeoxygenation catalyst of the present invention has a high deoxygenation efficiency, and has a high deoxygenation efficiency for oxygen-containing hydrocarbon gases. At the same time, it can overcome the influence of 3-chloropropene on the deoxygenation efficiency and also has a high deoxygenation efficiency for oxygen-containing hydrocarbon gases containing 3-chloropropene, with a deoxygenation efficiency of up to 90% or more. This may be because CeO2 itself has strong oxidizing properties, and the oxygen-rich holes CeO2 also have a lot of oxygen vacancies. In addition, the hydrodeoxygenation catalyst is porous. Therefore, the hydrodeoxygenation catalyst of the present invention has excellent oxygen adsorption capacity. The addition of alkali metal and / or alkaline earth metal precursors can improve the electron migration performance of the catalyst during the reaction process. The oxygen migration effect is used to make the hydrodeoxygenation reaction proceed smoothly, thereby reducing the influence of chlorinated hydrocarbons on the hydrodeoxygenation reaction.

[0033] (3) The hydrodeoxygenation catalyst described in this invention also has high deoxygenation efficiency under low temperature treatment conditions, which reduces the energy consumption of the deoxygenation process. Attached Figure Description

[0034] Figure 1 This is a transmission electron microscope (TEM) image of the hydrodeoxygenation catalyst prepared in Example 1. Detailed Implementation

[0035] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0036] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] The present invention provides a hydrodeoxygenation catalyst, the hydrodeoxygenation catalyst comprising oxygen-rich hole CeO2 and a metal active component supported on the oxygen-rich hole CeO2, and optional additives.

[0038] The additive is an alkali metal oxide and / or an alkaline earth metal oxide;

[0039] The active metal component is selected from at least one of Pd oxide, Au oxide, Pt oxide, Ag oxide, Ru oxide, and Rh oxide.

[0040] In this invention, the “oxygen-rich hole CeO2” is an oxygen-rich hole metal oxide, which means that CeO2 has many oxygen vacancies. An oxygen vacancy is a vacancy formed when an oxygen atom (oxygen ion) in the crystal lattice is removed, resulting in oxygen loss.

[0041] In a preferred embodiment, the hydrodeoxygenation catalyst has a porous structure; more preferably, the diameter of the pores is 2-50 nm.

[0042] In a preferred embodiment, to improve deoxygenation efficiency, the weight ratio of the metal active component to the oxygen-rich CeO2 is 0.01-5:100, wherein the metal active component is calculated as a metal element; preferably 0.3-5:100; specifically, it can be 0.3:100, 0.5:100, 0.8:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100 or 5:100.

[0043] In a preferred embodiment, the weight ratio of the additive to the oxygen-enriched CeO2 is 0-5:100, wherein the additive is calculated as a metal element; to further improve the deoxygenation efficiency, the weight ratio of the additive to the oxygen-enriched CeO2 is 1-2:100, wherein the additive is calculated as a metal element; specifically, it can be 1:100, 1.2:100, 1.4:100, 1.6:100, 1.8:100 or 2:100.

[0044] The "oxygen-containing hydrocarbon gas" mentioned in this invention refers to a mixture of oxygen, hydrogen, and hydrocarbon gases. Because such mixtures contain hydrogen and oxygen, they are prone to explosion at high temperatures. Therefore, a hydrodeoxygenation catalyst is used to remove the oxygen. This mixture generally comes from the process of preparing epichlorohydrin from hydrogen peroxide, which means that the mixture may also contain chlorinated hydrocarbons. Existing hydrodeoxygenation catalysts have poor treatment effects on oxygen-containing hydrocarbon gases containing chlorinated hydrocarbons. This is mainly because chlorine can form strong chemical adsorption with metal active centers, thereby increasing the coordination saturation of the metal active centers and reducing the deoxygenation efficiency.

[0045] The hydrodeoxygenation catalyst of this invention has high deoxygenation efficiency, exhibiting high deoxygenation efficiency for oxygen-containing hydrocarbon gases without chlorinated hydrocarbons. It can also overcome the influence of chlorinated hydrocarbons on the deoxygenation effect and has high deoxygenation efficiency for oxygen-containing hydrocarbon gases containing chlorinated hydrocarbons as well. This may be due to the strong oxidizing properties of CeO2 itself, the presence of numerous oxygen vacancies in oxygen-rich CeO2, and the porous nature of the hydrodeoxygenation catalyst. Therefore, the hydrodeoxygenation catalyst of this invention has excellent oxygen adsorption capacity. The addition of alkali metal and / or alkaline earth metal precursors can improve the electron migration performance of the catalyst during the reaction process. The oxygen migration effect facilitates the smooth progress of the hydrodeoxygenation reaction, thereby reducing the influence of chlorinated hydrocarbons on the hydrodeoxygenation reaction.

[0046] In this invention, there are no special limitations on the method for preparing the above-mentioned hydrodeoxygenation catalyst, as long as the above-mentioned hydrodeoxygenation catalyst can be prepared, it is not limited to the preparation method described below in this invention.

[0047] A second aspect of the present invention provides a method for preparing a hydrodeoxygenation catalyst, the method comprising the following steps:

[0048] (1) CeO2 is pretreated with gaseous materials under a protective atmosphere to obtain oxygen-rich vacancy CeO2;

[0049] (2) The precursor solution and the oxygen-rich vacancy CeO2 obtained in step (1) are mixed, and then solid-liquid separation, drying and calcination are performed.

[0050] In step (1), the gaseous material is selected from one or more of ammonia, organic amine vapor and water vapor;

[0051] In step (2), the precursor solution contains a metal-active component precursor and an optional auxiliary agent precursor;

[0052] The metal active component precursor is selected from at least one of Pd precursor, Au precursor, Pt precursor, Ag precursor, Ru precursor and Rh precursor;

[0053] The precursor of the adjuvant is an alkali metal precursor and / or an alkaline earth metal precursor.

[0054] In this invention, the metal active component precursor can be a salt of the corresponding metal, for example, palladium nitrate, sodium chloroaurate, platinum nitrate, silver nitrate, ruthenium trichloride hydrate, or hexachlororhodium salt.

[0055] In a preferred embodiment, the alkali metal in the additive precursor is selected from at least one of Li, Na, and K; the alkaline earth metal in the additive precursor is selected from at least one of Mg, Ca, Ba, and Sr.

[0056] In this invention, the precursor of the auxiliary agent can be an alkali metal salt or an alkaline earth metal salt. For example, the alkali metal salt can be lithium chloride, sodium chloride, sodium nitrate, potassium chloride, or potassium nitrate; the alkaline earth metal salt can be magnesium nitrate, calcium nitrate, barium nitrate, or strontium nitrate.

[0057] In this invention, in step (1), the protective atmosphere is selected from nitrogen atmosphere, helium atmosphere, neon atmosphere or argon atmosphere.

[0058] In this invention, in step (1), ammonia can be used directly to pretreat CeO2, or ammonia, organic amine and water vapor can be generated by vaporizing a substance that can be vaporized to produce ammonia, organic amine and water vapor to pretreat CeO2.

[0059] In a preferred embodiment, the vaporization temperature is 180-220°C; preferably 190-220°C.

[0060] In a specific implementation, the substance that can be vaporized to produce ammonia can be ammonia water, ammonium chloride, or ammonium nitrate.

[0061] In a specific embodiment, the organic amine may be ethylenediamine, diethylamine, triethylamine, or 1,6-hexanediol.

[0062] In this invention, in step (1), CeO2 is pretreated by introducing gaseous material to obtain oxygen-rich vacuoles CeO2.

[0063] In a preferred embodiment, the flow rate of the gaseous material is 5-40 mL / min; specifically, the flow rate of the gaseous material can be 5 mL / min, 10 mL / min, 15 mL / min, 20 mL / min, 25 mL / min, 30 mL / min, 35 mL / min or 40 mL / min.

[0064] In a preferred embodiment, in order to improve the oxygen adsorption capacity of oxygen-rich cavities CeO2 and improve the deoxygenation efficiency, in step (1), the volume ratio of the gaseous material to the weight of the CeO2 is 10-100 mL: 1 g; preferably 30-100 mL: 1 g; specifically, the volume ratio of the gaseous material to the weight of the CeO2 can be 30 mL: 1 g, 40 mL: 1 g, 50 mL: 1 g, 60 mL: 1 g, 70 mL: 1 g, 80 mL: 1 g, 90 mL: 1 g or 100 mL: 1 g.

[0065] In a preferred embodiment, in order to further improve the deoxygenation efficiency, the pretreatment conditions in step (1) include: a temperature of 300-800℃, a pressure of 0.1-0.5MPa, and a time of 1-10h; preferably, the temperature is 500-800℃, the pressure is 0.3-0.5MPa, and the time is 3-10h.

[0066] In the method for preparing a hydrodeoxygenation catalyst according to the present invention, in step (1), the "pressure" in the pretreatment conditions is absolute pressure.

[0067] In a preferred embodiment, in step (2), the solvent of the precursor solution is water. The precursor solution is obtained by mixing water, a metal active component precursor, and an optional auxiliary agent precursor. There are no special requirements for the amount of water used, as long as it can dissolve the metal active component precursor. Then, the oxygen-rich vacancy CeO2 obtained in step (1) is impregnated into the precursor solution, and then solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. More preferably, the impregnation method is equal volume impregnation.

[0068] In a preferred embodiment, to further improve the deoxygenation efficiency, in step (2), the weight ratio of the metal active component precursor to the oxygen-rich hole CeO2 is 0.01-5:100, wherein the metal active component precursor is calculated as a metal element; preferably 0.3-5:100; specifically, it can be 0.3:100, 0.5:100, 0.8:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100 or 5:100.

[0069] In a preferred embodiment, the weight ratio of the auxiliary precursor to the oxygen-enriched CeO2 is 0-5:100, wherein the auxiliary precursor is calculated as a metal element. To further improve the deoxygenation efficiency, the weight ratio of the auxiliary precursor to the oxygen-enriched CeO2 is 2-4:100.

[0070] In this invention, there are no special requirements for the method and conditions of solid-liquid separation and drying; any method and conditions conventionally used in the art for solid-liquid separation and drying are acceptable.

[0071] In a preferred embodiment, in step (2), the calcination conditions include: a temperature of 400-600℃ and a time of 3-10h; specifically, the temperature can be 400℃, 450℃, 500℃, 550℃ or 600℃; and the time can be 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.

[0072] The hydrodeoxygenation catalyst prepared by the above method has high deoxygenation efficiency and can also reduce the influence of strong chemisorption between chlorinated hydrocarbons and metal active centers, which increases the coordination saturation of metal active centers. This may be because CeO2 itself has strong oxidizing properties, and the above-mentioned gaseous materials etch CeO2, making it rich in oxygen holes. In addition, the hydrodeoxygenation catalyst is porous. Therefore, the hydrodeoxygenation catalyst of the present invention has excellent oxygen adsorption capacity. The addition of alkali metal and / or alkaline earth metal precursors can improve the electron migration performance of the catalyst during the reaction process. The oxygen migration effect enables the hydrodeoxygenation reaction to proceed smoothly, thereby improving the hydrogen-oxygen reaction activity and reducing the influence of chlorinated hydrocarbons on the hydrodeoxygenation reaction.

[0073] A third aspect of the present invention provides a hydrodeoxygenation catalyst prepared by the above method.

[0074] The fourth aspect of the present invention provides the application of the above-mentioned hydrodeoxygenation catalyst in oxygen-containing hydrocarbon gases.

[0075] The hydrodeoxygenation catalyst described in this invention is not only suitable for ordinary oxygen-containing hydrocarbon gases, but also has a good deoxygenation efficiency for oxygen-containing hydrocarbon gases containing chlorinated hydrocarbons. At the same time, the hydrodeoxygenation catalyst can also deoxygenate oxygen-containing hydrocarbon gases containing H2S, CO or HCl.

[0076] The fifth aspect of the present invention provides a method for treating oxygen-containing hydrocarbon gases, wherein the oxygen-containing hydrocarbon gases are contacted with a catalyst;

[0077] The catalyst is the aforementioned hydrodeoxygenation catalyst.

[0078] In a preferred embodiment, the content of chlorinated hydrocarbons in the oxygen-containing hydrocarbon gas is ≤5 vol%. In a specific embodiment, the chlorinated hydrocarbon is 3-chloropropene.

[0079] In a preferred embodiment, the contact conditions include an airspeed of 500-9000 h⁻¹. -1 The pressure is 0.1-1.5 MPa, and the temperature is 150-250℃; preferably, the space velocity is 2000-9000 h⁻¹. -1 The pressure is 0.3-1.5MPa and the temperature is 200-250℃.

[0080] In the method for processing oxygen-containing hydrocarbon gases according to the present invention, the "pressure" in the contact conditions refers to relative pressure.

[0081] The following examples further illustrate the hydrodeoxygenation catalyst, its preparation method, and its applications according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0082] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0083] Example 1

[0084] Preparation of hydrodeoxygenation catalyst A1:

[0085] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0086] (2) Water, palladium nitrate and potassium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched CeO2 obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-enriched CeO2 is 0.3:100, and the weight ratio of potassium chloride (calculated as metallic potassium) to oxygen-enriched CeO2 is 2:100. The calcination conditions are: temperature 500℃ and time 5h.

[0087] Example 2

[0088] Preparation of hydrodeoxygenation catalyst A2:

[0089] (1) Ethylenediamine was vaporized at 200℃. Under a nitrogen atmosphere, 10g of CeO2 powder was pretreated by passing the vaporized ethylenediamine at a rate of 5ml / min. The pretreatment conditions were: temperature 550℃, pressure 0.3MPa, time 3h. Then the organic amine was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich cavitation CeO2.

[0090] (2) Water, palladium nitrate, sodium nitrate and magnesium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched vacuoles CeO2 obtained in step (1) are impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-enriched vacuoles CeO2 is 1:100. The total weight ratio of the auxiliary precursor (calculated as metal) to the weight ratio of oxygen-enriched vacuoles CeO2 is 4:100. The weight ratio of auxiliary precursor sodium nitrate (calculated as metallic sodium) to auxiliary precursor magnesium chloride (calculated as metallic magnesium) is 1:1. The calcination conditions are: temperature 500℃, time 5h.

[0091] Example 3

[0092] Preparation of hydrodeoxygenation catalyst A3:

[0093] (1) Diethylamine was vaporized at 200℃. Under an argon atmosphere, 10g of CeO2 powder was pretreated by passing the generated diethylamine vapor through the gas at a rate of 25ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 5h. Then the organic amine was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0094] (2) Water, chloroplatinic acid, potassium nitrate and magnesium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched vacuoles CeO2 obtained in step (1) are impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of chloroplatinic acid (calculated as platinum metal) to oxygen-enriched vacuoles CeO2 is 1:100. The total weight ratio of the auxiliary precursor (calculated as metal) to the weight ratio of oxygen-enriched vacuoles CeO2 is 4:100. The weight ratio of auxiliary precursor potassium nitrate (calculated as potassium metal) to auxiliary precursor magnesium chloride (calculated as magnesium metal) is 2:8. The calcination conditions are: temperature 550℃ and time 5h.

[0095] Example 4

[0096] Preparation of hydrodeoxygenation catalyst A4:

[0097] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 30ml / min. The pretreatment conditions were: temperature 500℃, pressure 0.3MPa, time 5h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0098] (2) Water, chloroauric acid and magnesium nitrate are mixed to obtain a precursor solution. Then, the oxygen-enriched CeO2 obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of chloroauric acid (calculated as metallic gold) to oxygen-enriched CeO2 is 1:100, and the weight ratio of magnesium nitrate (calculated as metallic magnesium) to oxygen-enriched CeO2 is 3:100. The calcination conditions are: temperature 600℃ and time 4h.

[0099] Example 5

[0100] Preparation of hydrodeoxygenation catalyst A5:

[0101] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 20ml / min. The pretreatment conditions were: temperature 500℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0102] (2) Water, silver nitrate and potassium carbonate are mixed to obtain a precursor solution. Then, the oxygen-enriched vacuoles CeO2 obtained in step (1) are impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of silver nitrate (calculated as metallic silver) to oxygen-enriched vacuoles CeO2 is 5:100, and the weight ratio of potassium carbonate (calculated as metallic potassium) to oxygen-enriched vacuoles CeO2 is 4:100. The calcination conditions are: temperature 500℃ and time 5h.

[0103] Example 6

[0104] Preparation of hydrodeoxygenation catalyst A6:

[0105] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by passing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 3h. Then the organic amine was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0106] (2) Water and palladium nitrate are mixed to obtain a precursor solution. Then, the oxygen-rich hole CeO2 obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-rich hole CeO2 is 0.3:100. The calcination conditions are: temperature of 500℃ and time of 5h.

[0107] Example 7

[0108] Preparation of hydrodeoxygenation catalyst A7:

[0109] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 200℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich cavitary CeO2.

[0110] (2) Water, palladium nitrate and potassium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched CeO2 obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-enriched CeO2 is 0.3:100, and the weight ratio of potassium chloride (calculated as metallic potassium) to oxygen-enriched CeO2 is 2:100. The calcination conditions are: temperature 500℃ and time 5h.

[0111] Example 8

[0112] Preparation of hydrodeoxygenation catalyst A8:

[0113] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0114] (2) Water, palladium nitrate and potassium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched CeO2 obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-enriched CeO2 is 0.005:100, and the weight ratio of potassium chloride (calculated as metallic potassium) to oxygen-enriched CeO2 is 2:100. The calcination conditions are: temperature 500℃ and time 5h.

[0115] Comparative Example 1

[0116] Preparation of hydrodeoxygenation catalyst A10:

[0117] A precursor solution was prepared by mixing water, palladium nitrate, and potassium chloride. CeO2 was then impregnated into the precursor solution in an equal-volume impregnation manner. Solid-liquid separation was then performed, and the resulting solid material was dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to CeO2 was 0.3:100, and the weight ratio of potassium chloride (calculated as metallic potassium) to CeO2 was 2:100. The calcination conditions were: temperature 500℃ and time 5h.

[0118] Comparative Example 2

[0119] Preparation of hydrodeoxygenation catalyst A11:

[0120] (1) Under a nitrogen atmosphere, 10g CeO2 powder was pretreated by introducing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacuoles CeO2.

[0121] (2) Water and potassium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched vacuoles CeO2 obtained in step (1) are impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of potassium chloride (calculated as metallic potassium) to the weight of oxygen-enriched vacuoles CeO2 is 2:100. The calcination conditions are: temperature of 500℃ and time of 5h.

[0122] Comparative Example 3

[0123] Preparation of hydrodeoxygenation catalyst A12:

[0124] (1) Under nitrogen atmosphere, 10g of titanium dioxide powder was pretreated by passing ammonia gas at a rate of 5ml / min. The pretreatment conditions were: temperature 600℃, pressure 0.3MPa, time 3h. Then the ammonia gas was stopped and the temperature was lowered to room temperature (20℃) to obtain oxygen-rich vacant titanium dioxide.

[0125] (2) Water, palladium nitrate and potassium chloride are mixed to obtain a precursor solution. Then, the oxygen-enriched vacant titanium dioxide obtained in step (1) is impregnated into the precursor solution by equal volume impregnation. Then, solid-liquid separation is performed. The solid material obtained after solid-liquid separation is dried and calcined. The weight ratio of palladium nitrate (calculated as metallic palladium) to oxygen-enriched vacant titanium dioxide is 0.3:100, and the weight ratio of potassium chloride (calculated as metallic potassium) to oxygen-enriched vacant titanium dioxide is 2:100. The calcination conditions are: temperature of 500℃ and time of 5h.

[0126] Test case

[0127] (1) The structure of the hydrodeoxygenation catalyst prepared in Example 1 was characterized by transmission electron microscopy, and the results are as follows: Figure 1 As shown;

[0128] Depend on Figure 1 It is known that the hydrodeoxygenation catalyst of the present invention has a porous structure with a pore diameter of 2-50 nm.

[0129] (2) The content of active components in the hydrodeoxygenation catalysts prepared in the examples and comparative examples was determined, and the test results are shown in Table 1.

[0130] (3) The catalytic performance of the hydrodeoxygenation catalysts prepared in the examples and comparative examples was tested as follows: the hydrodeoxygenation catalyst was contacted with an oxygen-containing hydrocarbon gas containing 3-chloropropene, and the contact conditions were: space velocity of 2000 h⁻¹. -1 The pressure was 0.3 MPa and the temperature was 240 °C. The composition of the oxygen-containing hydrocarbon gas containing 3-chloropropene was: 2 vol% O2, 4.5 vol% H2, 1 vol% 3-chloropropene, and the remainder was methane. The test results are shown in Table 1.

[0131] Table 1

[0132]

[0133]

[0134] As can be seen from the results in Table 1, the hydrodeoxygenation catalyst of the present invention has a high deoxygenation efficiency in the hydrodeoxygenation process and its operation stability is also more durable, with a deoxygenation efficiency of up to 90% or more and an operation stability of up to 600 hours or more.

[0135] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrodeoxygenation catalyst, characterized in that, The hydrogen deoxygenation catalyst comprises oxygen-rich hole CeO2 and a metal active component supported on the oxygen-rich hole CeO2, as well as optional additives. The additive is an alkali metal oxide and / or an alkaline earth metal oxide; The active metal component is selected from at least one of Pd oxide, Au oxide, Pt oxide, Ag oxide, Ru oxide, and Rh oxide.

2. The hydrodeoxygenation catalyst according to claim 1, characterized in that, The hydrodeoxygenation catalyst has a porous structure; Preferably, the diameter of the pore is 2-50 nm.

3. The hydrodeoxygenation catalyst according to claim 1 or 2, characterized in that, The weight ratio of the metal active component to the oxygen-rich hole CeO2 is 0.01-5:100, wherein the metal active component is calculated as a metal element.

4. The hydrodeoxygenation catalyst according to any one of claims 1-3, characterized in that, The weight ratio of the additive to the oxygen-rich hole CeO2 is 0-5:100, wherein the additive is calculated as a metal element.

5. A method for preparing a hydrodeoxygenation catalyst, characterized in that, The method includes the following steps: (1) CeO2 is pretreated with gaseous materials under a protective atmosphere to obtain oxygen-rich vacancy CeO2; (2) The precursor solution and the oxygen-rich vacancy CeO2 obtained in step (1) are mixed, and then solid-liquid separation, drying and calcination are performed. In step (1), the gaseous material is selected from at least one of ammonia, organic amine vapor, and water vapor; In step (2), the precursor solution contains a metal-active component precursor and an optional auxiliary agent precursor; The metal active component precursor is selected from at least one of Pd precursor, Au precursor, Pt precursor, Ag precursor, Ru precursor and Rh precursor; The precursor of the adjuvant is an alkali metal precursor and / or an alkaline earth metal precursor.

6. The method according to claim 5, characterized in that, In step (1), the volume ratio of the gaseous material to the weight of CeO2 is 80-1000 mL: 1 g.

7. The method according to claim 5 or 6, characterized in that, In step (1), the pretreatment conditions include: temperature of 300-800℃, pressure of 0.1-0.5MPa, and time of 1-10h.

8. The method according to any one of claims 5-7, characterized in that, In step (2), the weight ratio of the metal active component precursor to the oxygen-rich hole CeO2 is 0.01-5:100, wherein the metal active component precursor is calculated as a metal element.

9. The method according to claim 8, characterized in that, In step (2), the weight ratio of the auxiliary precursor to the oxygen-rich hole CeO2 is 0-5:100, wherein the auxiliary precursor is calculated as a metal element.

10. The method according to claim 9, characterized in that, In step (2), the calcination conditions include a temperature of 400-600℃ and a time of 3-10h.

11. The hydrodeoxygenation catalyst prepared by the method of any one of claims 5-10.

12. The use of the hydrodeoxygenation catalyst according to any one of claims 1-4 and 11 in the treatment of oxygen-containing hydrocarbon gases.

13. A method for treating oxygen-containing hydrocarbon gases, characterized in that, Contacting oxygen-containing hydrocarbon gases with the catalyst; The catalyst is the hydrodeoxygenation catalyst according to any one of claims 1-4 and 11.

14. The method according to claim 13, characterized in that, The conditions for contact include: an airspeed of 500-9000 h⁻¹. -1 The pressure is 0.1-1.5MPa and the temperature is 150-250℃.

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