Nickel-based catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalyst preparation, and discloses a nickel-based catalyst as well as a preparation method and application thereof. The nickel-based catalyst contains a carrier, an active component and an auxiliary agent, the active component is Ni elementary substance and nickel oxide; the auxiliary agent is selected from one or more than two of oxides of Zn, Na, Mg, Zr, K and Cu; and the nickel oxide compound is selected from one or more than two of NiO, Ni3O4 and Ni2O3. The nickel-based catalyst has bifunctional activity, and can promote activation of hydrogen while promoting oxygen adsorption, so that the catalytic activity of the nickel-based catalyst is further improved, and the deoxidation efficiency of the catalyst is improved.

Description

Technical Field

[0001] The invention relates to the technical field of catalyst preparation, and in particular to a nickel-based catalyst and a preparation method and application thereof. Background Art

[0002] Catalytic oxidation reaction is one of the most common chemical reactions in the chemical production process. The incomplete reaction of raw materials (low-carbon hydrocarbons) and oxidants (air, oxygen, ozone, etc.) causes a large amount of oxidants to be enriched in the recycling of raw materials, which in turn leads to a great risk of explosion in the chemical production process. The "Petrochemical Combustible Gas Emission System Design Specification" stipulates that combustible gases with an oxygen content greater than 2% (v%) should not be discharged into the plant's combustible gas emission system, so the efficient treatment of oxygen in oxygen-containing tail gas has become a key issue that needs to be solved urgently.

[0003] At present, the main treatment method for raw gas containing hydrocarbon gas and oxygen is to dilute and discharge with inert gas, which not only increases the operating cost (consumption of a large amount of nitrogen) but also pollutes the environment with VOCs emissions. In recent years, catalytic oxidation has been widely studied due to its great advantages in economy, environmental protection, energy saving, etc. However, the catalysts commonly used in catalytic oxidation are precious metal (Pt, Pd, Au, Ir or Ru) catalysts, the raw materials are expensive, and there are still problems such as low deep deoxygenation efficiency. Therefore, the development of non-precious metal catalysts with high catalytic oxidation activity has received extensive attention from researchers.

[0004] Patent CN101745391B discloses a catalyst for removing trace oxygen from catalytic cracking dry gas, wherein the catalytic active component is composed of a main catalytic active component and a co-catalytic active component, wherein the main catalytic active component is precious metal palladium, the co-catalytic active component is selected from one or more of Ag, Au, Co, and Cr, and the carrier is selected from alumina, activated carbon, silicon oxide, or molecular sieve. However, the catalyst can only deoxygenate high-hydrogen dry gas, and can only react with trace oxygen under high reaction pressure (2.0 MPa) and high hydrogen content to achieve deep deoxygenation effect.

[0005] In terms of the preparation of deoxygenation catalysts, most of the catalysts reported so far are concentrated on precious metal catalysts. However, precious metals are expensive and scarce, and cannot be promoted on a large scale in the field of olefin deoxygenation. In addition, the deoxygenation efficiency of existing olefin deoxygenation catalysts is low, which seriously limits the large-scale commercialization of catalytic oxidation methods. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems existing in the prior art in the field of olefin deoxygenation, such as low deoxygenation efficiency of deoxygenation catalysts and high price of precious metal catalysts, and to provide a nickel-based catalyst and a preparation method and application thereof. The nickel-based catalyst has bifunctional activity, which can promote the activation of hydrogen while promoting the adsorption of oxygen, thereby further improving the catalytic activity of the nickel-based catalyst and improving the deoxygenation efficiency of the catalyst.

[0007] In order to achieve the above object, the present invention provides a nickel-based catalyst on one hand, wherein the nickel-based catalyst comprises a carrier, an active component and an additive;

[0008] The active components are Ni element and nickel oxide compound;

[0009] The nickel oxide compound is selected from NiO, Ni 3 O 4 and Ni 2 O 3 One or more of the following:

[0010] The auxiliary agent is selected from one or more oxides of Zn, Na, Mg, Zr, K and Cu.

[0011] Preferably, the molar ratio of Ni element to nickel oxide in the active component is 0.2-5:1.

[0012] Preferably, the active component is a combination of Ni and NiO, and the molar ratio of Ni to NiO is 1-2:1; or

[0013] The active components are Ni element and Ni 3 O 4 The combination of Ni and Ni 3 O 4 The molar ratio is 0.2-5:1; or

[0014] The active components are Ni element and Ni 2 O 3 The combination of Ni and Ni 2 O 3 The molar ratio is 0.4-5:1; or

[0015] The active components are Ni element, NiO and Ni 2 O 3 When Ni single substance, NiO and Ni 2 O 3 The molar ratio of is 0.4-4:0.4-8:1; or

[0016] The active components are Ni element, NiO and Ni 3 O 4When Ni single substance, NiO and Ni 3 O 4 The molar ratio of is 0.5-5:0.5-6:1; or

[0017] The active components are Ni element, Ni 3 O 4 and Ni 2 O 3 When Ni single substance, Ni 3 O 4 and Ni 2 O 3 The molar ratio is 0.25-4:0.25-4:1.

[0018] Preferably, the carrier is selected from Al 2 O 3 、SiO 2 , one or more of activated carbon and molecular sieve.

[0019] A second aspect of the present invention provides a method for preparing a nickel-based catalyst, the method comprising the following steps:

[0020] (1) immersing the support in a solution containing a nickel source and an additive precursor, followed by solid-liquid separation;

[0021] (2) calcining the solid phase obtained in step (1), and then reducing the calcined product.

[0022] Preferably, the calcination conditions include: temperature of 300-550° C. and time of 3-6 h.

[0023] Preferably, the reduction conditions include: temperature of 200-500° C., time of 3-12 h, and pressure of 0.1-0.25 MPa.

[0024] Preferably, the heating rate of the reduction process is 2-15°C / min.

[0025] Preferably, the auxiliary agent precursor is selected from one or more of Zn salt, Na salt, Mg salt, Zr salt, K salt and Cu salt.

[0026] Preferably, the carrier is selected from Al 2 O 3 、SiO 2 , one or more of activated carbon and molecular sieve.

[0027] Preferably, the reducing gas used in the reduction process is H 2 , H 2 Mixed gas with protective gas or H 2 Mixed gas with CO;

[0028] Preferably, the H 2 H in the mixed gas with the protective gas 2 The content is 5-20vol%.

[0029] Preferably, the molar ratio of the nickel source, the auxiliary agent precursor and the carrier is 20:1-5:100, wherein the nickel source and the auxiliary agent precursor are calculated as metal elements.

[0030] The third aspect of the present invention provides a nickel-based catalyst prepared by the above method.

[0031] A fourth aspect of the present invention provides a use of the above nickel-based catalyst in removing oxygen.

[0032] A fifth aspect of the present invention provides a method for deoxygenating olefins, the method comprising: mixing a feed gas containing hydrocarbon gas and oxygen with hydrogen, and then mixing and contacting the obtained mixed gas with a catalyst to perform a deoxygenation reaction;

[0033] Wherein, the content of hydrogen in the mixed gas is 0.1-1 vol%, the content of oxygen in the raw gas is 0.1-0.5 vol%; and the catalyst is the above-mentioned nickel-based catalyst.

[0034] Preferably, the pressure of the deoxygenation reaction is 0.1-0.3 MPa.

[0035] The active components of the nickel-based catalyst of the present invention are a composite of metal element Ni and nickel oxide. The non-precious metal Ni-based catalyst is used as a precursor. By effectively controlling the composition of the active components of the catalyst and the ratio of nickel element to nickel oxide in the active components, a bifunctional Ni-Ni catalyst surface is efficiently constructed. x O y The active phase enables the nickel-based catalyst of the present invention to not only promote the adsorption of oxygen in the catalytic oxidation reaction of olefins, but also promote the activation of hydrogen by the nickel-based catalyst, and at the same time has a higher H 2 Activation capacity and O 2 Adsorption-activation ability, thus further promoting the combination of oxygen and hydrogen in the raw gas to achieve the purpose of deep deoxygenation;

[0036] In addition, the auxiliary agent used in the nickel-based catalyst of the present invention can maintain the phase structure of the active component, and can also increase the content of the active phase through electron exchange between the auxiliary agent and the active component, thereby further improving the catalytic activity of the catalyst, that is, improving the deoxidation efficiency of the nickel-based catalyst;

[0037] The nickel-based catalyst of the present invention requires a lower reaction pressure when removing oxygen from the raw gas (a mixed gas containing hydrocarbon gas and oxygen), and also reduces the requirement for hydrogen concentration. The required hydrogen content is low, which further prevents the occurrence of side reactions such as hydrogen and hydrocarbon gas during the deoxygenation process, while improving the denitration efficiency of the raw gas and further reducing the oxygen content in the tail gas after the final treatment.

[0038] Furthermore, the raw material used for the nickel-based catalyst described in the present invention is nickel-based metal, which greatly reduces the cost of raw materials compared to precious metals Pt or Pd, and at the same time has excellent deoxidation efficiency, which is more convenient for industrial promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 Schematic diagram of the nickel-based catalyst of the present invention. DETAILED DESCRIPTION

[0040] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0041] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0042] In the present invention, unless otherwise specified, "space velocity" refers to "volume space velocity"; and pressure refers to absolute pressure.

[0043] The present invention provides a nickel-based catalyst, the specific structure of which is shown in FIG. Figure 1 The nickel-based catalyst comprises a carrier, an active component and an auxiliary agent (not shown in the figure). The active component and the auxiliary agent are attached to the surface of the carrier.

[0044] In the present invention, the active components of the nickel-based catalyst are Ni and nickel oxide, and the nickel oxide is selected from NiO, Ni 3 O 4 and Ni 2 O 3 By adjusting the ratio of Ni element and nickel oxide in the active component and the type of the active component, the surface of the nickel-based catalyst is provided with a bifunctional active phase, which can promote the activation of hydrogen while promoting the adsorption of oxygen, thereby improving the deoxidation efficiency of the catalyst.

[0045] In the nickel-based catalyst of the present invention, the auxiliary agent is selected from one or more oxides of Zn, Na, Mg, Zr, K and Cu, and specifically, the auxiliary agent is in the form of metal oxides. The auxiliary agent increases the content of the active component by exchanging electrons with the active component, maintains the configuration of the active component, and improves the catalytic activity of the nickel-based catalyst.

[0046] In the nickel-based catalyst of the present invention, the molar ratio of the carrier, the active component and the auxiliary agent is 100:20:1-5, wherein the active component and the auxiliary agent are both calculated as metal elements.

[0047] In a preferred embodiment, the molar ratio of Ni element and nickel oxide in the active component is 0.2-5: 1, preferably 0.21-3: 1. Specifically, the molar ratio of Ni element and nickel oxide in the active component can be 0.2: 1, 0.22: 1, 0.25: 1, 0.4: 1, 0.5: 1, 0.6: 1, 1: 1, 1.5: 1, 2: 1, 2.5: 1 or 3: 1.

[0048] In a preferred embodiment, the active component is a combination of Ni and NiO, and the molar ratio of Ni to NiO is 1-2: 1, preferably 1.2-1.8: 1, and more preferably 1.5: 1. Specifically, the molar ratio of Ni to NiO in the active component can be 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.7: 1 or 1.8: 1.

[0049] In a preferred embodiment, the active components are Ni element and Ni 3 O 4 The combination of Ni and Ni 3 O 4 The molar ratio of Ni and Ni in the active component is 0.2-5:1, preferably 0.5-3:1, and more preferably 0.6-2.5:1. 3 O 4 The molar ratio may be 0.5:1, 0.6:1, 0.7:1, 1:1, 1.5:1, 2:1 or 3:1.

[0050] In a preferred embodiment, the active components are Ni element and Ni 2 O 3 The combination of Ni and Ni 2 O 3 The molar ratio of Ni and Ni in the active component is 0.4-5:1, preferably 0.7-3:1, and more preferably 0.75-2.5:1. 2 O 3The molar ratio of may be 0.7:1, 1:1, 1.5:1, 1.6:1, 2:1, 2.5:1 or 3:1.

[0051] In a preferred embodiment, the active components are Ni element, NiO and Ni 2 O 3 When Ni single substance, NiO and Ni 2 O 3 The molar ratio of Ni:NiO and Ni in the active component is 0.4-4:0.4-8:1, preferably 0.4-2:1-3:1, and more preferably 0.5-1:1.5-2.5:1. 2 O 3 The molar ratio may be 0.5:1.5:1, 0.5:2:1, 0.8:1.5:1 or 1:2.5:1.

[0052] In a preferred embodiment, the active components are Ni element, NiO and Ni 3 O 4 When Ni single substance, NiO and Ni 3 O 4 The molar ratio of Ni:NiO and Ni in the active component is 0.5-5:0.5-6:1, preferably 1-3:1-4:1, and more preferably 1.5-2.5:2-4:1. 3 O 4 The molar ratio may be 1.5:2:1, 2:3:1, 2.5:3.5:1 or 2.5:4:1.

[0053] In a preferred embodiment, the active component is Ni element, Ni 3 O 4 and Ni 2 O 3 When Ni single substance, Ni 3 O 4 and Ni 2 O 3 The molar ratio of Ni and Ni in the active component is 0.25-4:0.25-4:1, preferably 0.5-1.5:0.3-2:1, and more preferably 0.55-1.2:0.3-1.5:1. 3 O 4 and Ni 2 O 3 The molar ratio may be 0.5:0.3:1, 0.5:0.5:1, 1:1:1 or 1.5:2:1.

[0054] In the nickel-based catalyst described in the present invention, the Ni element and nickel oxide in the active components form a composite active center. Compared with a single active center catalyst, it has more catalytic active sites and more functions. It can promote the adsorption of oxygen and the activation of hydrogen in the catalytic deoxygenation of olefins, thereby comprehensively improving the deoxygenation efficiency of the catalyst.

[0055] In the nickel-based catalyst of the present invention, the carrier can be selected from common carriers in the art. In a preferred embodiment, the carrier is selected from Al 2 O 3 、SiO 2 , activated carbon and molecular sieves. Specifically, the activated carbon may be conventional activated carbon in the art, and the molecular sieve may be selected from at least one of a HZSM-5 molecular sieve carrier, a 4A molecular sieve carrier, a MCM-22 molecular sieve carrier and a Y-type molecular sieve carrier.

[0056] According to some embodiments of the present invention, the nickel-based catalyst comprises a carrier and an active component and an additive supported on the carrier. The active component is a single substance of Ni and NiO, Ni 3 O 4 and Ni 2 O 3 At least one of the following; the auxiliary agent is selected from one or more of the oxides of Zn, Na, Mg, Zr, K and Cu; the carrier is selected from Al 2 O 3 、SiO 2 , one or more of activated carbon and molecular sieve.

[0057] According to some other embodiments of the present invention, the nickel-based catalyst comprises a carrier and an active component and an additive supported on the carrier. The active component is a single substance of Ni and NiO, Ni 3 O 4 and Ni 2 O 3 At least one of the following; the auxiliary agent is selected from one or more of the oxides of Zn, Na, Mg, Zr, K and Cu; the carrier is selected from Al 2 O 3 、SiO 2 , activated carbon and molecular sieve. In the nickel-based catalyst, the weight ratio of the carrier, the active component and the auxiliary agent is 100:20:1-5, wherein the active component and the auxiliary agent are both calculated as metal elements.

[0058] The present invention also provides a method for preparing the above nickel-based catalyst, the method comprising the following steps:

[0059] (1) immersing the support in a solution containing a nickel source and an additive precursor, followed by solid-liquid separation;

[0060] (2) calcining the solid phase obtained in step (1), and then reducing the calcined product.

[0061] In a specific embodiment, before the support is immersed in the solution containing the nickel source and the auxiliary agent precursor, the nickel source and the auxiliary agent precursor may be dissolved in water to obtain a solution containing the nickel source and the auxiliary agent precursor.

[0062] In a preferred embodiment, in step (1), the impregnation method can be excess impregnation, distributed impregnation or equal volume impregnation.

[0063] In a preferred embodiment, the nickel source is selected from NiCl 2 orNi(NO 3 ) 2 .

[0064] In a preferred embodiment, the auxiliary agent precursor is a soluble salt, preferably one or more selected from Zn salt, Na salt, Mg salt, Zr salt, K salt and Cu salt. Specifically, the auxiliary agent precursor is selected from Zn(NO 3 ) 2 、NaNO 3 Mg(NO 3 ) 2 、Zr(NO 3 ) 4 、KNO 3 and Cu(NO 3 ) 2 One or more of the following.

[0065] In a preferred embodiment, the carrier is selected from Al 2 O 3 、SiO 2 , one or more of activated carbon and molecular sieve.

[0066] In some embodiments, in the nickel-based catalyst, the weight ratio of the carrier, the active component and the auxiliary agent is 100:20:1-5, wherein the active component and the auxiliary agent are both calculated as metal elements.

[0067] In a specific embodiment, in step (1), the solid phase obtained after solid-liquid separation needs to be dried at a temperature of 80-120° C. for a drying time of 8-15 h.

[0068] In a specific embodiment, in order to further improve the catalytic performance of the nickel-based catalyst finally prepared, in step (2), the calcination conditions include: a temperature of 300-550°C, preferably 400-550°C; a time of 3-6h, preferably 3.5-5.5h. Specifically, the calcination temperature can be 300°C, 350°C, 400°C, 450°C, 500°C or 550°C; and the calcination time can be 3h, 4h, 5h or 6h.

[0069] In the present invention, the calcined material is subjected to reduction treatment, and the conditions of the reduction process are further controlled so that the surface of the nickel-based catalyst has a bifunctional Ni metal element and a Ni oxide active center, and the catalytic activity of the active component is further regulated by controlling the composition of the Ni oxide in the active component and the content ratio between the Ni metal element and the Ni oxide, so that the nickel-based catalyst of the present invention can promote the adsorption of oxygen and the activation of hydrogen, thereby further promoting the reaction between oxygen and hydrogen in the raw gas, improving the deoxidation effect of the nickel-based catalyst, and achieving deep deoxidation of the raw gas.

[0070] In the present invention, the auxiliary agent conducts electron flow with the active component during the calcination and reduction process, promotes the formation of the active phase and increases the content of the active component, and further maintains the configuration of the active component, etc., further improving the catalytic activity of the nickel-based catalyst, thereby improving the deoxygenation efficiency of the nickel-based catalyst in the catalytic oxidation of olefins.

[0071] In a preferred embodiment, in order to further improve the deoxidation efficiency of the nickel-based catalyst, the reduction conditions include: a temperature of 200-500°C, preferably 350-450°C; a time of 3-12h, preferably 6-10h; and a pressure of 0.1-0.25MPa. Specifically, the temperature during the reduction can be 200°C, 300°C, 400°C or 500°C; the time of the reduction can be 3h, 5h, 8h, 10h or 12h; and the pressure during the reduction can be 0.1MPa, 0.15MPa, 0.18MPa, 0.2MPa, 0.23MPa or 0.25MPa.

[0072] In a preferred embodiment, in order to further improve the catalytic efficiency of the nickel-based catalyst, the heating rate of the reduction process is controlled to be 2-15°C / min, more preferably 3-10°C / min. The heating rate of the reduction process refers to the heating rate of the process of raising the ambient temperature of the material to the reduction target temperature during the reduction process. Specifically, the heating rate of the reduction process can be 2°C / min, 5°C / min, 6°C / min, 8°C / min, 10°C / min, 12°C / min or 15°C / min.

[0073] In the present invention, the reducing gas used in the reduction process is H 2 , H 2 Mixed gas with protective gas or H 2 and CO; specifically, the reducing gas may be pure H 2 , H 2 Mixed gas with protective gas or H 2 Mixture with CO.

[0074] In a preferred embodiment, when the reducing gas is H 2 When the mixed gas is H 2 The content of H in the reducing gas is 5-20 vol%, preferably 5-15 vol%. 2 The content of may be 5 vol%, 10 vol%, 15 vol% or 20 vol%.

[0075] In a specific embodiment, the molar ratio of the nickel source, the auxiliary agent precursor and the carrier is 20:1-5:100, wherein the nickel source and the auxiliary agent precursor are calculated as metal elements.

[0076] The present invention further provides a nickel-based catalyst prepared by the above preparation method.

[0077] The present invention can also provide an application of the nickel-based catalyst in removing oxygen. Preferably, the nickel-based catalyst is used to remove oxygen from a raw gas containing hydrocarbon gas and oxygen by catalytic oxidation, wherein the oxygen content in the raw gas is 0.1-0.5 vol%.

[0078] The present invention can also provide a method for deoxygenating olefins, which comprises: mixing a raw gas containing hydrocarbon gas and oxygen with hydrogen, and then mixing and contacting the obtained mixed gas with a catalyst to perform a deoxygenation reaction.

[0079] In a specific embodiment, the hydrocarbon gas may be at least one of C1-C4 alkanes, C2-C4 alkenes and C2-C4 alkynes.

[0080] In a specific embodiment, the content of hydrogen in the mixed gas is 0.1-1 vol%, preferably 0.3-0.6 vol%; the content of oxygen in the raw gas is 0.1-0.5 vol%; and the catalyst is the above-mentioned nickel-based catalyst.

[0081] In the present invention, the nickel-based catalyst can achieve the removal of low-concentration oxygen in the raw gas and achieve deep deoxygenation of the raw gas. In addition, in the presence of the nickel-based catalyst, the deoxygenation reaction does not need to be carried out under conditions of a higher hydrogen content, further avoiding the reaction of hydrogen with hydrocarbon gases in the raw gas, reducing the generation of side reactions, and further achieving deep deoxygenation of the raw gas.

[0082] In the present invention, the pressure of the deoxygenation reaction is 0.1-0.3 MPa. Specifically, the pressure of the deoxygenation reaction can be 0.1 MPa (normal pressure), 0.15 MPa, 0.2 MPa, 0.25 MPa or 0.3 MPa. The pressure required for the deoxygenation reaction is lower and the conditions are milder.

[0083] In a specific embodiment, the nickel-based catalyst of the present invention can remove low-content oxygen in the feed gas, and can achieve deep removal of oxygen under conditions of lower content of hydrogen and lower reaction pressure.

[0084] The present invention will be described in detail below through examples, but the protection scope of the present invention is not limited thereto. The examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.

[0085] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.

[0086] Example 1

[0087] (1) Put Ni(NO 3 ) 2 and Zn(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Zn(NO 3 ) 2 Then, the carrier Al is impregnated with an excessive amount of 2 O 3 Immersed in Ni(NO 3 ) 2 and Zn(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、Zn(NO 3 ) 2 and carrier Al 2 O 3The weight ratio of Ni(NO 3 ) 2 and Zn(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0088] (2) The dried solid phase was calcined at a temperature of 550°C for 3 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 450°C in a reducing atmosphere of pure H 2 , the reduction time is 6h, the reduction pressure is 0.2MPa, and the heating rate during reduction is 2℃ / min, and a Ni-based catalyst is obtained; in-situ XPS detection by characterization means shows that the active components in the Ni-based deoxygenation catalyst are Ni and NiO, and the molar ratio is 3:2. XRD and XPS test characterization show that the auxiliary agent is Zn oxide;

[0089] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0090] (4) The feed gas (composed of 99.25 vol% ethylene, 0.25 vol% oxygen and 0.5 vol% hydrogen) was introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction were: reaction space velocity 2000 h -1 , reaction pressure 0.2MPa, reaction temperature 120℃.

[0091] Example 2

[0092] (1) Put Ni(NO 3 ) 2 and NaNO 3 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and NaNO 3 Then, the support Al was impregnated with equal volume 2 O 3 Immersed in Ni(NO 3 ) 2 and NaNO 3 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、NaNO 3 and carrier Al 2 O 3 The weight ratio of Ni(NO 3 ) 2 and NaNO 3 The weight of the metal element is expressed as follows);

[0093] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of pure H 2 The reduction time was 8 h, the reduction pressure was 0.1 MPa, and the heating rate during reduction was 3 °C / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization showed that the active components in the Ni-based deoxygenation catalyst were Ni and Ni 3 O 4 , and the molar ratio is 3:5. XRD and XPS test characterization show that the auxiliary agent is Na oxide;

[0094] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0095] (4) The feed gas (composed of 99.25 vol% ethylene, 0.25 vol% oxygen and 0.5 vol% hydrogen) was introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction were: reaction space velocity 2000 h -1 , reaction pressure 0.2MPa, reaction temperature 120℃.

[0096] Example 3

[0097] (1) Put Ni(NO 3 ) 2 and Mg(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Mg(NO 3 ) 2 Then, the carrier SiO 2 Immersed in Ni(NO 3 ) 2 and Mg(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 Mg(NO 3 ) 2 and carrier SiO 2 The weight ratio of Ni(NO 3 ) 2 and Mg(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0098] (2) The dried solid phase was calcined at a temperature of 450°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of pure H 2 The reduction time was 8 h, the reduction pressure was 0.15 MPa, and the heating rate during reduction was 3 °C / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization showed that the active components in the Ni-based deoxygenation catalyst were Ni and Ni 2 O 3 , and the molar ratio is 5:2. XRD and XPS test characterizations show that the auxiliary agent is Mg oxide;

[0099] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0100] (4) The feed gas (composed of 99.25 vol% ethylene, 0.25 vol% oxygen and 0.5 vol% hydrogen) was introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction were: reaction space velocity 2000 h -1 , reaction pressure 0.2MPa, reaction temperature 120℃.

[0101] Example 4

[0102] (1) Put Ni(NO 3 ) 2 and Zr(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Zr(NO 3 ) 2 Then, the carrier SiO 2 Immersed in Ni(NO 3 ) 2 and Zr(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、Zr(NO 3 ) 2 and carrier SiO 2 The weight ratio of the dosage is 20:3:100 (Ni(NO 3 ) 2 and Zr(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0103] (2) The dried solid phase was calcined at a temperature of 450°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of 15 vol% H 2 and 85 vol% N 2 The Ni-based catalyst was obtained by in-situ XPS detection. The active components of the Ni-based deoxygenation catalyst are Ni, NiO and Ni. 3 O 4 , and the molar ratio is 2:3:1. XRD and XPS test characterization show that the auxiliary agent is Zr oxide;

[0104] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0105] (4) The feed gas (composed of 99.25 vol% ethylene, 0.25 vol% oxygen and 0.5 vol% hydrogen) was introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction were: reaction space velocity 2000 h -1 , reaction pressure 0.25MPa, reaction temperature 130℃.

[0106] Example 5

[0107] (1) Put Ni(NO 3 ) 2 and KNO 3 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and KNO 3 Then, the carrier activated carbon was impregnated with Ni(NO 3 ) 2 and KNO 3 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、KNO 3 The weight ratio of Ni(NO 3 ) 2 and KNO 3 The weight of the metal element is expressed as follows);

[0108] (2) The dried solid phase was calcined at a temperature of 450°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of pure H 2The reduction time was 8 h, the reduction pressure was 0.1 MPa, and the heating rate during reduction was 3 °C / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization showed that the active components in the Ni-based deoxygenation catalyst were Ni, NiO and Ni 2 O 3 , and the molar ratio is 2:6:3. XRD and XPS test characterization show that the auxiliary agent is K oxide;

[0109] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0110] (4) The feed gas (composed of 99.25 vol% ethylene, 0.25 vol% oxygen and 0.5 vol% hydrogen) was introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction were: reaction space velocity 2000 h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0111] Example 6

[0112] (1) Put Ni(NO 3 ) 2 and Cu(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Cu(NO 3 ) 2 Then, the carrier HZSM-5 molecular sieve was impregnated with Ni(NO 3 ) 2 and Cu(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、Cu(NO 3 ) 2 The metal weight ratio of the HZSM-5 molecular sieve to the carrier is 20:4:100 (Ni(NO 3 ) 2 and Cu(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0113] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of 10 vol% H 2 and 90 vol% N 2The reduction time was 8h, the reduction pressure was 0.25MPa, and the heating rate during reduction was 3℃ / min to obtain a Ni-based catalyst. The in-situ XPS test showed that the active components of the Ni-based deoxygenation catalyst were Ni, Ni 3 O 4 and Ni 2 O 3 , and the molar ratio is 2:3:2. XRD and XPS test characterization show that the auxiliary agent is Cu oxide;

[0114] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0115] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.3MPa, reaction temperature 120℃.

[0116] Example 7

[0117] (1) Put Ni(NO 3 ) 2 and Cu(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Cu(NO 3 ) 2 Then, the carrier MCM-22 molecular sieve was impregnated with Ni(NO 3 ) 2 and Cu(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、Cu(NO 3 ) 2 The metal weight ratio of the amount of the carrier MCM-22 molecular sieve is 20:4:100 (Ni(NO 3 ) 2 and Cu(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0118] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of pure H 2The reduction time was 8 h, the reduction pressure was 0.1 MPa, and the heating rate during reduction was 3 °C / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization showed that the active components in the Ni-based deoxygenation catalyst were Ni, Ni 3 O 4 and Ni 2 O 3 , and the molar ratio is 2:1:3. XRD and XPS test characterization show that the auxiliary agent is Cu oxide;

[0119] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0120] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0121] Example 8

[0122] (1) Put Ni(NO 3 ) 2 and NaNO 3 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and NaNO 3 Then, the carrier Y-type molecular sieve is impregnated with Ni(NO 3 ) 2 and NaNO 3 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、NaNO 3 The weight ratio of the amount of the carrier Y-type molecular sieve is 20:5:100 (Ni(NO 3 ) 2 and NaNO 3 The weight of the metal element is expressed as follows);

[0123] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of 5 vol% H 2 and 95 vol% N 2The Ni-based catalyst was obtained by in-situ XPS detection. The active components of the Ni-based deoxygenation catalyst are Ni and Ni. 3 O 4 , and the molar ratio is 5:2. XRD and XPS test characterization show that the auxiliary agent is Na oxide;

[0124] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0125] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0126] Example 9

[0127] (1) Put Ni(NO 3 ) 2 and NaNO 3 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and NaNO 3 Then, the Y-type molecular sieve carrier and the MCM-22 molecular sieve mixture (the weight of the Y-type molecular sieve carrier and the MCM-22 molecular sieve is 1:1) are impregnated in Ni(NO 3 ) 2 and NaNO 3 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、NaNO 3 The weight ratio of the amount of the carrier Y-type molecular sieve is 20:5:100 (Ni(NO 3 ) 2 and NaNO 3 The weight of the metal element is expressed as follows);

[0128] (2) The dried solid phase was calcined at a temperature of 450° C. for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400° C. in a reducing atmosphere of 5 vol% H 2 and 95 vol% N 2The reduction time was 8h, the reduction pressure was 0.1MPa, and the heating rate during reduction was 3℃ / min to obtain a Ni-based catalyst. The in-situ XPS test showed that the active components of the Ni-based deoxygenation catalyst were Ni and Ni 3 O 4 , and the molar ratio is 3:2. XRD and XPS test characterization show that the auxiliary agent is Na oxide;

[0129] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0130] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0131] Example 10

[0132] (1) Put Ni(NO 3 ) 2 and Mg(NO 3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Mg(NO 3 ) 2 Then, the carrier HZSM-5 molecular sieve and MCM-22 molecular sieve mixture (the weight of HZSM-5 molecular sieve and MCM-22 molecular sieve is 1:1) are impregnated in Ni(NO 3 ) 2 and Mg(NO 3 ) 2 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 Mg(NO 3 ) 2 The metal ratio of the support is 20:5:100 (Ni(NO 3 ) 2 and Mg(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0133] (2) The dried solid phase was calcined at a temperature of 550° C. for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 450° C. in a reducing atmosphere of 5 vol% H 2and 95 vol% N 2 The Ni-based catalyst was obtained by in-situ XPS detection. The active components of the Ni-based deoxygenation catalyst are Ni and Ni. 2 O 3 , and the molar ratio is 3:4. XRD and XPS test characterization show that the auxiliary agent is Mg oxide;

[0134] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0135] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0136] Comparative Example 1

[0137] (1) Put Ni(NO 3 ) 2 Dissolve in deionized water to obtain Ni(NO 3 ) 2 solution; then the carrier SiO 2 Immersed in Ni(NO 3 ) 2 The solid phase was dried at 120 °C for 10 h. 3 ) 2 and carrier SiO 2 The metal weight ratio of the dosage is 20:100 (Ni(NO 3 ) 2 Weight is measured in terms of metal element);

[0138] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of pure H 2 , the reduction time is 8h, the reduction pressure is 0.1MPa, and the heating rate during reduction is 3℃ / min, and a Ni-based catalyst is obtained; in-situ XPS detection by characterization means shows that the active component in the Ni-based deoxygenation catalyst is Ni;

[0139] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0140] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0141] Comparative Example 2

[0142] (1) Put Ni(NO 3 ) 2 Dissolve in deionized water to obtain Ni(NO 3 ) 2 solution; then the carrier Al was impregnated with equal volume 2 O 3 Immersed in Ni(NO 3 ) 2 The solid phase was dried at 120 °C for 10 h. 3 ) 2 and carrier Al 2 O 3 The weight ratio of the dosage is 10:100 (Ni(NO 3 ) 2 Weight is measured in terms of metal element);

[0143] (2) The dried solid phase was calcined at a temperature of 550°C for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400°C in a reducing atmosphere of 10 vol% H 2 and 95 vol% N 2 The reduction time is 8h, the reduction pressure is 0.1MPa, and the heating rate during reduction is 3℃ / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization means shows that the active component in the Ni-based deoxygenation catalyst is Ni.

[0144] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0145] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0146] Comparative Example 3

[0147] (1) Put Ni(NO 3 ) 2 and Ca(NO3 ) 2 Dissolved in deionized water to obtain Ni(NO 3 ) 2 and Ca(NO 3 ) 2 Then, the Y-type molecular sieve carrier was impregnated with Ni(NO 3 ) 2 and NaNO 3 The solid-liquid separation was followed by drying the obtained solid phase at 120°C for 10 h; Ni(NO 3 ) 2 、Ca(NO 3 ) 2 The metal weight ratio of the Y-type molecular sieve to the carrier is 20:5:100 (Ni(NO 3 ) 2 and Ca(NO 3 ) 2 The weight of the metal element is expressed as follows);

[0148] (2) The dried solid phase was calcined at a temperature of 450° C. for 4 h; the calcined product was then placed in a fixed bed reactor for reduction at a temperature of 400° C. in a reducing atmosphere of 5 vol% H 2 and 95 vol% N 2 The reduction time was 8h, the reduction pressure was 0.1MPa, and the heating rate during reduction was 3℃ / min to obtain a Ni-based catalyst. In-situ XPS detection by characterization means showed that the active components in the Ni-based deoxygenation catalyst were Ni and NiO, and the molar ratio was Ni:NiO=15:1.

[0149] (3) After the reduction is completed, the bed temperature of the fixed bed reactor is lowered to room temperature, and the catalyst bed is purged with nitrogen for 30 minutes;

[0150] (4) The feed gas (consisting of 99.25% ethylene, 0.25% oxygen and 0.5% hydrogen) is introduced into a fixed bed reactor for gas phase deoxygenation reaction. The conditions for the deoxygenation reaction are: reaction space velocity 2000h -1 , reaction pressure 0.25MPa, reaction temperature 120℃.

[0151] Test Case

[0152] Gas chromatography was used to detect the oxygen content in the tail gas after final deoxygenation of Examples 1-10 and Comparative Examples 1-3, and the deoxygenation rate was calculated using the formula: (oxygen content in raw gas - oxygen content in tail gas) ÷ oxygen content in raw gas. The results are shown in Table 1.

[0153] Table 1

[0154]

[0155]

[0156] It can be seen from the results in Table 1 that in the olefin deoxygenation process, the nickel-based catalyst of the present invention has a higher deoxygenation rate and a better deoxygenation effect, and can achieve deep deoxygenation of the feed gas.

[0157] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A nickel-based catalyst, characterized in that The nickel-based catalyst contains a carrier, an active component and an additive; The active components are Ni element and nickel oxide; The nickel oxide is selected from one or more of NiO, Ni3O4 and Ni2O3; The auxiliary agent is selected from one or more oxides of Zn, Na, Mg, Zr, K and Cu.

2. The nickel-based catalyst according to claim 1, characterized in that The molar ratio of Ni element to nickel oxide in the active component is 0.2-5:

1.

3. The nickel-based catalyst according to claim 1 or 2, characterized in that The active component is a combination of Ni and NiO, and the molar ratio of Ni to NiO is 1-2:1; or The active component is a combination of Ni and Ni3O4, and the molar ratio of Ni to Ni3O4 is 0.2-5:1; or The active component is a combination of Ni and Ni2O3, and the molar ratio of Ni to Ni2O3 is 0.4-5:1; or When the active components are simple Ni, NiO and Ni2O3, the molar ratio of simple Ni, NiO and Ni2O3 is 0.4-4:0.4-8:1; or When the active components are Ni, NiO and Ni3O4, the molar ratio of Ni, NiO and Ni3O4 is 0.5-5:0.5-6:1; or When the active components are Ni element, Ni3O4 and Ni2O3, the molar ratio of Ni element, Ni3O4 and Ni2O3 is 0.25-4:0.25-4:

1.

4. The nickel-based catalyst according to claim 1, characterized in that The carrier is selected from one or more of Al2O3, SiO2, activated carbon and molecular sieve.

5. A method for preparing a nickel-based catalyst, characterized in that: The method comprises the following steps: (1) immersing the support in a solution containing a nickel source and an additive precursor, followed by solid-liquid separation; (2) calcining the solid phase obtained in step (1), and then reducing the calcined product.

6. The method for preparing a nickel-based catalyst according to claim 5, characterized in that: The calcination conditions include: a temperature of 300-550° C. and a calcination time of 3-6 hours.

7. The method for preparing a nickel-based catalyst according to claim 5, characterized in that: The reduction conditions include: temperature of 200-500° C., time of 3-12 h, and pressure of 0.1-0.25 MPa.

8. The method for preparing a nickel-based catalyst according to claim 5 or 7, characterized in that: The heating rate of the reduction process is 2-15°C / min.

9. The method for preparing a nickel-based catalyst according to claim 5, characterized in that: The auxiliary agent precursor is selected from one or more of Zn salt, Na salt, Mg salt, Zr salt, K salt and Cu salt.

10. The method for preparing a nickel-based catalyst according to claim 5, characterized in that: The carrier is selected from one or more of Al2O3, SiO2, activated carbon and molecular sieve.

11. The method for preparing a nickel-based catalyst according to any one of claims 5, 7 or 8, characterized in that: The reducing gas used in the reduction process is H2, a mixture of H2 and protective gas, or a mixture of H2 and CO; Preferably, the H2 content in the mixed gas of H2 and protective gas is 5-20 vol%.

12. The method for preparing a nickel-based catalyst according to any one of claims 5, 9 or 10, characterized in that: The molar ratio of the nickel source, the auxiliary agent precursor and the carrier is 20:1-5:100, wherein the nickel source and the auxiliary agent precursor are calculated as metal elements.

13. A nickel-based catalyst prepared according to the method for preparing a nickel-based catalyst according to any one of claims 5 to 12.

14. Use of the nickel-based catalyst according to any one of claims 1 to 4 or the nickel-based catalyst according to claim 13 in removing oxygen.

15. A method for deoxygenating olefins, characterized in that: The method comprises: mixing a raw gas containing hydrocarbon gas and oxygen with hydrogen, and then mixing and contacting the obtained mixed gas with a catalyst to perform a deoxygenation reaction; Wherein, the content of hydrogen in the mixed gas is 0.1-1 vol%, and the content of oxygen in the raw gas is 0.1-0.5 vol%; The catalyst is the nickel-based catalyst according to any one of claims 1 to 4 or the nickel-based catalyst according to claim 13.

16. The method for deoxygenating olefins according to claim 15, characterized in that: The pressure of the deoxygenation reaction is 0.1-0.3 MPa.

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