ZrO2-containing olefin deoxidation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the field of catalysts, and discloses a ZrO2-containing olefin deoxidation catalyst as well as a preparation method and application thereof. The ZrO2-containing olefin deoxidation catalyst comprises a carrier and an active component loaded on the carrier, the carrier contains ZrO2 and an auxiliary agent, the auxiliary agent is selected from one or more than two of Cu oxide, Zn oxide, Na oxide and K oxide, and the active component is Pd oxide. The ZrO2-containing olefin deoxidation catalyst has high catalytic activity, can perform deep deoxidation on olefin feed gas with low oxygen content, has a deoxidation rate up to 99.76%, and has a good application prospect in the aspect of olefin deoxidation.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and particularly to an olefin deoxidation catalyst containing ZrO2, a preparation method thereof, and an application thereof. Background Art

[0002] The catalytic oxidation reaction is one of the most common chemical reactions in the chemical production process. Propylene oxide is a very important raw material for organic compounds and is the third largest propylene derivative after polypropylene and acrylonitrile. The incomplete reaction of propylene, the raw material for the preparation of propylene oxide, and the oxidant (hydrogen peroxide), as well as the self-decomposition reaction of the oxidant (hydrogen peroxide), cause a large amount of oxygen to accumulate in the recycled propylene. The presence of oxygen increases the risk of combustion and explosion in the system. At the same time, the oxygen-containing tail gas cannot enter the flare system when the oxygen concentration is >2% by volume. Therefore, the efficient treatment of oxygen in the oxygen-containing tail gas has become a key problem to be solved urgently.

[0003] Currently, the main treatment method for hydrocarbon oxygen-containing tail gas is dilution and emission with inert gas. Many domestic enterprises such as Changling Branch of Sinopec adopt the method of mixing and diluting with N2. This method not only increases the operating cost (a large amount of nitrogen consumption) but also causes environmental pollution due to the emission of VOCs. In recent years, catalytic deoxidation is an effective deoxidation method and has received extensive attention due to its great advantages in economy, environmental protection, energy conservation, etc., and also has important applications in industry. However, there is still a problem of low efficiency in the deep deoxidation of noble metal catalysts. Therefore, the development of catalysts with high catalytic oxidation activity or efficient carriers has become a research hotspot and difficulty for researchers.

[0004] CN101745391B is a catalyst for removing trace oxygen from catalytic cracking dry gas. The catalyst includes a carrier and a catalytic active component. Among them, the catalytic active component consists of a main catalytic active component and a co-catalytic active component. The main catalytic active component is noble metal palladium, and the palladium content is 0.01-0.5% by weight of the catalyst. The co-catalytic active component is selected from one or more of Ag, Au, Co, and Cr, and the content is 0.05-1.0%. The carrier is selected from alumina, activated carbon, silica, or molecular sieve. However, this catalyst for removing trace oxygen from catalytic cracking dry gas is only for deoxidizing catalytic cracking dry gas with a relatively high hydrogen content, and can only be deeply deoxidized under relatively high reaction pressure (2.0 MPa) and conditions of trace oxygen.

[0005] Patent CN1175478A (a high-strength, high heat resistance and anti-poisoning deoxidation catalyst) discloses a high-strength and high heat resistance catalyst for hydrogenation deoxidation in hydrogen, nitrogen and inert gases. The catalyst uses TiO2 as the main carrier, and the active components are noble metals palladium and / or platinum. The catalyst is loaded with active components by the impregnation method and then strengthened at high temperature (500 - 750 °C) in a reducing atmosphere. Calculated by the weight of the catalyst, the noble metal content is 0.01 - 5.0%. This catalyst has high activity, and the deoxidation purification depth can reach 0.02 ppm. However, this catalyst requires high-temperature H2 reduction, increasing the cost and operation risk. Summary of the Invention

[0006] The object of the present invention is to overcome the problems of poor deoxidation effect and high cost of the existing olefin deoxidation catalyst containing ZrO2, and to provide an olefin deoxidation catalyst containing ZrO2. This olefin deoxidation catalyst containing ZrO2 has high catalytic efficiency. When applied in olefin deoxidation, it can also perform deep deoxidation on olefin raw gas with low oxygen content, and requires lower reaction pressure and lower hydrogen content, making the operation more convenient.

[0007] To achieve the above object, on the one hand, the present invention provides an olefin deoxidation catalyst containing ZrO2, which includes a carrier and active components loaded on the carrier;

[0008] The carrier contains ZrO2 and an additive. The additive is selected from one or more of Cu oxide, Zn oxide, Na oxide and K oxide, and the active component is Pd oxide.

[0009] Preferably, the weight ratio of Pd oxide to ZrO2 is 0.05 - 0.3:100, where Pd oxide is calculated as metal.

[0010] Preferably, the weight ratio of the additive to ZrO2 is 0.5 - 20:100, where the additive is calculated as metal.

[0011] Preferably, the ZrO2 is tetragonal ZrO2, composite ZrO2 or monoclinic ZrO2.

[0012] On the second aspect, the present invention provides a method for preparing an olefin deoxidation catalyst containing ZrO2, which includes the following steps:

[0013] (1) Mix ZrO2 and the precursor solution of the additive, and then perform the first calcination;

[0014] (2) Load metal Pd onto the material obtained in step (1), and then perform the second calcination;

[0015] The promoter precursor is selected from one or more of copper salts, zinc salts, sodium salts, and potassium salts.

[0016] Preferably, the ZrO2 is tetragonal ZrO2, composite-phase ZrO2, or monoclinic ZrO2.

[0017] Preferably, the method for preparing the tetragonal ZrO2 includes: mixing a Zr salt, a surfactant, an organic solvent, and ammonia water, followed by crystallization and then calcination;

[0018] The conditions for the crystallization include: a temperature of 100 - 200 °C and a time of 2 - 15 h;

[0019] The conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0020] Preferably, the method for preparing the composite-phase ZrO2 includes: mixing a Zr salt, urea, and an organic solvent, followed by crystallization and then calcination;

[0021] The conditions for the crystallization include: a temperature of 120 - 300 °C and a time of 6 - 12 h;

[0022] The conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0023] Preferably, the method for preparing the monoclinic ZrO2 includes: mixing a Zr salt, urea, and an organic solvent, followed by crystallization and then calcination;

[0024] The conditions for the crystallization include: a temperature of 120 - 350 °C and a time of 20 - 30 h;

[0025] The conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0026] Preferably, in step (1), the weight ratio of the amount of the promoter precursor to ZrO2 is 1 - 20:100, where the promoter precursor is calculated as metal.

[0027] Preferably, the conditions for the first calcination include: a temperature of 350 - 500 °C and a time of 3 - 6 h.

[0028] Preferably, in step (2), the weight ratio of the amount of metal Pd to ZrO2 is 0.1 - 0.3:100.

[0029] Preferably, in step (2), the loading method is selected from impregnation, ion sputtering, or electrochemical deposition.

[0030] Preferably, in step (2), the conditions for the second calcination include: a temperature of 300 - 500 °C and a time of 3 - 5 h.

[0031] The third aspect of the present invention provides an olefin deoxidation catalyst containing ZrO2 prepared by the above method.

[0032] The fourth aspect of the present invention provides the application of the above olefin deoxidation catalyst containing ZrO2 in olefin deoxidation reaction.

[0033] The fifth aspect of the present invention provides a method for olefin deoxidation reaction, in which the raw material gas is contacted with the catalyst;

[0034] The raw material gas contains olefin, oxygen and hydrogen; the catalyst is the above olefin deoxidation catalyst containing ZrO2.

[0035] Preferably, the content of oxygen in the raw material gas is ≤0.25% by volume, and the volume ratio of hydrogen to oxygen is ≤4.

[0036] Preferably, the conditions of the contact include: the space velocity is 2000 - 5000 h -1 , the pressure is 0.1 - 0.4 MPa, and the temperature is 100 - 200 °C.

[0037] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0038] (1) The catalytic efficiency of the olefin deoxidation catalyst containing ZrO2 of the present invention is high. This may be because the ZrO2 in the olefin deoxidation catalyst containing ZrO2 has efficient oxygen vacancies, which promotes the adsorption and activation ability of oxygen. The active component Pd oxide is highly dispersed, and at the same time, the additives contained in the carrier promote the interaction between the active component Pd oxide and the carrier, thereby improving the catalytic activity;

[0039] (2) The cost of the olefin deoxidation catalyst containing ZrO2 of the present invention is relatively low, which is mainly due to the high utilization rate of metal Pd in the preparation process.

[0040] (3) When the olefin deoxidation catalyst containing ZrO2 of the present invention is applied in the olefin deoxidation reaction, the required reaction pressure and the required hydrogen content are relatively low, and the operation is more convenient. Specific Embodiments

[0041] The following details the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only for explaining and illustrating the present invention, and are not used to limit the present invention.

[0042] The endpoints and any values within the ranges disclosed herein are not limited to the exact ranges or values. 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, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0043] On the one hand, the present invention provides an olefin deoxidation catalyst containing ZrO2. The olefin deoxidation catalyst containing ZrO2 includes a carrier and an active component supported on the carrier.

[0044] The carrier contains ZrO2 and an auxiliary agent. The auxiliary agent is selected from one or more of Cu oxide, Zn oxide, Na oxide, and K oxide. The active component is Pd oxide.

[0045] In a preferred embodiment, in order to improve the interaction between the active component Pd oxide and the carrier and enhance the catalytic activity, the weight ratio of Pd oxide to ZrO2 is 0.05 - 0.3:100, where Pd oxide is calculated as the metal. Specifically, it can be 0.05:100, 0.1:100, 0.2:100, or 0.3:100.

[0046] In a preferred embodiment, in order to further promote the interaction between the active component Pd oxide and the carrier, promote oxygen adsorption while promoting the activation of hydrogen, and thus further improve the catalytic activity, the weight ratio of the auxiliary agent to ZrO2 is 0.5 - 20:100, where the auxiliary agent is calculated as the metal. Specifically, it can be 0.5:100, 5:100, 10:100, 15:100, or 20:100.

[0047] In a preferred embodiment, in order to better promote the interaction between the active component Pd oxide and ZrO2, the ZrO2 is tetragonal ZrO2, composite-phase ZrO2, or monoclinic ZrO2.

[0048] In the present invention, the composite-phase ZrO2 includes two or more crystal forms. Specifically, the composite-phase ZrO2 contains both tetragonal ZrO2 and monoclinic ZrO2.

[0049] The olefin deoxidation catalyst containing ZrO2 of the present invention has high catalytic activity, mainly because ZrO2 has efficient oxygen vacancies, which promotes the oxygen adsorption and activation ability. The auxiliary agent contained in the carrier promotes the interaction between Pd oxide and the ZrO2-containing carrier, promotes oxygen adsorption while also promoting the activation of hydrogen, thereby improving the catalytic activity of the catalyst.

[0050] The second aspect of the present invention provides a method for preparing an olefin deoxidation catalyst containing ZrO2, which method comprises the following steps:

[0051] (1) Mix ZrO2 and a promoter precursor solution, and then perform a first calcination;

[0052] (2) Load metal Pd onto the material obtained in step (1), and then perform a second calcination;

[0053] The promoter precursor is selected from one or more of copper salts, zinc salts, sodium salts, and potassium salts.

[0054] In a preferred embodiment, in order to better promote the interaction between metal Pd and ZrO2, the ZrO2 is tetragonal ZrO2, composite phase ZrO2, or monoclinic ZrO2.

[0055] In a preferred embodiment, the method for preparing the tetragonal ZrO2 comprises: mixing a Zr salt, a surfactant, an organic solvent, and ammonia water, followed by crystallization, and then calcination; the conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0056] In a preferred embodiment, the crystallization conditions for preparing the tetragonal ZrO2 include: a temperature of 100 - 200 °C and a time of 2 - 15 h; specifically, the crystallization temperature can be 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, or 200 °C; the crystallization time can be 2 h, 4 h, 6 h, 8 h, 10 h, 12 h, or 15 h.

[0057] In a preferred embodiment, the method for preparing the tetragonal ZrO2 further comprises performing solid-liquid separation, washing, and drying treatments after crystallization and before calcination. There are no special requirements for the specific treatment methods of solid-liquid separation, washing, and drying, and conventional usage methods in the art can be used. For example, deionized water and absolute ethanol can be used to wash the solid intermediate material after solid-liquid separation; the drying conditions include: a temperature of 120 - 180 °C and a time of 12 - 24 h.

[0058] In a specific embodiment, the method for preparing the tetragonal ZrO2 is as follows: Mix ZrOCl2·8H2O, sodium dodecyl sulfate, acetylacetone, absolute ethanol, and ammonia water with a mass concentration of 25%, stir, then place the mixed solution in a stainless steel hydrothermal autoclave lined with polytetrafluoroethylene for crystallization, then perform solid-liquid separation, washing, and drying, and finally perform calcination.

[0059] In a preferred embodiment, the method for preparing the composite-phase ZrO₂ includes: mixing a Zr salt, urea, and an organic solvent, followed by crystallization and then calcination; the conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0060] In a preferred embodiment, the crystallization conditions for preparing the composite-phase ZrO₂ include: a temperature of 120 - 300 °C and a time of 6 - 12 h; specifically, the crystallization temperature can be 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, or 300 °C; the crystallization time can be 6 h, 8 h, 10 h, or 12 h.

[0061] In a preferred embodiment, the method for preparing the composite-phase ZrO₂ further includes solid-liquid separation, washing, and drying treatments after crystallization and before calcination. There are no special requirements for the specific treatment methods of solid-liquid separation, washing, and drying, and conventional usage methods in the art can be used. For example, deionized water and absolute ethanol can be used to wash the solid intermediate material after solid-liquid separation; the drying conditions include: a temperature of 120 - 180 °C and a time of 12 - 24 h.

[0062] In a specific embodiment, the method for preparing the composite-phase ZrO₂ is as follows: adding Zr(NO₃)₄·5H₂O and urea to anhydrous methanol and stirring, then placing the mixed solution in a stainless-steel hydrothermal autoclave lined with polytetrafluoroethylene for crystallization, followed by solid-liquid separation, washing, and drying, and finally calcination.

[0063] In a preferred embodiment, the method for preparing the monoclinic-phase ZrO₂ includes: mixing a Zr salt, urea, and an organic solvent, followed by crystallization and then calcination; the conditions for the calcination include: a temperature of 300 - 600 °C and a time of 2 - 8 h.

[0064] In a preferred embodiment, the crystallization conditions for preparing the monoclinic-phase ZrO₂ include: a temperature of 120 - 350 °C and a time of 20 - 30 h; specifically, the crystallization temperature can be 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, 300 °C, 320 °C, or 350 °C; the crystallization time can be 20 h, 22 h, 24 h, 26 h, 28 h, or 30 h.

[0065] In a preferred embodiment, the method for preparing the monoclinic ZrO2 further includes performing solid-liquid separation, washing, and drying treatments after crystallization and before calcination. There are no special requirements for the specific treatment methods of solid-liquid separation, washing, and drying, and conventional usage methods in the art can be adopted. For example, deionized water and absolute ethanol can be used to wash the solid intermediate material after solid-liquid separation; the drying conditions include: a temperature of 120-180 °C and a time of 12-24 h.

[0066] In a specific embodiment, the method for preparing the monoclinic ZrO2 is as follows: Zr(NO3)4·5H2O and urea are added to anhydrous methanol and stirred, and then the mixed solution is placed in a stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining for crystallization, followed by solid-liquid separation, washing, and drying, and finally calcination.

[0067] In the present invention, there are no special requirements for the Zr salt, and water-soluble Zr salts commonly used in the art can be used. For example, it can be one or more of ZrOCl2, ZrOCl2·8H2O, Zr(NO3)4, and Zr(NO3)4·5H2O.

[0068] In the present invention, there are no special requirements for the surfactant, and anionic surfactants commonly used in the art can be used. For example, it can be sodium dodecyl sulfate and / or sodium dodecylbenzenesulfonate.

[0069] In the present invention, there are no special requirements for the organic solvent, and organic solvents commonly used in the art can be used. For example, it can be one or more of acetylacetone, ethanol, methanol, diethylene glycol monoethyl ether, and ethylene glycol.

[0070] In the present invention, there are no special requirements for the mass concentration of ammonia water, and ammonia water concentrations commonly used in the art can be used. For example, it can be 10%, 15%, 20%, or 25%.

[0071] In a preferred embodiment, in order to improve the catalytic activity, step (1) further includes pretreating ZrO2 before mixing to remove impurities on the surface of ZrO2 and better mix ZrO2 and the promoter precursor solution; specifically, argon is used to pretreat ZrO2 by ion sputtering using an ion sputtering machine.

[0072] In the method of the present invention, there are no special requirements for the copper salt, zinc salt, sodium salt, and potassium salt, and soluble copper salts, zinc salts, sodium salts, and potassium salts commonly used in the art can be used. For example, the copper salt can be copper nitrate, copper chloride, or copper sulfate; the zinc salt can be zinc nitrate, zinc chloride, or zinc sulfate; the sodium salt can be sodium nitrate, sodium sulfate, or sodium chloride; the potassium salt can be potassium nitrate, potassium chloride, or potassium sulfate.

[0073] In a preferred embodiment, in step (1), ZrO2 and the promoter precursor solution are mixed by impregnation.

[0074] In a more preferred embodiment, in step (1), in order to better adjust the electronic properties of metallic Pd, further promote the interaction between Pd oxide and ZrO2, thereby promoting oxygen adsorption and hydrogen activation, and further improving the catalytic activity, the weight ratio of the promoter precursor to ZrO2 is 1-20:100, wherein the promoter precursor is calculated as metal; specifically, it can be 1:100, 5:100, 10:100, 15:100 or 20:100.

[0075] In a preferred embodiment, step (1) further includes a drying treatment after mixing and before the first calcination, and the drying conditions include: a temperature of 120-180 °C and a time of 10-24 h.

[0076] In a preferred embodiment, in step (1), the conditions of the first calcination include: a temperature of 350-500 °C and a time of 3-6 h; specifically, the temperature can be 350 °C, 400 °C, 450 °C or 500 °C; the time can be 3 h, 4 h, 5 h or 6 h.

[0077] In a preferred embodiment, in step (2), in order to improve the interaction between metallic Pd and ZrO2 and improve the catalytic activity, the weight ratio of metallic Pd to ZrO2 is 0.1-0.3:100; specifically, the weight ratio of metallic Pd to ZrO2 can be 0.1:100, 0.15:100, 0.2:100, 0.25:100 or 0.3:100.

[0078] In a preferred embodiment, in order to improve the utilization rate and dispersion of metallic Pd, thereby improving the catalytic activity, in step (2), the loading method is selected from impregnation, ion sputtering or electrochemical deposition.

[0079] In a more preferred embodiment, in step (2), the loading method is ion sputtering. By using the ion sputtering method, metallic Pd can be loaded on the ZrO2-containing carrier in an almost atomic-level manner, improving the high dispersion of metallic Pd and further improving the utilization rate of Pd metal, thereby reducing the operation cost and improving the catalytic activity.

[0080] In a preferred embodiment, in step (2), the conditions of the second calcination include: a temperature of 300-500 °C and a time of 3-5 h; specifically, the temperature can be 300 °C, 350 °C, 400 °C, 450 °C or 500 °C; the time can be 3 h, 4 h or 5 h.

[0081] The olefin deoxygenation catalyst containing ZrO2 prepared by the above method has high catalytic efficiency. This is mainly because ZrO2 has efficient oxygen vacancies, which promotes the adsorption and activation of oxygen. The promoter contained in the support can also adjust the electronic properties of metallic Pd, thereby promoting the interaction between Pd oxide and the support containing ZrO2, promoting the adsorption of oxygen and the activation of hydrogen, and then improving the catalytic activity.

[0082] The third aspect of the present invention provides an olefin deoxygenation catalyst containing ZrO2 prepared by the above method.

[0083] The fourth aspect of the present invention provides the application of the above olefin deoxygenation catalyst containing ZrO2 in the olefin deoxygenation reaction.

[0084] When the olefin deoxygenation catalyst containing ZrO2 described in the present invention is applied in the olefin deoxygenation reaction, it has high catalytic efficiency. This is mainly because in the olefin deoxygenation catalyst containing ZrO2 described in the present invention, Pd oxide interacts with the support containing the promoter and ZrO2, promoting the adsorption of oxygen and the activation of hydrogen, improving the catalytic activity, and then improving the deoxygenation efficiency.

[0085] The fifth aspect of the present invention provides a method for olefin deoxygenation reaction, in which the raw material gas is contacted with the catalyst;

[0086] The raw material gas contains olefin, oxygen and hydrogen; the catalyst is the above olefin deoxygenation catalyst containing ZrO2.

[0087] The olefin deoxygenation catalyst containing ZrO2 described in the present invention also has a good deoxygenation effect on the raw material gas with a low oxygen content and a small volume ratio of hydrogen to oxygen, and does not have strict requirements for environmental conditions. It still has a good deoxygenation effect under low pressure and relatively low temperature, and the deoxygenation rate is above 90%, and can reach up to 99.76%.

[0088] In a preferred embodiment, the olefin is ethylene and / or propylene.

[0089] In a preferred embodiment, the content of oxygen in the raw material gas ≤ 0.25% by volume, and the volume ratio of hydrogen to oxygen ≤ 4; specifically, the content of oxygen can be 0.25% by volume, 0.2% by volume, 0.15% by volume, 0.1% by volume or 0.05% by volume; the volume ratio of hydrogen to oxygen can be 4, 3, 2 or 1.

[0090] In the present invention, "space velocity" all refers to "volume space velocity", and the pressure all refers to absolute pressure.

[0091] In a preferred embodiment, the conditions of the contact include: the space velocity is 2000 - 5000 h -1, the pressure is 0.1 - 0.4 MPa, and the temperature is 100 - 200 °C; specifically, the space velocity can be 2000 h -1 -1, 3000 h -1 -1, 4000 h -1 -1 or 5000 h -1 -1; the pressure can be 0.1 MPa, 0.2 MPa, 0.3 MPa or 0.4 MPa; the temperature can be 100 °C, 120 °C, 140 °C, 160 °C, 180 °C or 200 °C.

[0092] The following further illustrates an olefin deoxidation catalyst containing ZrO2 and its preparation method and application according to the present invention through examples. The examples are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.

[0093] The experimental methods in the following examples are all conventional methods in the art unless otherwise specified. The experimental materials used in the following examples can all be commercially obtained unless otherwise specified.

[0094] Example 1

[0095] (1) Mix 9 g of sodium dodecyl sulfate, 30 mL of 25% by mass ammonia water, 3 mL of acetylacetone, 15 mL of absolute ethanol and 6.6 g of ZrOCl2·8H2O and stir, then place the mixed solution in a 100 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene liner at 180 °C for crystallization for 6 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, and place the dried solid-phase intermediate material in a tube furnace and calcine it at 450 °C for 3 h to obtain tetragonal ZrO2 (t-ZrO2);

[0096] Use an ion sputtering machine to pretreat t-ZrO2 by ion sputtering of argon. Mix the pretreated t-ZrO2 with an aqueous solution of Cu(NO3)2, then dry it at 120 °C for 10 h, and finally place it in a tube furnace for the first calcination. The temperature of the first calcination is 450 °C and the time is 4 h. Among them, the weight ratio of the dosage of Cu(NO3)2 (calculated as metal) to t-ZrO2 is 10:100 to obtain an intermediate product;

[0097] (2) Use an ion sputtering machine to load metallic Pd onto the intermediate product obtained in step (1) by ion sputtering, and finally conduct a second calcination in a tube furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metallic Pd to t-ZrO2 is 0.3:100.

[0098] Example 2

[0099] (1) Mix 9 g of sodium dodecyl sulfate, 30 mL of 25% ammonia water by mass concentration, 3 mL of acetylacetone, 15 mL of absolute ethanol, and 6.6 g of ZrOCl2·8H2O and stir. Then place the mixed solution in a 100 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 6 h. Separate the solid and liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, place the dried solid-phase intermediate material in a tube furnace, and calcine it at 450 °C for 3 h to obtain tetragonal ZrO2 (t-ZrO2);

[0100] Use an ion sputtering machine to pretreat t-ZrO2 by ion sputtering with argon. Mix the pretreated t-ZrO2 with an aqueous solution of Zn(NO3)2, and then dry it at 120 °C for 10 h. Finally, place it in a tube furnace for the first calcination. The temperature of the first calcination is 450 °C and the time is 4 h. Among them, the weight ratio of Zn(NO3)2 (calculated as metal) to the amount of t-ZrO2 used is 10:100 to obtain an intermediate product;

[0101] (2) Use an ion sputtering machine to load metallic Pd onto the intermediate product obtained in step (1) by ion sputtering, and finally conduct a second calcination in a tube furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metallic Pd to t-ZrO2 is 0.3:100.

[0102] Example 3

[0103] (1) Mix 9 g of sodium dodecyl sulfate, 30 mL of 25% ammonia water by mass concentration, 3 mL of acetylacetone, 15 mL of absolute ethanol and 6.6 g of ZrOCl₂·8H₂O and stir. Then place the mixed solution in a 100 mL stainless steel hydrothermal reactor with a polytetrafluoroethylene liner at 180 °C for crystallization for 6 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, place the dried solid-phase intermediate material in a tube furnace, and calcine it at 450 °C for 3 h to obtain tetragonal ZrO₂ (t-ZrO₂);

[0104] Use an ion sputtering machine to pretreat t-ZrO₂ by ion sputtering of argon gas. Mix the pretreated t-ZrO₂ with an aqueous NaNO₃ solution, then dry it at 120 °C for 10 h, and finally place it in a tube furnace for the first calcination. The temperature of the first calcination is 450 °C and the time is 4 h. Among them, the weight ratio of NaNO₃ (calculated as metal) to the amount of t-ZrO₂ is 3:100 to obtain an intermediate product;

[0105] (2) Use an ion sputtering machine to load metal Pd onto the intermediate product obtained in step (1) by ion sputtering. Finally, conduct the second calcination in a tube furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metal Pd to t-ZrO₂ is 0.3:100.

[0106] Example 4

[0107] (1) Mix 9 g of sodium dodecyl sulfate, 30 mL of 25% ammonia water by mass concentration, 3 mL of acetylacetone, 15 mL of absolute ethanol and 6.6 g of ZrOCl₂·8H₂O and stir. Then place the mixed solution in a 100 mL stainless steel hydrothermal reactor with a polytetrafluoroethylene liner at 180 °C for crystallization for 6 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, place the dried solid-phase intermediate material in a tube furnace, and calcine it at 450 °C for 3 h to obtain tetragonal ZrO₂ (t-ZrO₂);

[0108] Using an ion sputtering machine, argon gas was used to pretreat t-ZrO2 by ion sputtering. The pretreated t-ZrO2 was mixed with an aqueous solution of KNO3, and then dried at 120 °C for 10 h. Finally, it was placed in a tube furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of KNO3 (calculated as metal) to the amount of t-ZrO2 was 3:100 to obtain an intermediate product;

[0109] (2) Using an ion sputtering machine, metallic Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering. Finally, it was placed in a tube furnace for the second calcination. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metallic Pd to t-ZrO2 was 0.3:100.

[0110] Example 5

[0111] (1) 34.3 g of Zr(NO3)4·5H2O and 48 g of urea were added to 200 mL of anhydrous methanol, and the mixture was water-bathed at 70 °C for 25 min. Then, the mixed solution was placed in a 250 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 12 h. The crystallized intermediate material was subjected to solid-liquid separation, and the solid-phase intermediate material was washed with deionized water and anhydrous ethanol. The washed solid-phase intermediate material was placed in an oven at 120 °C for drying for 12 h. The dried solid-phase intermediate material was placed in a tube furnace and calcined at 500 °C for 4 h to obtain a composite phase ZrO2 (mt-ZrO2);

[0112] Using an ion sputtering machine, argon gas was used to pretreat mt-ZrO2 by ion sputtering. The pretreated mt-ZrO2 was mixed with an aqueous solution of Cu(NO3)2, and then dried at 120 °C for 10 h. Finally, it was placed in a tube furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of Cu(NO3)2 (calculated as metal) to the amount of mt-ZrO2 was 10:100 to obtain an intermediate product;

[0113] (2) Using an ion sputtering machine, metallic Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering. Finally, it was placed in a tube furnace for the second calcination. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metallic Pd to mt-ZrO2 was 0.3:100.

[0114] Example 6

[0115] (1) 34.3 g of Zr(NO3)4·5H2O and 48 g of urea were added to 200 mL of anhydrous methanol, and the mixture was subjected to a water bath at 70 °C for 25 min. Then, the mixed solution was placed in a 250 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 12 h. The solid-liquid separation of the crystallized intermediate material was carried out, and the solid-phase intermediate material was washed with deionized water and anhydrous ethanol. The washed solid-phase intermediate material was placed in an oven at 120 °C for drying for 12 h. The dried solid-phase intermediate material was placed in a tube furnace and calcined at 500 °C for 4 h to obtain composite-phase ZrO2 (mt-ZrO2);

[0116] The mt-ZrO2 was pretreated by ion sputtering of argon gas using an ion sputtering machine. The pretreated mt-ZrO2 was mixed with an aqueous Zn(NO3)2 solution, and then dried at 120 °C for 10 h. Finally, it was placed in a tube furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of Zn(NO3)2 (calculated as metal) to the amount of mt-ZrO2 used was 10:100 to obtain an intermediate product;

[0117] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering using an ion sputtering machine. Finally, it was placed in a tube furnace for the second calcination. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to mt-ZrO2 was 0.3:100.

[0118] Example 7

[0119] (1) 34.3 g of Zr(NO3)4·5H2O and 48 g of urea were added to 200 mL of anhydrous methanol, and the mixture was subjected to a water bath at 70 °C for 25 min. Then, the mixed solution was placed in a 250 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 12 h. The solid-liquid separation of the crystallized intermediate material was carried out, and the solid-phase intermediate material was washed with deionized water and anhydrous ethanol. The washed solid-phase intermediate material was placed in an oven at 120 °C for drying for 12 h. The dried solid-phase intermediate material was placed in a tube furnace and calcined at 500 °C for 4 h to obtain composite-phase ZrO2 (mt-ZrO2);

[0120] The mt-ZrO2 was pretreated by passing argon through ion sputtering using an ion sputtering machine. The pretreated mt-ZrO2 was mixed with an aqueous solution of NaNO3, then dried at 120 °C for 10 h, and finally placed in a tubular furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of NaNO3 (calculated as metal) to the amount of mt-ZrO2 used was 3:100 to obtain an intermediate product;

[0121] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering using an ion sputtering machine, and finally the second calcination was carried out in a tubular furnace. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to mt-ZrO2 was 0.3:100.

[0122] Example 8

[0123] (1) 34.3 g of Zr(NO3)4·5H2O and 48 g of urea were added to 200 mL of anhydrous methanol, and the mixture was water-bathed at 70 °C for 25 min. Then the mixed solution was placed in a 250 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene liner at 180 °C for crystallization for 12 h. The solid-liquid separation was carried out on the crystallized intermediate material, and the solid-phase intermediate material was washed with deionized water and anhydrous ethanol. The washed solid-phase intermediate material was placed in an oven at 120 °C for drying for 12 h. The dried solid-phase intermediate material was placed in a tubular furnace and calcined at 500 °C for 4 h to obtain a composite phase ZrO2 (mt-ZrO2);

[0124] The mt-ZrO2 was pretreated by passing argon through ion sputtering using an ion sputtering machine. The pretreated mt-ZrO2 was mixed with an aqueous solution of KNO3, then dried at 120 °C for 10 h, and finally placed in a tubular furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of KNO3 (calculated as metal) to the amount of mt-ZrO2 used was 3:100 to obtain an intermediate product;

[0125] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering using an ion sputtering machine, and finally the second calcination was carried out in a tubular furnace. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to mt-ZrO2 was 0.3:100.

[0126] Example 9

[0127] (1) First, add 17.1 g of Zr(NO3)4·5H2O to 50 mL of deionized water and stir mechanically. Add 38.7 g of urea to 200 mL of deionized water, then mix the above urea aqueous solution and Zr salt aqueous solution, and stir mechanically for 30 min. Then place the mixed solution in a 300 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 20 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 60 °C for drying for 12 h, place the dried solid-phase intermediate material in a tubular furnace, and calcine at 500 °C for 4 h to obtain monoclinic ZrO2 (m-ZrO2);

[0128] Use an ion sputtering machine to pretreat m-ZrO2 by ion sputtering with argon. Mix the pretreated m-ZrO2 with an aqueous solution of Cu(NO3)2, then dry at 120 °C for 10 h, and finally place it in a tubular furnace for the first calcination. The temperature of the first calcination is 450 °C and the time is 4 h. Among them, the weight ratio of Cu(NO3)2 (calculated as metal) to the amount of m-ZrO2 used is 10:100 to obtain an intermediate product;

[0129] (2) Use an ion sputtering machine to load metal Pd onto the intermediate product obtained in step (1) by ion sputtering. Finally, perform the second calcination in a tubular furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metal Pd to m-ZrO2 is 0.3:100.

[0130] Example 10

[0131] (1) First, add 17.1 g of Zr(NO3)4·5H2O to 50 mL of deionized water and stir mechanically. Add 38.7 g of urea to 200 mL of deionized water, then mix the above urea aqueous solution and Zr salt aqueous solution, and stir mechanically for 30 min. Then place the mixed solution in a 300 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 20 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 60 °C for drying for 12 h, place the dried solid-phase intermediate material in a tubular furnace, and calcine at 500 °C for 4 h to obtain monoclinic ZrO2 (m-ZrO2);

[0132] The m-ZrO2 was pretreated by passing argon through an ion sputtering machine in the form of ion sputtering. The pretreated m-ZrO2 was mixed with an aqueous solution of Zn(NO3)2, and then dried at 120 °C for 10 h. Finally, it was placed in a tube furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of the amount of Zn(NO3)2 (calculated as metal) to m-ZrO2 was 10:100 to obtain an intermediate product;

[0133] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by an ion sputtering machine in the form of ion sputtering. Finally, it was placed in a tube furnace for the second calcination. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to m-ZrO2 was 0.3:100.

[0134] Example 11

[0135] (1) First, 17.1 g of Zr(NO3)4·5H2O was added to 50 mL of deionized water and mechanically stirred. 38.7 g of urea was added to 200 mL of deionized water, and then the above urea aqueous solution and Zr salt aqueous solution were mixed and mechanically stirred for 30 min. Then, the mixed solution was placed in a 300 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 20 h. The solid-liquid separation was carried out on the crystallized intermediate material, and the solid-phase intermediate material was washed with deionized water and absolute ethanol. The washed solid-phase intermediate material was placed in an oven at 60 °C and dried for 12 h. The dried solid-phase intermediate material was placed in a tube furnace and calcined at 500 °C for 4 h to obtain monoclinic ZrO2 (m-ZrO2);

[0136] The m-ZrO2 was pretreated by passing argon through an ion sputtering machine in the form of ion sputtering. The pretreated m-ZrO2 was mixed with an aqueous solution of NaNO3, and then dried at 120 °C for 10 h. Finally, it was placed in a tube furnace for the first calcination. The temperature of the first calcination was 450 °C and the time was 4 h. Among them, the weight ratio of the amount of NaNO3 (calculated as metal) to m-ZrO2 was 3:100 to obtain an intermediate product;

[0137] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by an ion sputtering machine in the form of ion sputtering. Finally, it was placed in a tube furnace for the second calcination. The temperature of the second calcination was 400 °C and the time was 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to m-ZrO2 was 0.3:100.

[0138] Example 12

[0139] (1) First, add 17.1 g of Zr(NO3)4·5H2O to 50 mL of deionized water and stir mechanically. Add 38.7 g of urea to 200 mL of deionized water, then mix the above urea aqueous solution and Zr salt aqueous solution, and stir mechanically for 30 min. Then place the mixed solution in a 300 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene liner at 180 °C for crystallization for 20 h. Separate the solid and liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 60 °C for drying for 12 h, place the dried solid-phase intermediate material in a tubular furnace, and calcine it at 500 °C for 4 h to obtain monoclinic ZrO2 (m-ZrO2);

[0140] Use an ion sputtering machine to pretreat m-ZrO2 by ion sputtering with argon. Mix the pretreated m-ZrO2 with an aqueous KNO3 solution, then dry it at 120 °C for 10 h, and finally place it in a tubular furnace for the first calcination. The temperature of the first calcination is 450 °C and the time is 4 h. Among them, the weight ratio of KNO3 (calculated as metal) to the amount of m-ZrO2 used is 3:100 to obtain an intermediate product;

[0141] (2) Use an ion sputtering machine to load metal Pd onto the intermediate product obtained in step (1) by ion sputtering. Finally, perform the second calcination in a tubular furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metal Pd to m-ZrO2 is 0.3:100.

[0142] Comparative Example 1

[0143] (1) Mix 9 g of sodium dodecyl sulfate, 30 mL of ammonia water with a mass concentration of 25%, 3 mL of acetylacetone, 15 mL of absolute ethanol and 6.6 g of ZrOCl2·8H2O and stir. Then place the mixed solution in a 100 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene liner at 180 °C for crystallization for 6 h. Separate the solid and liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and absolute ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, place the dried solid-phase intermediate material in a tubular furnace, and calcine it at 450 °C for 3 h to obtain tetragonal ZrO2 (t-ZrO2). Use an ion sputtering machine to pretreat t-ZrO2 by ion sputtering with argon;

[0144] (2) Use an ion sputtering machine to load metallic Pd onto the intermediate product obtained in step (1) by ion sputtering, and finally conduct a second calcination in a tube furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metallic Pd to t-ZrO2 is 0.3:100.

[0145] Comparative Example 2

[0146] (1) Add 34.3 g of Zr(NO3)4·5H2O and 48 g of urea to 200 mL of anhydrous methanol, perform a water bath at 70 °C for 25 min, and then place the mixed solution in a 250 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 12 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and anhydrous ethanol, place the washed solid-phase intermediate material in an oven at 120 °C for drying for 12 h, place the dried solid-phase intermediate material in a tube furnace, and calcine at 500 °C for 4 h to obtain a composite phase ZrO2 (mt-ZrO2). Use an ion sputtering machine to pretreat mt-ZrO2 by ion sputtering with argon;

[0147] (2) Use an ion sputtering machine to load metallic Pd onto the intermediate product obtained in step (1) by ion sputtering, and finally conduct a second calcination in a tube furnace. The temperature of the second calcination is 400 °C and the time is 4 h. Among them, the working gas of the ion sputtering machine is argon, the working temperature of the ion sputtering machine is 25 °C, and the weight ratio of metallic Pd to mt-ZrO2 is 0.3:100.

[0148] Comparative Example 3

[0149] (1) First, add 17.1 g of Zr(NO3)4·5H2O to 50 mL of deionized water and stir mechanically. Add 38.7 g of urea to 200 mL of deionized water, and then mix the above urea aqueous solution and Zr salt aqueous solution and stir mechanically for 30 min. Then place the mixed solution in a 300 mL stainless steel hydrothermal autoclave with a polytetrafluoroethylene lining at 180 °C for crystallization for 20 h. Separate the solid-liquid of the crystallized intermediate material, wash the solid-phase intermediate material with deionized water and anhydrous ethanol, place the washed solid-phase intermediate material in an oven at 60 °C for drying for 12 h, place the dried solid-phase intermediate material in a tube furnace, and calcine at 500 °C for 4 h to obtain monoclinic ZrO2 (m-ZrO2). Use an ion sputtering machine to pretreat m-ZrO2 by ion sputtering with argon;

[0150] (2) The metal Pd was loaded onto the intermediate product obtained in step (1) by ion sputtering using an ion sputtering machine, and then a second calcination was carried out in a tube furnace at a temperature of 400 °C for 4 h. Among them, the working gas of the ion sputtering machine was argon, the working temperature of the ion sputtering machine was 25 °C, and the weight ratio of metal Pd to m-ZrO2 was 0.3:100.

[0151] Comparative Example 4

[0152] The method of Example 1 was implemented, except that the same weight of metal Ag was used to replace the metal Pd in step (2).

[0153] Comparative Example 5

[0154] The method of Example 5 was implemented, except that the same weight of metal Ag was used to replace the metal Pd in step (2).

[0155] Comparative Example 6

[0156] The method of Example 9 was implemented, except that the same weight of metal Ag was used to replace the metal Pd in step (2).

[0157] Test Example

[0158] The samples prepared in the examples and comparative examples were tested for catalytic activity. The test method was as follows: The samples were loaded into a fixed-bed reactor, and the raw material gas was passed into the fixed-bed reactor to contact the samples. Among them, the raw material gas consisted of 99.25 vol% of ethylene, 0.25 vol% of oxygen, and 0.5 vol% of hydrogen. The contact conditions were: the space velocity was 3000 h -1 , the pressure was 0.2 MPa, and the temperature was 120 °C. The deoxidation rate was calculated based on the final oxygen content in the raw material gas. The test results are shown in Table 1;

[0159] Table 1

[0160]

[0161]

[0162] It can be seen from the results in Table 1 that the olefin deoxidation catalyst containing ZrO2 described in the present invention has good catalytic activity. The olefin deoxidation catalyst containing ZrO2 has high catalytic activity, can deeply deoxidize olefin raw material gas with low oxygen content, and the deoxidation rate can reach up to 99.76%. It has good application prospects in olefin deoxidation.

[0163] 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 technical concept of the present invention, 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 regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. An olefin deoxidation catalyst containing ZrO2, characterized in that, The olefin deoxidation catalyst containing ZrO2 comprises a support and an active component supported on the support; The support contains ZrO2 and a promoter, the promoter is selected from one or more of Cu oxide, Zn oxide, Na oxide and K oxide, and the active component is Pd oxide.

2. The olefin deoxidation catalyst containing ZrO2 according to claim 1, characterized in that, The weight ratio of Pd oxide to ZrO2 is 0.05 - 0.3:100, wherein Pd oxide is calculated as metal; Preferably, the weight ratio of the promoter to ZrO2 is 0.5 - 20:100, wherein the promoter is calculated as metal.

3. The olefin deoxidation catalyst containing ZrO2 according to claim 1 or 2, characterized in that, The ZrO2 is tetragonal ZrO2, composite ZrO2 or monoclinic ZrO2.

4. A method for preparing an olefin deoxygenation catalyst containing ZrO2, characterized in that, The method comprises the following steps: (1) Mix ZrO2 and a promoter precursor solution, and then perform a first calcination; (2) Load metal Pd onto the material obtained in step (1), and then perform a second calcination; The promoter precursor is selected from one or more of copper salts, zinc salts, sodium salts and potassium salts.

5. The method according to claim 4, wherein The ZrO2 is tetragonal ZrO2, composite ZrO2 or monoclinic ZrO2.

6. The method according to claim 5, wherein The preparation method of the tetragonal ZrO2 comprises: mixing a Zr salt, a surfactant, an organic solvent and ammonia water, then performing crystallization, and then performing calcination; The conditions of the crystallization include: the temperature is 100 - 200 °C, and the time is 2 - 15 h; The conditions of the calcination include: the temperature is 300 - 600 °C, and the time is 2 - 8 h.

7. The method according to claim 5, wherein The preparation method of the composite ZrO2 comprises: mixing a Zr salt, urea and an organic solvent, then performing crystallization, and then performing calcination; The conditions of the crystallization include: the temperature is 120 - 300 °C, and the time is 6 - 12 h; The conditions of the calcination include: the temperature is 300 - 600 °C, and the time is 2 - 8 h.

8. The method according to claim 5, wherein The preparation method of the monoclinic ZrO2 comprises: mixing a Zr salt, urea and an organic solvent, then performing crystallization, and then performing calcination; The conditions of the crystallization include: the temperature is 120 - 350 °C, and the time is 20 - 30 h; The conditions of the calcination include: the temperature is 300 - 600 °C, and the time is 2 - 8 h.

9. The method according to any one of claims 4 to 8, characterized in that In step (1), the weight ratio of the promoter precursor to the amount of ZrO2 used is 1 - 20:100, wherein the promoter precursor is calculated as metal; Preferably, the conditions of the first calcination include: the temperature is 350 - 500 °C, and the time is 3 - 6 h.

10. The method according to any one of claims 4-9, characterized in that, In step (2), the weight ratio of the amount of metal Pd to ZrO2 used is 0.1 - 0.3:100; Preferably, in step (2), the loading method is selected from impregnation, ion sputtering or electrochemical deposition; Preferably, in step (2), the conditions of the second calcination include: the temperature is 300 - 500 °C, and the time is 3 - 5 h.

11. An olefin deoxidation catalyst containing ZrO2 prepared by the method according to any one of claims 4 - 10.

12. Use of the olefin deoxidation catalyst containing ZrO2 according to any one of claims 1 - 3 and 11 in an olefin deoxidation reaction.

13. A method for the deoxygenation reaction of olefins, characterized in that, Contact the feed gas with the catalyst; The feed gas contains olefins, oxygen and hydrogen; The catalyst is an olefin deoxidation catalyst containing ZrO2 as described in any one of claims 1-3 and 11.

14. The method according to claim 13, wherein The content of oxygen in the raw material gas is ≤ 0.25% by volume, and the volume ratio of hydrogen to oxygen is ≤ 4.

15. The method according to claim 13 or 14, characterized in that, The conditions for the contact include: the space velocity is 2000 - 5000 h -1 , the pressure is 0.1 - 0.4 MPa, and the temperature is 100 - 200 °C.

Images