Method for catalyzing PEE hydrofining by Ni-APO-34 catalyst

Abstract

The invention provides a method for catalyzing PEE hydrofining by a Ni-APO-34 catalyst. The method comprises the following steps: mixing a phosphorus source, an aluminum source, a nickel source and a first solution to obtain a Ni-P-Al precursor; mixing the Ni-P-Al precursor, a structure-directing agent, a seed crystal and a second solution to obtain a Ni-APO-34 molecular sieve; the method comprises the following steps: mixing a Ni-APO-34 molecular sieve, initial PEE and a solvent in a high-pressure reaction kettle to obtain a mixture, and carrying out hydrofining on the mixture under a preset pressure intensity of 1-5 MPa to prepare final PEE from the mixture. By preparing the catalyst which has a uniform microporous structure and can selectively adsorb hydrogen molecules and form high local hydrogen concentration in a pore channel, the actual hydrogen concentration in the pore channel still meets the hydrogenation reaction requirement under the condition that the hydrogen pressure environment is relatively low, and compared with traditional Raney nickel, high-pressure side reaction inhibition is not needed, so that the preparation method is simple, and the cost is low. And the production cost and the maintenance cost are effectively saved.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical product preparation, and particularly to a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst. Background Art

[0002] A compressor is a driven fluid machine that boosts low-pressure gas to high-pressure gas. It is the heart of a refrigeration system. It sucks in low-temperature and low-pressure refrigerant gas from the suction pipe, compresses it, and then discharges high-temperature and high-pressure refrigerant gas to the exhaust pipe, providing power for the refrigeration cycle.

[0003] Polyvinyl ether (PEEE) is an important refrigerant oil (lubricating oil) for compressors. However, during its preparation process, functional groups such as carbon-carbon double bonds, aldehyde groups, and acetals are generated at the end groups, and these functional groups will affect the stability of the refrigerant oil. To improve the stability of the refrigerant oil, currently, anhydrous AlCl3 is generally used as an acid catalyst and Raney nickel as a hydrogenation active component to synthesize high-quality polyvinyl ether in one step under ultra-high pressure conditions (30 MPa).

[0004] However, due to the large reaction pressure required for synthesizing lubricating oil, the requirements for production equipment are extremely high, resulting in correspondingly increased production costs and maintenance costs. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, aiming to solve the technical problem in the prior art that when synthesizing high-quality polyvinyl ether in one step under ultra-high pressure conditions, the reaction pressure requirement is large, the requirements for production equipment are extremely high, resulting in correspondingly increased production costs and maintenance costs.

[0006] To achieve the above purpose, the present invention provides a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, including the following steps:

[0007] Mix a phosphorus source, an aluminum source, a nickel source, and a first solution to form a first mixed solution. Under closed conditions, perform a first stirring treatment and a first hydrothermal treatment on the first mixed solution to obtain a first treated solution. Perform a first filtration treatment and a first drying treatment on the first treated solution to obtain a Ni-P-Al precursor.

[0008] Mix the Ni-P-Al precursor, a structure-directing agent, seeds, and a second solution to form a second mixed solution. Under closed conditions, perform a second stirring treatment and a second hydrothermal treatment on the second mixed solution to obtain a second treated solution. Perform a second filtration treatment, a second drying treatment, and a calcination treatment on the second treated solution to obtain a Ni-APO-34 molecular sieve.

[0009] Mix the Ni-APO-34 molecular sieve, the initial PEE and the solvent in a high-pressure reactor to obtain a mixture. Replace the hydrogen in the high-pressure reactor, and carry out hydrorefining on the mixture at a preset pressure to prepare the mixture into the final PEE. The preset pressure is 1 MPa to 5 MPa.

[0010] Furthermore, the phosphorus source is phosphoric acid or phosphorous acid, the aluminum source is pseudoboehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate or aluminum sol, and the nickel source is nickel nitrate, nickel chloride or nickel sulfate.

[0011] Furthermore, both the first solution and the second solution are water, and the solvent is cyclohexane or n-hexane.

[0012] Furthermore, the mixing ratio of the phosphorus source, the aluminum source and the nickel source is 1:1:0.0001 to 1:1:0.1.

[0013] Furthermore, the temperature of the first hydrothermal treatment is 60°C to 160°C, and the time of the first hydrothermal treatment is 2 h to 24 h.

[0014] Furthermore, the mixing ratio of the Ni-P-Al precursor, the structure directing agent and the second solution is 1:(1 - 5):(0.5 - 5).

[0015] Furthermore, the temperature of the second hydrothermal treatment is 150°C to 220°C, and the time of the second hydrothermal treatment is 12 h to 240 h.

[0016] Furthermore, the mass ratio of the Ni-APO-34 molecular sieve to the initial PEE is 0.005:1 to 0.1:1.

[0017] Furthermore, the temperature of the hydrotreating is 90°C to 250°C.

[0018] Furthermore, the hydrogen pressure of the hydrotreating is 2.5 MPa.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: By preparing the Ni-APO-34 molecular sieve, which has a uniform microporous structure, the pores of which can selectively adsorb hydrogen molecules to form a high local hydrogen concentration inside the pores, that is, when the hydrogen pressure environment is relatively low (1 MPa to 5 MPa), the actual hydrogen concentration in the pores is still sufficient to meet the requirements of the hydrogenation reaction, realizing a high-pressure environment at the microscale; Nickel atoms are introduced into the Ni-APO-34 molecular sieve, which exist in the molecular sieve framework in the form of single atoms to form highly dispersed active sites. Compared with traditional Raney nickel, more Ni active sites supported by the Ni-APO-34 molecular sieve are exposed and the reaction path is shorter, which reduces the reaction energy barrier and does not require high-pressure compensation; The microporous structure of the Ni-APO-34 molecular sieve only allows small-sized unstable end-group functional groups (such as double bonds, aldehyde groups, and acetal groups) in the initial PEE to enter the pores to contact the Ni active sites, while the long-chain main structure is blocked outside to accurately locate the hydrogenation target, reducing the consumption of ineffective hydrogen and avoiding many non-selective side reactions (such as over-hydrogenation or cracking). Compared with traditional Raney nickel, high pressure is not required to inhibit side reactions, effectively saving production costs and maintenance costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a flow chart of the method for catalytic hydrogenation refining of PEE by the Ni-APO-34 catalyst in Example 1 of the present invention;

[0021] The following specific embodiments will further illustrate the present invention in conjunction with the above-mentioned drawings. SPECIFIC EMBODIMENTS

[0022] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. Several embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the disclosure of the present invention more thorough and comprehensive.

[0023] It should be noted that when an element is referred to as being "fixed to" another element, it can be directly on the other element or there may also be a middle element. When an element is considered to be "connected" to another element, it can be directly connected to the other element or there may be a middle element at the same time. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are only for the purpose of illustration.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this invention belongs. The terms used in the description of this invention herein are for the purpose of describing specific embodiments only and are not intended to limit the invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0025] Please refer to Figure 1 , Embodiment 1 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, comprising the following steps:

[0026] S10: Mix a phosphorus source, an aluminum source, a nickel source and a first solution to form a first mixed solution, perform a first stirring treatment and a first hydrothermal treatment on the first mixed solution under a closed condition to obtain a first treated solution, and perform a first filtration treatment and a first drying treatment on the first treated solution to obtain a Ni-P-Al precursor;

[0027] Preferably, the phosphorus source is phosphoric acid or phosphorous acid, the aluminum source is pseudo-boehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate or aluminum sol, and the nickel source is nickel nitrate, nickel chloride or nickel sulfate. In this embodiment, the phosphorus source is phosphoric acid, the aluminum source is aluminum hydroxide, and the nickel source is nickel nitrate. The first solution is water. The mixing ratio of the phosphorus source, the aluminum source and the nickel source is 1:1:0.0001.

[0028] The temperature of the first hydrothermal treatment is 60°C, and the time of the first hydrothermal treatment is 2 h.

[0029] S20: Mix the Ni-P-Al precursor, a structure-directing agent, seeds and a second solution to form a second mixed solution, perform a second stirring treatment and a second hydrothermal treatment on the second mixed solution under a closed condition to obtain a second treated solution, and perform a second filtration treatment, a second drying treatment and a calcination treatment on the second treated solution to obtain a Ni-APO-34 molecular sieve;

[0030] Preferably, the structure-directing agent is tetraethylammonium hydroxide, triethylamine, diethylamine, ethylamine, triethanolamine or ethanolamine. In this embodiment, the structure-directing agent is triethanolamine. The second solution is water. The mixing ratio of the Ni-P-Al precursor, the structure-directing agent and the second solution is 1:1:0.5. The temperature of the second hydrothermal treatment is 150 °C, and the time of the second hydrothermal treatment is 12 h. It should be noted that the seed crystal is a tiny crystal of the Ni-APO-34 molecular sieve, which is obtained by pre-synthesis. By setting the seed crystal, it provides the same crystal structure and pore topology as the Ni-APO-34 molecular sieve, ensures the directional growth of crystals in subsequent reactions, avoids the generation of impurity phases, and by setting the seed crystal, it can serve as a ready-made crystal nucleus, reducing the nucleation induction period and shortening the acquisition time of the Ni-APO-34 molecular sieve.

[0031] S30: Mix the Ni-APO-34 molecular sieve, the initial PEE and the solvent in a high-pressure reactor to obtain a mixture. Replace the air in the high-pressure reactor with hydrogen, and carry out hydrorefining on the mixture at a preset pressure to prepare the mixture into the final PEE. The preset pressure is 1 MPa to 5 MPa;

[0032] The initial PEE is prepared by a traditional cationic polymerization process, and its end groups will generate functional groups such as carbon-carbon double bonds, aldehyde groups and acetals. The hydrogen replacement means introducing hydrogen into the high-pressure reactor so that the air or other residual gases in the high-pressure reactor are completely replaced by hydrogen, ensuring that the reaction environment is a pure hydrogen atmosphere. The step of replacing the air in the high-pressure reactor with hydrogen is specifically: performing a vacuum treatment on the high-pressure reactor; introducing hydrogen into the high-pressure reactor after the vacuum treatment to complete a single cycle; repeating the single cycle several times until the oxygen content in the high-pressure reactor is less than a preset threshold. The preset threshold is 100 ppm. It should be noted that when performing several single cycle operations, the hydrogen pressure is less than 1 MPa. The mass ratio of the Ni-APO-34 molecular sieve to the initial PEE is 0.005:1. The temperature of the hydrotreatment is 90 °C, and the hydrogen pressure of the hydrotreatment is 2.5 MPa. Preferably, the solvent is cyclohexane or n-hexane. In this embodiment, the solvent is cyclohexane.

[0033] By preparing the Ni-APO-34 molecular sieve, which has a uniform microporous structure, the pores of which can selectively adsorb hydrogen molecules to form a high local hydrogen concentration inside the pores, that is, when the hydrogen pressure environment is relatively low (1 MPa to 5 MPa), the actual hydrogen concentration in the pores is still sufficient to meet the requirements of the hydrogenation reaction, achieving a high-pressure environment at the microscale; nickel atoms are introduced into the Ni-APO-34 molecular sieve, which exist in the molecular sieve framework in the form of single atoms to form highly dispersed active sites. Compared with traditional Raney nickel, more Ni active sites loaded on the Ni-APO-34 molecular sieve are exposed and the reaction path is shorter, which reduces the reaction energy barrier and does not require high-pressure compensation; the microporous structure of the Ni-APO-34 molecular sieve only allows small-sized unstable end-group functional groups (such as double bonds, aldehyde groups, and acetal groups) in the initial PEE to enter the pores to contact the Ni active sites, while the long-chain main structure is blocked outside to accurately locate the hydrogenation target, reducing the consumption of ineffective hydrogen and avoiding many non-selective side reactions (such as over-hydrogenation or cracking). Compared with traditional Raney nickel, high pressure is not required to inhibit side reactions, effectively saving production costs and maintenance costs.

[0034] Example 2 of the present invention provides a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE with the Ni-APO-34 catalyst described in Example 1 in that

[0035] The mixing ratio of the phosphorus source, the aluminum source, and the nickel source is 1:1:0.1.

[0036] Example 3 of the present invention provides a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE with the Ni-APO-34 catalyst described in Example 1 in that

[0037] The temperature of the first hydrothermal treatment is 160 °C.

[0038] Example 4 of the present invention provides a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE with the Ni-APO-34 catalyst described in Example 1 in that

[0039] The time of the first hydrothermal treatment is 24 h.

[0040] Example 5 of the present invention provides a method for catalytic hydrorefining of PEE with a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE with the Ni-APO-34 catalyst described in Example 1 in that

[0041] The mixing ratio of the Ni-P-Al precursor, the structure-directing agent, and the second solution is 1:5:5.

[0042] Example 6 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0043] The temperature of the second hydrothermal treatment is 220 °C.

[0044] Example 7 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0045] The time of the second hydrothermal treatment is 240 h.

[0046] Example 8 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0047] The mass ratio of the Ni-APO-34 molecular sieve to the initial PEE is 0.1:1.

[0048] Example 9 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0049] The temperature of the hydrotreating is 250 °C.

[0050] Comparative Example 1 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0051] The mixing ratio of the phosphorus source, the aluminum source, and the nickel source is 1:0.8:0.00005.

[0052] Comparative Example 2 of the present invention provides a method for catalytic hydrorefining of PEE using a Ni-APO-34 catalyst, which is different from the method for catalytic hydrorefining of PEE using the Ni-APO-34 catalyst described in Example 1 in that

[0053] The temperature of the first hydrothermal treatment is 200 °C.

[0054] Comparative Example 3 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0055] the time of the first hydrothermal treatment is 1 h.

[0056] Comparative Example 4 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0057] the mixing ratio of the Ni-P-Al precursor, the structure-directing agent and the second solution is 1:0.5:0.2.

[0058] Comparative Example 5 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0059] the temperature of the second hydrothermal treatment is 250 °C.

[0060] Comparative Example 6 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0061] the time of the second hydrothermal treatment is 8 h.

[0062] Comparative Example 7 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0063] the mass ratio of the Ni-APO-34 molecular sieve to the initial PEE is 0.002:1.

[0064] Comparative Example 8 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0065] the temperature of the hydrotreating is 300 °C.

[0066] Comparative Example 9 of the present invention provides a method for the hydrorefining of PEE catalyzed by a Ni-APO-34 catalyst, which is different from the method for the hydrorefining of PEE catalyzed by the Ni-APO-34 catalyst described in Example 1 in that,

[0067] Anhydrous AlCl3 and Raney nickel were synthesized into the final PEE under the calibrated pressure by a one-step synthesis method, and the calibrated pressure was 30 MPa. That is, in this comparative example, the functional groups generated during the preparation of the final PEE were avoided by a traditional hydrogenation method.

[0068] The final PEE was prepared according to the Ni-APO-34 catalyst-catalyzed PEE hydrorefining method described in the above Examples 1 to 9 and Comparative Examples 1 to 9, and the performance of the obtained final PEE was detected. Specifically, the performance detection included thermal decomposition temperature detection, evaporation loss rate detection, and high-temperature viscosity retention rate detection. The steps of the thermal decomposition temperature detection included: taking 10 mg of the final PEE and performing vacuum drying treatment on it; placing the vacuum-dried final PEE in a detector and heating the detector, and the heating rate was 10 °C / min; during the heating process, a mass-temperature curve corresponding to the final PEE was obtained, a first tangent was made in its mass stable section, and a second tangent was made in its mass decreasing section, and the thermal decomposition temperature was determined based on the intersection of the first tangent and the second tangent. The steps of the evaporation loss rate detection included: taking 2 g of the final PEE with an initial mass and placing it in an oven, adjusting the oven to a preset temperature, and after heating the final PEE for a preset time, weighing the mass of the final PEE after heating. In this example, the preset temperature was 150 °C, the preset time was 24 h, and the evaporation loss rate = (initial mass - mass after heating) / initial mass * 100%. The specific steps of the high-temperature viscosity retention rate detection included: obtaining the initial viscosity of the final PEE, placing the final PEE in a parallel plate fixture, and heating it to the test temperature. After heating the final PEE for a preset time at the test temperature, the final viscosity of the final PEE was obtained, and the viscosity retention rate = final viscosity / initial viscosity * 100%. According to the above detection methods, the detection results are shown in Table 1 below:

[0069] Table 1

[0070]

[0071] , as can be seen from the above table, the final PEE obtained by the Ni-APO-34 catalyst-catalyzed PEE hydrorefining method in this application is the same as the final PEE synthesized under high pressure by the one-step synthesis method in terms of the relevant indicators characterizing the stability of PEE, such as thermal decomposition temperature, evaporation loss rate, and high-temperature viscosity retention rate. That is, by the method in this application, the preparation of the final PEE with the same performance can be completed under low-pressure conditions, which effectively saves the production cost and maintenance cost. By controlling the process parameters and mass ratios in this application, it can be ensured that the obtained final PEE maintains better stability.

[0072] In the description of this specification, the descriptions with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0073] The above-described embodiments merely represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but should not be construed as a limitation on the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims

1. A method for hydrorefining PEE catalyzed by a Ni-APO-34 catalyst, characterized in that, It includes the following steps: Mix a phosphorus source, an aluminum source, a nickel source and a first solution to form a first mixed solution. Carry out a first stirring treatment and a first hydrothermal treatment on the first mixed solution under a closed condition to obtain a first treated solution. Carry out a first filtration treatment and a first drying treatment on the first treated solution to obtain a Ni-P-Al precursor; Mix the Ni-P-Al precursor, a structure-directing agent, seeds and a second solution to form a second mixed solution. Carry out a second stirring treatment and a second hydrothermal treatment on the second mixed solution under a closed condition to obtain a second treated solution. Carry out a second filtration treatment, a second drying treatment and a calcination treatment on the second treated solution to obtain a Ni-APO-34 molecular sieve; Mix the Ni-APO-34 molecular sieve, an initial PEE and a solvent in a high-pressure reaction kettle to obtain a mixture. Carry out a hydrogen replacement on the high-pressure reaction kettle, and carry out hydrorefining on the mixture under a preset pressure to prepare the mixture into a final PEE, and the preset pressure is 1 MPa to 5 MPa.

2. The method for hydrorefining PEE catalyzed by the Ni-APO-34 catalyst according to claim 1, characterized in that, The phosphorus source is phosphoric acid or phosphorous acid, the aluminum source is pseudo-boehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate or aluminum sol, and the nickel source is nickel nitrate, nickel chloride or nickel sulfate.

3. The Ni-APO-34 catalyst-catalyzed hydrorefining method for PEE according to claim 1, characterized in that, Both the first solution and the second solution are water, and the solvent is cyclohexane or n-hexane.

4. The Ni-APO-34 catalyst-catalyzed hydrorefining method of PEE according to claim 1, wherein The mixing ratio of the phosphorus source, the aluminum source and the nickel source is 1:1:0.0001 to 1:1:0.

1.

5. The Ni-APO-34 catalyst-catalyzed hydrorefining method for PEE according to claim 1, characterized in that, The temperature of the first hydrothermal treatment is 60°C to 160°C, and the time of the first hydrothermal treatment is 2 h to 24 h.

6. The Ni-APO-34 catalyst-catalyzed hydrorefining method of PEE according to claim 1, characterized in that The mixing ratio of the Ni-P-Al precursor, the structure-directing agent and the second solution is 1:(1 to 5):(0.5 to 5).

7. The method for hydrorefining PEE by using the Ni-APO-34 catalyst according to claim 1, characterized in that, The temperature of the second hydrothermal treatment is 150°C to 220°C, and the time of the second hydrothermal treatment is 12 h to 240 h.

8. The Ni-APO-34 catalyst-catalyzed hydrorefining method for PEE according to claim 1, wherein The mass ratio of the Ni-APO-34 molecular sieve to the initial PEE is 0.005:1 to 0.1:

1.

9. The method for hydrorefining PEE by using the Ni-APO-34 catalyst according to claim 1, characterized in that, The temperature of the hydrotreatment is 90°C to 250°C.

10. The method for hydrorefining PEE catalyzed by the Ni-APO-34 catalyst according to claim 1, characterized in that, The hydrogen pressure of the hydrotreatment is 2.5 MPa.

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