CN102728393A - Non-loaded type nano hydrogenation deoxidation catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a non-loaded nano hydrogenation deoxygenation catalyst and a preparation method thereof. A non-supported nanometer hydrogenation deoxygenation catalyst, which uses nickel, molybdenum, and tungsten compounds as precursors of active components, and the required precursors are mechanically milled and calcined to form catalysts in the form of metal sulfides. The components of the required precursor are composed by mass percentage: nickel nitrate 3%-40%, molybdenum oxide 1%-40%, tungsten oxide 1%-70%, sulfur 5%-70%. The method of constant temperature annealing after high-energy ball milling under the action of protective atmosphere is adopted to prepare nanometer catalyst body particles. The invention prepares a non-supported nano-catalyst with high hydrodeoxygenation catalytic activity through a simple and effective method. The catalyst has high activity, high deoxygenation selectivity, high stability, simple production method and low cost, and can be widely used in Hydrodeoxygenation and refining of coal-to-oil, bio-oil and other new petroleum alternative energy sources.

Description

A kind of non-supported nano hydrogenation deoxygenation catalyst and preparation method thereof

technical field

The invention relates to a non-loaded nano hydrogenation deoxygenation catalyst and a preparation method thereof, belonging to the technical field of preparation of deoxygenation catalysts for petroleum alternative energy sources with high oxygen content.

Background technique

In recent years, China has become the world's second largest energy consumer. The rapid economic development has made petroleum energy more and more important in national economic and social development, and the demand for petroleum resources is also increasing year by year. The lack of oil resources and the continuous rise of international oil prices have made countries around the world begin to seek and develop emerging alternative energy sources. However, the primary products of emerging petroleum alternative energy sources such as coal-to-oil and bio-oil have low heat of combustion, poor stability, and corrosion, which limit their large-scale industrial application. The existence of these defects is related to the high oxygen content. Related literature shows that the oxygen content in some biomass oils is as high as 50wt%. At the same time, the raw materials also contain sulfur- and nitrogen-containing compounds. The existence of these compounds inhibits the progress of the hydrodeoxygenation process. Compared with hydrodesulfurization and hydrodenitrogenation, hydrodeoxygenation is more complicated and difficult.

For solid catalysts, not only the types and contents of active components, additives, and types and properties of supports affect the activity of the catalysts, but the preparation method is also an important factor affecting the performance of the catalysts. At present, the preparation methods of solid catalyst mainly include: processing of natural resources, precipitation method, impregnation method, mixing method, and plasma exchange method. Patent CN1458232A discloses a hydrogenation catalyst containing γ-Al ₂ O ₃ precursor, with W and Ni as active components, and F or B as auxiliary agent, which is suitable for petroleum fractionation. Hydrogenation and dearomatization performance, but the hydrogenation activity is not ideal for Fischer-Tropsch synthetic oils with high olefins and oxygenates. Patent CN101270300A discloses a hydrodeoxygenation catalyst for the production of biodiesel, using non-precious metal nickel, molybdenum, cobalt, tungsten salt as the precursor of the active component, titanium dioxide as the carrier to prepare the catalyst by repeated impregnation, and using palm oil As an example, the evaluation is carried out on a miniature fixed reactor. The reaction results show that the catalytic activity does not change much after repeated regenerations, and the catalyst has high catalytic activity and good stability. Patent CN1597859A discloses a catalyst for Fischer-Tropsch synthesis, hydrogenation, deoxygenation and olefin saturation, as well as its preparation method and application. Nickel oxide, cobalt oxide, copper oxide, iron oxide, titanium oxide, lanthanum oxide and carriers are co-impregnated and impregnated The catalyst was prepared by the method, and the experimental results show that the catalyst has high activity for oil hydrodeoxygenation and olefin saturation, and is suitable for hydrofinishing of iron-based slurry bed Fischer-Tropsch synthetic oil with high content of oxygenates and olefins.

However, the above methods all have the disadvantages of complex production process, poor dispersion and uniformity, poor deoxygenation and hydrogenation activity for bio-oil products, unstable catalyst performance, and easy deactivation to varying degrees. Therefore, the development of catalysts with higher catalytic activity for hydrodeoxygenation will always be one of the researchers' research priorities.

In 2001, US Patent 6299760B1 disclosed a non-supported NiMoW three-way hydrodesulfurization catalyst-NEBULA, which has a catalytic activity 4 times higher than that of traditional catalysts. It can be said that the NEBULA catalyst is the first real leap in catalyst composition and activity since the development of hydrorefining catalysts in the 1950s. Their research work has attracted widespread attention, and many researchers have shifted their research focus to this new catalyst. Three-way catalytic system and try to apply it to petroleum hydrorefining process.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art and provide a primary product hydrodeoxygenation activity, high selectivity, and good stability for primary product hydrodeoxygenation of coal-to-oil, bio-oil and other petroleum alternative energy sources. Catalyst and method for its preparation. To remove the oxygen contained in the primary products of petroleum alternative energy such as coal-to-oil and bio-oil, and improve its combustion calorific value, stability and corrosion resistance.

The present invention is a non-supported nano hydrodeoxygenation catalyst. The catalyst uses nickel, molybdenum, and tungsten compounds as the precursor of the active component. The precursor is mechanically milled and calcined to form a catalyst in the form of a metal sulfide. The precursor is composed of the following components by mass percentage:

Nickel nitrate 3%-40%,

Molybdenum oxide 1%-40%,

Tungsten oxide 1%-70%,

Sulfur 5%-70%.

The preparation method of a kind of non-loaded nanometer hydrogenation deoxygenation catalyst of the present invention is to take nickel nitrate, molybdenum oxide, tungsten oxide and sulfur respectively according to the weight ratio of each component of the precursor of the hydrogenation deoxygenation catalyst designed, under the protective atmosphere After ball milling to a particle size of 80-400nm, heating to 600-900° C. for constant temperature annealing for 15-120 minutes under a protective atmosphere, and cooling to room temperature with the furnace to obtain a non-supported nanometer hydrogenation deoxygenation catalyst.

A kind of preparation method of the non-loaded nano hydrogenation deoxygenation catalyst of the present invention, during ball milling, add dehydrated alcohol to the mixture of nickel nitrate, molybdenum oxide, tungsten oxide and sulfur as process control agent; The addition amount of described dehydrated alcohol It is 1-10% of the total mass of the mixture.

The invention discloses a method for preparing a non-supported nanometer hydrogenation deoxygenation catalyst. The technical conditions of the ball milling are as follows: stainless steel balls are used as the ball milling medium, the ball-to-material ratio is 10-100:1, and the ball milling speed is 200-800r/min. The ball milling time is 2-48h.

The invention relates to a preparation method of a non-loaded nano hydrogenation deoxygenation catalyst, wherein the constant temperature annealing temperature is 600-900° C., and the constant temperature time is 15-120 minutes.

The invention discloses a method for preparing a non-supported nanometer hydrogenation deoxygenation catalyst. The constant temperature annealing adopts a tube furnace, and the ball-milled powder and the sublimed sulfur as a supplementary sulfur source are respectively placed in three different porcelain boats and placed in molybdenum boats. It should be ensured that the molybdenum boat is placed in the heating center area of the tube furnace and the porcelain boat filled with sublimated sulfur should be placed upstream of the protective atmosphere.

The invention relates to a preparation method of a non-loaded nano hydrogenation deoxygenation catalyst, wherein the protective atmosphere is argon or nitrogen.

The mechanism of the present invention is briefly described as follows: phenols are the most common compounds in coal-to-oil and bio-oil hydrodeoxygenation refining processes, and the main reaction mechanism of phenols hydrodeoxygenation is: (1) C _R -OH bond direct hydrogen (2) C _{R -CR} bond hydrogenation and C _R -OH bond hydrogenation combined hydrogenation pathway (HYD), where C _R represents the carbon atom on the benzene ring. The active components of hydrodeoxygenation catalysts are mainly transition metal elements and their compounds, including Mo and W of Group VB and Ni, Co, Fe, Pb and Pt of Group VIII. The present invention adopts the ternary component compound containing Ni, Mo, W by means of the instant high-temperature and high-pressure effect produced by high-energy ball milling, and regulates its microstructure through annealing to prepare a nano-catalyst, which increases the specific surface area of the catalyst and makes the catalyst more stable. The effective metal active sites on the surface increase, and the contact area between the catalyst and the reactant increases, thereby effectively increasing the reactivity of the catalyst.

Advantage of the present invention and beneficial effect are embodied in:

The unsupported nano hydrodeoxygenation catalyst prepared by the invention is suitable for new petroleum alternative energy sources such as coal-to-oil and biomass oil. Taking tetramethylphenol as the model compound, the reaction pressure in the high-pressure reactor was 3MPa, the reaction temperature was 300°C, the stirring rate of the reactor motor was 800r/min, and the gas chromatography (GC9790Ⅱ) was used for analysis and characterization. The hydrodeoxygenated product was analyzed and characterized by Shimadzu QP-2010S GC/MS was calibrated, and it was determined that the peak of methylcyclohexane appeared at about 2.3min, the peak of tetramethylcyclohexene appeared at about 2.6min, and the peak of toluene appeared at about 2.8min. The peak of tetramethylphenol appeared at about 17.7min. The products of the hydrodeoxygenation reaction of tetramethylphenol by the catalyst include hydrogenation products such as toluene, methylcyclohexane and methylcyclohexene, and no oxygen-containing products such as methylcyclohexanol and methylcyclohexanone have been found. After a long period of continuous operation, the reaction still maintains a high conversion rate, which shows that the catalyst has the advantages of high deoxygenation selectivity to tetramethylphenol, good stability, high conversion rate, and easy realization of reaction conditions. It makes it possible to apply it to the hydrodeoxygenation and refining treatment of various new petroleum alternative energy sources such as coal-to-oil and bio-oil.

In summary, the catalyst of the present invention has good hydrodeoxygenation activity, high selectivity and good stability for primary products of petroleum alternative energy such as coal-to-oil and bio-oil, and the reaction conditions are easy to realize. It can effectively remove the oxygen contained in the primary products of petroleum alternative energy such as coal-to-oil and bio-oil, and improve its combustion calorific value, stability and corrosion resistance. It is suitable for hydrodeoxygenation and refining treatment of various new petroleum alternative energy sources such as coal-to-oil and bio-oil.

Description of drawings:

Accompanying drawing 1 is the X-ray diffraction (XRD) spectrum of the non-supported nano hydrodeoxygenation catalyst prepared in the embodiment of the present invention.

In Fig. 1, curve (a) is the X-ray diffraction (XRD) spectrum of the non-supported nano hydrodeoxygenation catalyst prepared in Example 1;

Curve (b) is the X-ray diffraction (XRD) spectrum of the non-supported nano hydrodeoxygenation catalyst prepared in Example 2;

Curve (c) is the X-ray diffraction (XRD) spectrum of the non-supported nano hydrodeoxygenation catalyst prepared in Example 3;

Curve (d) is the X-ray diffraction (XRD) pattern of the non-supported nano hydrodeoxygenation catalyst prepared in Example 4;

Curve (e) is the X-ray diffraction (XRD) spectrum of the non-supported nano hydrodeoxygenation catalyst prepared in Example 5.

It can be seen from Figure 1 that nickel, molybdenum and tungsten exist in the form of sulfide, and the sulfide products of nickel, molybdenum and tungsten are NiS, MoS ₂ and WS ₂ . (002), (100), (105), (103), (110) and (112) represent typical characteristic peaks of MoS ₂ and WS ₂ . The characteristic peaks of MoS ₂ and WS ₂ are narrow and sharp, indicating that the catalysts have good stacking structure, crystallization properties and small particle size in the c-axis direction. Due to the addition of nickel _as an additive, Ni atoms are mainly located at the edge positions of the _{MoS 2} and WS ₂ layered structures. Weak, so these S atoms are easily eliminated to form more sulfur vacancies (unsaturated coordination sites), which are considered as catalytic active centers. Because the catalyst particles are fine, the number of active sites increases, which can greatly increase the catalytic activity of the catalyst.

Detailed ways:

The technical characteristics of the present invention will be described in detail below in conjunction with specific embodiments.

Example 1:

Weigh 5.82g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O), 2.88g of molybdenum trioxide (MoO ₃ ), 4.64g of tungsten trioxide (WO ₃ ) and 1.66g of sublimed sulfur as raw materials. The weight percentage of components is 38.8% nickel nitrate, 19.2% molybdenum trioxide, 30.9% tungsten trioxide, 11.1% sublimated sulfur, 0.15ml absolute ethanol as process control agent, and stainless steel balls as ball milling medium under the protection of argon atmosphere , the ball-to-material ratio is 15:1, the ball milling speed is 400r/min, and the ball milling time is 24h for mechanical ball milling. The mixed powder after mechanical ball milling is placed under the protection of argon atmosphere for 1.5h constant temperature annealing at 600°C. A sufficient amount of sulfur is used to ensure complete vulcanization of the mixed powder, and the black non-supported nano hydrodeoxygenation catalyst can be prepared after cooling to room temperature with the furnace, and the particle size of the catalyst is 100-200nm.

Add 0.2g of catalyst, 100mL of decahydronaphthalene, and 2.77g of tetramethylphenol into a 250ml autoclave, fill it with hydrogen, the initial hydrogen pressure is 3.0MPa, start stirring and heating, and stop the reaction after reacting at 300°C for 5 hours. The first three samples were taken every 40 minutes, and the last three samples were taken out with a small volume of liquid samples every 1 hour, analyzed and characterized by a gas chromatograph (GC9790Ⅱ), and the hydrodeoxygenated product was calibrated by Shimadzu QP-2010S GC/MS , Calculate the conversion rate of 4-methylphenol. The analysis results of Example 1 show that the peak of methylcyclohexane occurred at about 2.3min, the peak of tetramethylcyclohexene occurred at about 2.6min, the peak of toluene occurred at about 2.8min, and the peak of tetramethylcyclohexene occurred at about 2.8min. The peak of phenol appears at about 17.7min. The product of tetramethylphenol hydrodeoxygenation reaction contains hydrogenation products such as toluene, methylcyclohexane and tetramethylcyclohexene, and no oxygen-containing products such as tetramethylcyclohexanol and tetramethylcyclohexanone are found , indicating that the deoxygenation selectivity of the catalyst is very high. The distribution, peak area and peak area percentage of hydrodeoxygenation products are shown in Table 1. Finally, the conversion rate of tetramethylphenol is 100% within five hours.

Each material peak area and content before and after the reaction in Table 1 embodiment

Example 2:

Weigh 2.91g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O), 4.32g of molybdenum trioxide (MoO ₃ ), 6.96g of tungsten trioxide (WO ₃ ) and 0.81g of sublimed sulfur as raw materials. The weight percentage content of the components is 19.4% of nickel nitrate, 28.8% of molybdenum trioxide, 46.4% of tungsten trioxide, 5.4% of sublimated sulfur. The ball is used as the ball milling medium, the ball-to-material ratio is 15:1, the ball milling speed is 400r/min, and the ball milling time is 24h for mechanical ball milling, and the mixed powder after mechanical ball milling is placed under the protection of argon atmosphere and annealed at 600°C for 1.5 h, add sufficient amount of sulfur to ensure complete vulcanization of the mixed powder, and cool down to room temperature with the furnace to prepare a black unsupported nano hydrodeoxygenation catalyst with a particle size of 80-100nm.

Add 0.2g of catalyst, 100mL of decahydronaphthalene, and 2.77g of tetramethylphenol into a 250ml autoclave, fill it with hydrogen, the initial hydrogen pressure is 3.0MPa, start stirring and heating, and stop the reaction after reacting at 300°C for 5 hours. The first three samples were taken every 40 minutes, and the last three samples were taken out with a small volume of liquid samples every 1 hour, analyzed and characterized by a gas chromatograph (GC9790Ⅱ), and the hydrodeoxygenated product was calibrated by Shimadzu QP-2010S GC/MS , Calculate the conversion rate of 4-methylphenol. The analysis results of Example 2 show that the peak of methylcyclohexane occurred at about 2.3min, the peak of tetramethylcyclohexene occurred at about 2.6min, and the peak of toluene occurred at about 2.8min. The peak of phenol appears at about 17.7min. The product of tetramethylphenol hydrodeoxygenation reaction contains hydrogenation products such as toluene, methylcyclohexane and tetramethylcyclohexene, and no oxygen-containing products such as tetramethylcyclohexanol and tetramethylcyclohexanone are found , indicating that the deoxygenation selectivity of the catalyst is very high. The distribution, peak area and peak area percentage of hydrodeoxygenation products are shown in Table 2. Finally, the conversion rate of tetramethylphenol is 100% within five hours.

Each material peak area and content before and after the reaction in the present embodiment of table two

Example 3:

Weigh 0.58g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O), 1.44g of molybdenum trioxide (MoO ₃ ), 2.32g of tungsten trioxide (WO ₃ ) and 10.66g of sublimed sulfur as raw materials. Component weight percentage content, nickel nitrate 3.9%, molybdenum trioxide 9.6%, tungsten trioxide 15.5%, sublimated sulfur 71%, 1.5ml of absolute ethanol as a process control agent, under the protection of an argon atmosphere, stainless steel balls are used as a ball milling medium , the ball-to-material ratio is 15:1, the ball milling speed is 400r/min, and the ball milling time is 24h for mechanical ball milling. The mixed powder after mechanical ball milling is placed under the protection of argon atmosphere for 1.5h constant temperature annealing at 600°C. A sufficient amount of sulfur is used to ensure complete vulcanization of the mixed powder, and the black non-supported nano hydrodeoxygenation catalyst can be prepared after cooling to room temperature with the furnace, and the particle size of the catalyst is 100-200nm.

Add 0.2g of catalyst, 100mL of decahydronaphthalene, and 2.77g of tetramethylphenol into a 250ml autoclave, fill it with hydrogen, the initial hydrogen pressure is 3.0MPa, start stirring and heating, and stop the reaction after reacting at 300°C for 5 hours. The first three samples were taken every 40 minutes, and the last three samples were taken out with a small volume of liquid samples every 1 hour, analyzed and characterized by a gas chromatograph (GC9790Ⅱ), and the hydrodeoxygenated product was calibrated by Shimadzu QP-2010S GC/MS , Calculate the conversion rate of 4-methylphenol. The analysis result of embodiment 3 shows, what occur at about 2.3min is the peak of methylcyclohexane, what occurs at about 2.6min is the peak of tetramethylcyclohexene, what occurs at about 2.8min is the peak of toluene, tetramethylcyclohexene The peak of phenol appears at about 17.7min. The product of tetramethylphenol hydrodeoxygenation reaction contains hydrogenation products such as toluene, methylcyclohexane and tetramethylcyclohexene, and no oxygen-containing products such as tetramethylcyclohexanol and tetramethylcyclohexanone are found , indicating that the deoxygenation selectivity of the catalyst is very high. The distribution, peak area and peak area percentage of hydrodeoxygenation products are shown in Table 3. Finally, the conversion rate of tetramethylphenol is 100% within five hours.

Each material peak area and content before and after the reaction in the present embodiment of table three

Example 4:

Weigh 2.91g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O), 4.32g of molybdenum trioxide (MoO ₃ ), 6.96g of tungsten trioxide (WO ₃ ) and 0.81g of sublimed sulfur as raw materials. Component weight percentage content is nickel nitrate 19.4%, molybdenum trioxide 28.8%, tungsten trioxide 46.4%, sublimated sulfur 5.4%, the mixture is used as raw material, 1ml absolute ethanol is used as process control agent, 1ml absolute ethanol is used as process control agent , under the protection of argon atmosphere, stainless steel balls are used as the ball milling medium, the ball-to-material ratio is 15:1, the ball milling speed is 400r/min, and the ball milling time is 24h for mechanical ball milling, and the mixed powder after mechanical ball milling is placed in argon Annealing at 700°C for 0.25 hours under the protection of air atmosphere, with sufficient sulfur in front to ensure complete vulcanization of the mixed powder, cooling to room temperature with the furnace, and then a black non-supported nano hydrodeoxygenation catalyst can be prepared, the particle size of the catalyst is 200-300nm .

Add 0.2g of catalyst, 100mL of decahydronaphthalene, and 2.77g of tetramethylphenol into a 250ml autoclave, fill it with hydrogen, the initial hydrogen pressure is 3.0MPa, start stirring and heating, and stop the reaction after reacting at 300°C for 5 hours. The first three samples were taken every 40 minutes, and the last three samples were taken out with a small volume of liquid samples every 1 hour, analyzed and characterized by a gas chromatograph (GC9790Ⅱ), and the hydrodeoxygenated product was calibrated by Shimadzu QP-2010S GC/MS , Calculate the conversion rate of 4-methylphenol. The analysis results of Example 4 show that the peak of methylcyclohexane occurred at about 2.3min, the peak of tetramethylcyclohexene occurred at about 2.6min, the peak of toluene occurred at about 2.8min, and the peak of tetramethylcyclohexene occurred at about 2.8min. The peak of phenol appears at about 17.7min. The product of tetramethylphenol hydrodeoxygenation reaction contains hydrogenation products such as toluene, methylcyclohexane and tetramethylcyclohexene, and no oxygen-containing products such as tetramethylcyclohexanol and tetramethylcyclohexanone are found , indicating that the deoxygenation selectivity of the catalyst is very high. The product distribution, peak area and peak area percentage are shown in Table 4. Finally, the conversion rate of tetramethylphenol is 100% within five hours.

Each material peak area and content before and after the reaction in the present embodiment of table four

Example 5:

Weigh 2.91g of nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O), 4.32g of molybdenum trioxide (MoO ₃ ), 6.96g of tungsten trioxide (WO ₃ ) and 0.81g of sublimed sulfur as raw materials. The weight percentage content of the components is 19.4% of nickel nitrate, 28.8% of molybdenum trioxide, 46.4% of tungsten trioxide, 5.4% of sublimated sulfur. The ball is used as the ball milling medium, the ball-to-material ratio is 15:1, the ball milling speed is 400r/min, and the ball milling time is 24h for mechanical ball milling, and the mixed powder after mechanical ball milling is placed under the protection of argon atmosphere and annealed at 600°C for 2 hours. A sufficient amount of sulfur is pre-empted to ensure the complete vulcanization of the mixed powder. After cooling to room temperature with the furnace, a black unsupported nano-hydrodeoxygenation catalyst can be prepared. The particle size of the catalyst is 300-400nm.

Add 0.2g of catalyst, 100mL of decahydronaphthalene, and 2.77g of tetramethylphenol into a 250ml autoclave, fill it with hydrogen, the initial hydrogen pressure is 3.0MPa, start stirring and heating, and stop the reaction after reacting at 300°C for 5 hours. The first three samples were taken every 40 minutes, and the last three samples were taken out with a small volume of liquid samples every 1 hour, analyzed and characterized by a gas chromatograph (GC9790Ⅱ), and the hydrodeoxygenated product was calibrated by Shimadzu QP-2010S GC/MS , Calculate the conversion rate of 4-methylphenol. The analysis results of Example 5 show that the peak of methylcyclohexane occurred at about 2.3min, the peak of tetramethylcyclohexene occurred at about 2.6min, the peak of toluene occurred at about 2.8min, and the peak of tetramethylcyclohexene occurred at about 2.8min. The peak of phenol appears at about 17.7min. The product of tetramethylphenol hydrodeoxygenation reaction contains hydrogenation products such as toluene, methylcyclohexane and tetramethylcyclohexene, and no oxygen-containing products such as tetramethylcyclohexanol and tetramethylcyclohexanone are found , indicating that the deoxygenation selectivity of the catalyst is very high. The product distribution, peak area and peak area percentage are shown in Table 5. Finally, the conversion rate of tetramethylphenol is 100% within five hours.

Each material peak area and content before and after the reaction in the present embodiment of table five

Claims (6)

1. non-loading type nano hydrogenation dehydrogenation catalyst; It is the presoma of active component that said catalyst adopts the compound of nickel, molybdenum, tungsten; Said presoma constitutes catalyst through mechanical ball milling, calcining with the form of metal sulfide, and said presoma is made up of following component by mass percentage:

Nickel nitrate 3%-40%,

Molybdenum oxide 1%-40%,

Tungsten oxide 1%-70%,

Sulphur 5%-70%.

2. the preparation method of a kind of non-loading type nano hydrogenation dehydrogenation catalyst according to claim 1; It is characterized in that: get nickel nitrate, molybdenum oxide, tungsten oxide and sulphur respectively by each composition weight proportioning of presoma of the hydrogenation deoxidation catalyst that designs and mix; After ball milling to granularity is 80-400nm under protective atmosphere; Under protective atmosphere, be heated to 600-900 ℃ of cycle annealing 15-120 minute, and cooled to room temperature with the furnace, obtain non-loading type nano hydrogenation dehydrogenation catalyst.

3. the preparation method of a kind of non-loading type nano hydrogenation dehydrogenation catalyst according to claim 2 is characterized in that: during ball milling, and to nickel nitrate, molybdenum oxide, tungsten oxide adds absolute ethyl alcohol as process control agent in the mixture of sulphur; The addition of said absolute ethyl alcohol is the 1-10% of said mixture gross mass.

4. the preparation method of a kind of non-loading type nano hydrogenation dehydrogenation catalyst according to claim 3; It is characterized in that: the process conditions of said ball milling are: with stainless steel ball as ball-milling medium; Ratio of grinding media to material is 10-100:1, and rotational speed of ball-mill is 200-800r/min, and the ball milling time is 2-120h.

5. the preparation method of a kind of non-loading type nano hydrogenation dehydrogenation catalyst according to claim 4 is characterized in that: said cycle annealing temperature is 600-900 ℃, and the cycle annealing time is 15-120 minute.

6. the preparation method of a kind of non-loading type nano hydrogenation dehydrogenation catalyst according to claim 5 is characterized in that: said protective atmosphere is argon gas or nitrogen.

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