Catalyst as well as preparation method and application thereof

Abstract

The invention provides a catalyst as well as a preparation method and application thereof. The catalyst includes: nickel particles; a molecular sieve on which the nickel particles are loaded; based on the same mass of the catalyst and the pure molecular sieve, the acid concentration of the catalyst is higher than that of the pure molecular sieve. The acid concentration of the catalyst is higher than that of the pure molecular sieve, so that the catalyst can effectively perform deoxidation, the nickel particles are beneficial to catalytic hydrogenation, and the catalyst can effectively perform hydrodeoxygenation through mutual cooperation between the higher acid concentration and the nickel particles; in addition, in the catalyst provided by the embodiment of the invention, the nickel particles are loaded on the molecular sieve, the price is low, and the catalyst is suitable for large-scale application.

Description

Technical Field

[0001] The present application relates to the field of catalytic technology, and in particular to a catalyst and a preparation method and use thereof. Background Art

[0002] Biomass derivatives and coal direct liquefaction oil have attracted much attention in the production of fine chemicals and fuels. For example, phenolic bio-oil obtained by rapid pyrolysis of lignocellulose is considered to be a promising alternative to fossil fuels; there are also a large number of phenolic compounds in coal direct liquefaction oil. However, phenolic oil cannot be used directly due to various physical and chemical defects, the most critical of which is that the high oxygen content leads to the shortcomings of the oil itself, such as low energy density, high viscosity and low stability. Therefore, hydrodeoxygenation upgrading of phenolic oil is an important way to produce high-quality alkane bio-oil. At present, a variety of noble metal (such as Pd, Pt and Ru) loaded molecular sieve catalysts can catalyze the hydrodeoxygenation of phenolic bio-oil, but the effect is not ideal, and the high cost and scarce earth reserves limit the large-scale use of noble metal-based catalysts. Therefore, the research and development of catalysts with low prices and high efficiency of hydrodeoxygenation performance is imminent. Summary of the invention

[0003] In view of this, an embodiment of the present application provides a catalyst that solves the problems of high catalyst prices and poor catalytic effects in the prior art.

[0004] In a first aspect, the present application provides a catalyst, the catalyst comprising:

[0005] Nickel particles;

[0006] A molecular sieve, wherein the nickel particles are supported on the molecular sieve;

[0007] Based on the same mass of the catalyst and pure molecular sieve, the acid concentration of the catalyst is higher than that of the pure molecular sieve.

[0008] Further, based on the same mass of the catalyst and the pure molecular sieve, the ratio of the acid concentration of the catalyst to the acid concentration of the pure molecular sieve is greater than 1 and less than or equal to 2;

[0009] Preferably, the silicon to aluminum ratio of the molecular sieve is 5 to 300;

[0010] Preferably, the molecular sieve comprises at least one of HZSM-5, HY and Hβ molecular sieves.

[0011] Furthermore, the particle size of the nickel particles is 3 to 7 nm;

[0012] Preferably, the content of the nickel particles is 5-40 wt % based on the total mass of the catalyst.

[0013] The second aspect of the present application provides a method for preparing the above-mentioned catalyst, comprising:

[0014] Adding the auxiliary agent and the nickel salt solution to water to obtain a first mixed solution;

[0015] placing the molecular sieve in a solution containing aqueous ammonia, and then performing a first drying treatment to obtain a first solid;

[0016] The first solid is mixed with the first mixed solution, and then subjected to a second drying process to obtain a second solid;

[0017] The second solid is calcined in a reducing atmosphere to obtain the catalyst.

[0018] Further, the molar ratio of the auxiliary agent to the nickel salt is greater than 0 and less than or equal to 5;

[0019] Preferably, the auxiliary agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and triamine citrate;

[0020] Preferably, the nickel salt includes at least one of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate.

[0021] Further, placing the molecular sieve in a solution containing aqueous ammonia comprises:

[0022] The molecular sieve is placed in water, the pH of the mixed system is adjusted to 9.0-12.0 using aqueous ammonia, and the mixture is mixed under stirring for 1-10 hours;

[0023] Preferably, the temperature of the first drying process is 60-100°C.

[0024] Further, mixing the first solid with the first mixed solution comprises:

[0025] placing the first solid in water to obtain a suspension;

[0026] adding the first mixed solution into the suspension;

[0027] Preferably, the second drying process comprises evaporation.

[0028] Furthermore, the step of calcining the second solid in a reducing atmosphere includes: placing the second solid in a hydrogen atmosphere and calcining at a temperature of 400-700°C.

[0029] The third aspect of the present application provides a use of the above-mentioned catalyst, using the catalyst to perform hydrogenation and deoxygenation on oxygen-containing organic matter, and / or using the catalyst to perform hydrogenation on unsaturated hydrocarbons.

[0030] Furthermore, the use of the catalyst to hydrodeoxygenate oxygen-containing organic matter satisfies at least one of the following conditions:

[0031] The mass ratio of the catalyst to the reaction substrate is 1 to 50 wt%;

[0032] The reaction pressure is 1-5 MPa;

[0033] The reaction temperature is 100 to 300°C; and

[0034] The reaction time is 0.5 to 24 hours;

[0035] And / or, the use of the catalyst to hydrogenate unsaturated hydrocarbons satisfies at least one of the following conditions:

[0036] The mass ratio of the catalyst to the reaction substrate is 1 to 50 wt%;

[0037] The reaction pressure is 1-5 MPa;

[0038] The reaction temperature is 100 to 300°C; and

[0039] The reaction time is 0.5 to 24 hours;

[0040] Preferably, the oxygen-containing organic matter includes at least one of aliphatic oxygen-containing organic matter and aromatic oxygen-containing organic matter.

[0041] The catalyst provided in the embodiment of the present application has an acid concentration higher than that of pure molecular sieve of the same mass, so that the catalyst can effectively carry out deoxygenation, and the nickel particles are conducive to catalytic hydrogenation. The higher acid concentration cooperates with the nickel particles, so that the catalyst can effectively carry out hydrogenation and deoxygenation; and in the catalyst of the embodiment of the present application, nickel particles are loaded on the molecular sieve, which has a lower price and is suitable for large-scale application. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The NH3-programmed temperature desorption spectra of the catalysts of Example 1 and Comparative Example 1 of the present application are shown in FIG.

[0043] Figure 2 This is a transmission electron microscope image of the catalyst of Example 1 of the present application.

[0044] Figure 3 This is a transmission electron microscope image of the catalyst of Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0045] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0046] In addition, in order to better illustrate the present application, numerous specific details are given in the following specific embodiments. It should be understood by those skilled in the art that the present application can also be implemented without certain specific details. In some examples, methods and means well known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.

[0047] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0048] In addition, the terms “first”, “second”, etc., if used, are merely used to distinguish between the descriptions and should not be understood as indicating or implying relative importance.

[0049] In a first aspect, the present application provides a catalyst, which includes: nickel particles; a molecular sieve, the nickel particles are loaded on the molecular sieve; based on the same mass of the catalyst and the pure molecular sieve, the acid concentration of the catalyst is higher than the acid concentration of the pure molecular sieve.

[0050] It should be noted that the pure molecular sieve refers to a molecular sieve that is not loaded with nickel particles, or a molecular sieve that has not undergone any treatment.

[0051] The catalyst provided in the embodiment of the present application has an acid concentration higher than that of pure molecular sieve of the same mass, so that the catalyst can effectively carry out deoxygenation, and the nickel particles are conducive to catalytic hydrogenation. The higher acid concentration cooperates with the nickel particles, so that the catalyst can effectively carry out hydrogenation and deoxygenation; and in the catalyst of the embodiment of the present application, nickel particles are loaded on the molecular sieve, which has a lower price and is suitable for large-scale application.

[0052] In one embodiment, based on the same mass of the catalyst and the pure molecular sieve, the ratio of the acid concentration of the catalyst to the acid concentration of the pure molecular sieve is greater than 1 and less than or equal to 2, for example, it can be 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2. Thus, the catalyst hydrogenation effect is better. Relative to the above acid concentration ratio range, when the ratio of the acid concentration of the catalyst to the acid concentration of the pure molecular sieve is less than 1, the selectivity of the hydrodeoxygenation product is low.

[0053] In one embodiment, the molecular sieve has a silicon-aluminum ratio of 5 to 300, such as 5, 50, 100, 150, 200, 250 or 300. Thus, the molecular sieve has a suitable silicon-aluminum ratio and has more acid sites, which is beneficial to the catalytic deoxidation of the catalyst.

[0054] In one embodiment, the molecular sieve includes at least one of HZSM-5, HY and Hβ molecular sieves. Therefore, the molecular sieve has a suitable silicon-aluminum ratio, a stable structure, is conducive to the deoxygenation reaction, and has a low price, which is suitable for large-scale application. In a preferred embodiment, the molecular sieve is a HY molecular sieve, which has more acid sites and is more conducive to catalytic deoxygenation.

[0055] In one embodiment, the particle size of the nickel particles is 3 to 7 nm, for example, 3 nm, 4 nm, 5 nm, 5.2 nm, 6 nm or 7 nm. As a result, the dispersion of the nickel particles in the catalyst is high, so that the catalytic hydrogenation effect of the catalyst is excellent. It is understandable that the smaller the particle size of the nickel particles in the catalyst, the higher the dispersion of the nickel particles. It should be noted that the particle size of the nickel particles refers to the maximum distance between any two points in the nickel particles.

[0056] In one embodiment, based on the total mass of the catalyst, the content of the nickel particles is 5-40wt%, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, etc. Thus, the content of the nickel particles is appropriate, and the effect of catalytic hydrodeoxygenation is excellent. Relative to the content of the above-mentioned nickel particles, when the content of the nickel particles is less than 5wt%, the effect of the catalyst catalytic hydrodeoxygenation is relatively poor, and when the content of the nickel particles is higher than 40wt%, the nickel particles are easy to agglomerate, resulting in a relatively poor effect of the catalyst catalytic hydrodeoxygenation.

[0057] The second aspect of the present application provides a method for preparing the above-mentioned catalyst, which comprises the following steps.

[0058] It should be noted that the catalyst is consistent with the previous description and will not be described in detail here.

[0059] S100: Adding an additive and a nickel salt solution to water to obtain a first mixed solution.

[0060] In one embodiment, the auxiliary agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and triamine citrate. Thus, the auxiliary agent is easy to form a complex with nickel. In one embodiment, the nickel salt includes at least one of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate. Thus, the material source is wide, the price is low, and it is suitable for large-scale application.

[0061] In one embodiment, the molar ratio of the auxiliary agent to the nickel salt is greater than 0 and less than or equal to 5, for example, it can be 0.5, 1, 2, 3, 4 or 5. Relative to the above molar ratio range, when the molar ratio of the auxiliary agent to the nickel salt is greater than 5, when the catalyst is obtained for hydrodeoxygenation, more carbon deposits are deposited in the reaction system, and the hydrodeoxygenation effect is not ideal.

[0062] S200: placing the molecular sieve in a solution containing aqueous ammonia, and then performing a first drying treatment to obtain a first solid.

[0063] In one embodiment, placing the molecular sieve in a solution containing aqueous ammonia includes: placing the molecular sieve in water, adjusting the pH of the mixed system to 9.0-12.0 (for example, 9.0, 10.0, 11.0 or 12.0, etc.) using aqueous ammonia, and mixing under stirring for 1-10 hours (for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, etc.). It can be understood that the molecular sieve is B acid, and the molecular sieve contains hydrogen protons. The ammonium ions in the aqueous ammonia can replace part of the hydrogen protons in the molecular sieve with ammonium ions, and the ammonium ions on the surface of the molecular sieve are more easily exchanged with other ions such as nickel ions.

[0064] For example, after the additive forms a complex with nickel, the nickel in the complex has a valence of +2, and the complex can form a very strong fixing effect with -O- in B acid, which is stronger than a hydrogen bond.

[0065] In one embodiment, the temperature of the first drying treatment is 60-100°C, for example, 60°C, 70°C, 80°C, 90°C or 100°C. Thus, the temperature of the first drying treatment is appropriate, and the ammonium ions can be firmly fixed on the surface of the molecular sieve. With respect to the temperature range of the first drying treatment, when the temperature of the first drying treatment is lower than 60°C, the drying effect is not ideal; when the temperature range of the first drying treatment is higher than 100°C, the NH4 + The decomposed molecular sieve turns back to the hydrogen type molecular sieve and loses the ion exchange ability. For example, when the temperature of the first drying treatment is 120°, the final yield of phenol hydrodeoxygenation under the same reaction conditions drops to 42.7%.

[0066] S300: mixing the first solid with the first mixed solution, and then performing a second drying process to obtain a second solid.

[0067] It can be understood that the first solid includes a molecular sieve and ammonium ions located on the surface of the molecular sieve; in the process of mixing the first solid with the first mixed solution, the ammonium ions in the first solid undergo ion exchange with the chelate containing nickel ions in the first mixed solution, and the nickel is directly connected to the surface of the molecular sieve, so that the nickel ions can be more evenly distributed on the surface of the molecular sieve.

[0068] In one embodiment, the mixing of the first solid and the first mixed solution comprises: placing the first solid in water to obtain a suspension; and adding the first mixed solution to the suspension. Thus, the first solid and the first mixed solution are mixed more evenly, ammonium ions are more likely to exchange ions with nickel ions, and nickel ions are more evenly distributed on the surface of the molecular sieve.

[0069] In one embodiment, the second drying treatment comprises evaporation, whereby stirring may be performed during evaporation, and stirring allows the first solid to contact the first mixed solution more fully.

[0070] S400: calcining the second solid in a reducing atmosphere to obtain the catalyst.

[0071] In one embodiment, the step of calcining the second solid in a reducing atmosphere includes: placing the second solid in a hydrogen atmosphere and calcining at a temperature of 400-700°C (for example, 400°C, 500°C, 600°C or 700°C, etc.). Thus, during the calcination process, the organic matter in the nickel-containing complex can prevent the nickel particles from agglomerating, and under the action of the reducing atmosphere and the nickel particles, the organic matter is gradually decomposed to form methane gas, causing the molecular sieve to break up, increasing the specific surface area of ​​the catalyst, and exposing more acidic sites to the catalyst; and, during the reduction process, with the formation of nickel particles, the nickel particles facilitate the conversion of non-framework aluminum in the molecular sieve into framework aluminum, and the framework aluminum is acidic, thereby increasing the acid concentration of the catalyst.

[0072] In a specific embodiment, the method for preparing the catalyst comprises the following steps:

[0073] (1) A chelating agent and a nickel salt in a molar ratio of 0-5 are dissolved in deionized water to form a first mixed solution.

[0074] (2) The molecular sieves were dispersed in 50 mL of deionized water, the pH of the system was adjusted to 9.0 using 1 mol / L ammonia water, and the mixture was stirred for 2 h under this condition. The molecular sieves were then washed by centrifugation and dried at 80° C. overnight.

[0075] (3) The product obtained in the step is dispersed in 25 mL of deionized water to form a suspension, and the metal composite solution is added, stirred and evaporated to dryness to obtain a powder.

[0076] (4) reducing the powder obtained in step (3) in a H2 environment at 400-700°C to obtain a catalyst.

[0077] The catalyst preparation method of the embodiment of the present application is simple, has abundant raw material sources, low cost, and is suitable for industrial production.

[0078] The third aspect of the present application provides a use of the above-mentioned catalyst, using the catalyst to perform hydrogenation and deoxygenation on oxygen-containing organic matter, and / or using the catalyst to perform hydrogenation on unsaturated hydrocarbons.

[0079] Illustratively, the catalyst of the embodiment of the present application has a high alkane yield in the catalytic hydrodeoxygenation reaction and mild reaction conditions, and has a high industrial application value.

[0080] It should be noted that the catalyst is consistent with the previous description and will not be described in detail here.

[0081] In one embodiment, the use of the catalyst to hydrodeoxygenate oxygen-containing organic matter satisfies at least one of the following conditions: the mass ratio of the catalyst to the reaction substrate is 1 to 50 wt% (for example, it can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, etc.); the reaction pressure is 1 to 5 MPa (for example, it can be 1 MPa, 2 MPa, 3 MPa, 4 MPa or 5 MPa, etc.); the reaction temperature is 100 to 300°C (for example, it can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C or 500°C, etc.); and the reaction time is 0.5 to 24 h (for example, it can be 1 h, 5 h, 10 h, 15 h, 20 h or 24 h, etc.).

[0082] In one embodiment, the use of the catalyst to hydrogenate unsaturated hydrocarbons satisfies at least one of the following conditions: the mass ratio of the catalyst to the reaction substrate is 1 to 50 wt% (for example, it can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%, etc.); the reaction pressure is 1 to 5 MPa (for example, it can be 1 MPa, 2 MPa, 3 MPa, 4 MPa or 5 MPa, etc.); the reaction temperature is 100 to 300°C (for example, it can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C or 500°C, etc.); and the reaction time is 0.5 to 24 h (for example, it can be 1 h, 5 h, 10 h, 15 h, 20 h or 24 h, etc.).

[0083] In one embodiment, the oxygen-containing organic matter includes at least one of an aliphatic oxygen-containing organic matter and an aromatic oxygen-containing organic matter.

[0084] The present application is further described below in conjunction with specific embodiments. It should be noted that the following embodiments are only used to explain the present application and cannot be understood as limiting the present application.

[0085] Example 1

[0086] The preparation method of the catalyst comprises the following steps:

[0087] Dissolve 1.514g of triammine citrate and 3.794g of nickel nitrate hexahydrate in 100mL of deionized water to form a first mixed solution. Disperse 1g of HY molecular sieve with a silicon-aluminum ratio of 10 in 50mL of deionized water, adjust the pH of the system to 9.0 with 1mol / L of ammonia water, and stir and mix for 2h under this condition. Then wash the molecular sieve by centrifugation and dry it at 80°C overnight. Place 500mg of the treated molecular sieve in 25mL of deionized water to form a suspension, add 8.7mL of the first mixed solution and stir for 30min, then evaporate to dryness at 90°C to obtain a catalyst precursor powder, reduce the catalyst precursor in a H2 environment at 500°C for 4h, and obtain a highly dispersed, high-acid concentration molecular sieve-loaded Ni catalyst after cooling, and name it 1 # The NH3-programmed temperature desorption spectrum of the catalyst in this embodiment is as follows Figure 1 As shown in the transmission electron microscope (TEM) Figure 2 As shown. Figure 1 and Figure 2 It can be seen that the catalyst of this embodiment has a higher dispersion and acid concentration.

[0088] Comparative Example 1

[0089] The preparation method of the catalyst comprises the following steps:

[0090] 3.794 g of nickel nitrate hexahydrate was dissolved in 100 mL of deionized water to form a first mixed solution. 500 mg of HY molecular sieve with a silicon-aluminum ratio of 10 was placed in 25 mL of deionized water to form a suspension, and 8.7 mL of the first mixed solution was added and stirred for 30 min, then evaporated to dryness at 90 ° C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500 ° C for 4 h, and after cooling, a molecular sieve-supported Ni catalyst was obtained, which was named Comparative 1. # The NH3-programmed temperature desorption spectrum of the catalyst in this comparative example is as follows Figure 1 As shown in the transmission electron microscope (TEM) Figure 3 shown.

[0091] Comparative Example 2

[0092] The preparation method of the catalyst comprises the following steps:

[0093] 1.514 g of triammonium citrate and 3.794 g of nickel nitrate hexahydrate were dissolved in 100 mL of deionized water to form a first mixed solution. 500 mg of HY molecular sieve with a silicon-aluminum ratio of 10 was placed in 25 mL of deionized water to form a suspension, and 8.7 mL of the first mixed solution was added and stirred for 30 min, then evaporated to dryness at 90 ° C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500 ° C for 4 h, and after cooling, a molecular sieve-supported Ni catalyst was obtained, which was named Comparative 5. # .

[0094] Comparative Example 3

[0095] The preparation method of the catalyst comprises the following steps:

[0096] Dissolve 1.514g of triammine citrate and 3.794g of cobalt nitrate hexahydrate in 100mL of deionized water to form a first mixed solution. Disperse 1g of HY molecular sieve with a silicon-aluminum ratio of 10 in 50mL of deionized water, adjust the pH of the system to 9.0 with 1mol / L of ammonia water, and stir and mix for 2h under this condition. Then wash the molecular sieve by centrifugation and dry it at 80°C overnight. Place 500mg of the treated molecular sieve in 25mL of deionized water to form a suspension, add 8.7mL of the first mixed solution and stir for 30min, then evaporate to dryness at 90°C to obtain a catalyst precursor powder, reduce the catalyst precursor in a H2 environment at 500°C for 4h, and obtain a highly dispersed high acid concentration molecular sieve loaded Ni catalyst after cooling, and name it as Comparison 6 # .

[0097] Comparative Example 4

[0098] The preparation method of the catalyst comprises the following steps:

[0099] Dissolve 3.794g of nickel nitrate hexahydrate in 100mL of deionized water to form a first mixed solution. Disperse 1g of HY molecular sieve with a silicon-aluminum ratio of 10 in 50mL of deionized water, adjust the pH of the system to 9.0 with 1mol / L of ammonia water, and stir and mix for 2h under this condition. Then wash the molecular sieve by centrifugation and dry it at 80°C overnight. Place 500mg of the treated molecular sieve in 25mL of deionized water to form a suspension, add 8.7mL of the first mixed solution and stir for 30min, then evaporate to dryness at 90°C to obtain a catalyst precursor powder, reduce the catalyst precursor in a H2 environment at 500°C for 4h, and obtain a highly dispersed high acid concentration molecular sieve loaded Ni catalyst after cooling, and name it as Comparison 7 # .

[0100] Example 2

[0101] The preparation method of the catalyst comprises the following steps:

[0102] Dissolve 1.514g of triammine citrate and 3.794g of nickel nitrate hexahydrate in 100mL of deionized water to form a first mixed solution. Disperse 1g of HZSM-5 molecular sieve with a silicon-aluminum ratio of 130 in 50mL of deionized water, adjust the pH of the system to 9.0 with 1mol / L of ammonia water, and stir and mix for 2h under this condition. Then wash the molecular sieve by centrifugation and dry it at 80°C overnight. Calcine the dried sample at 500°C for 4h. Place 500mg of the treated molecular sieve in 25mL of deionized water to form a suspension, add 8.7mL of the first mixed solution and stir for 30min, then evaporate to dryness at 90°C to obtain a catalyst precursor powder, reduce the catalyst precursor in a H2 environment at 500°C for 4h, and obtain a highly dispersed, high-acid concentration molecular sieve-loaded Ni catalyst after cooling and name it 2 # .

[0103] Comparative Example 5

[0104] The preparation method of the catalyst comprises the following steps:

[0105] 3.794 g of nickel nitrate hexahydrate was dissolved in 100 mL of deionized water to form a first mixed solution. 500 mg of HZSM-5 molecular sieve with a silicon-aluminum ratio of 130 was placed in 25 mL of deionized water to form a suspension, and 8.7 mL of the first mixed solution was added and stirred for 30 min, then evaporated to dryness at 90 ° C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500 ° C for 4 h, and after cooling, a molecular sieve-supported Ni catalyst was obtained, which was named Comparative 2 # .

[0106] Example 3

[0107] The preparation method of the catalyst comprises the following steps:

[0108] 1.514g of triammine citrate and 3.794g of nickel nitrate hexahydrate were dissolved in 100mL of deionized water to form a first mixed solution. 1g of Hβ molecular sieve with a silicon-aluminum ratio of 25 was dispersed in 50mL of deionized water, and the pH of the system was adjusted to 9.0 with 1mol / L of ammonia water, and stirred and mixed for 2h under this condition. The molecular sieve was then washed by centrifugation and dried at 80°C overnight. The dried sample was calcined at 500°C for 4h. 500mg of the treated molecular sieve was placed in 25mL of deionized water to form a suspension, and 8.7mL of the first mixed solution was added and stirred for 30min, then evaporated to dryness at 90°C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500°C for 4h. After cooling, a highly dispersed and high acid concentration molecular sieve-loaded Ni catalyst was obtained, which was named 3 # .

[0109] Comparative Example 6

[0110] The preparation method of the catalyst comprises the following steps:

[0111] 3.794 g of nickel nitrate hexahydrate was dissolved in 100 mL of deionized water to form a first mixed solution. 500 mg of Hβ molecular sieve with a silicon-aluminum ratio of 25 was placed in 25 mL of deionized water to form a suspension, and 8.7 mL of the first mixed solution was added and stirred for 30 min, then evaporated to dryness at 90 ° C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500 ° C for 4 h, and after cooling, a molecular sieve-supported Ni catalyst was obtained, which was named Comparative 3. # .

[0112] Example 4

[0113] The preparation method of the catalyst comprises the following steps:

[0114] Dissolve 1.514g of triammine citrate and 3.794g of nickel nitrate hexahydrate in 100mL of deionized water to form a first mixed solution. Disperse 1g of HY molecular sieve with a silicon-aluminum ratio of 20 in 50mL of deionized water, adjust the pH of the system to 9.0 with 1mol / L of ammonia water, and stir and mix for 2h under this condition. Then wash the molecular sieve by centrifugation and dry it at 80°C overnight. Calcine the dried sample at 500°C for 4h. Place 500mg of the treated molecular sieve in 25mL of deionized water to form a suspension, add 8.7mL of the first mixed solution and stir for 30min, then evaporate to dryness at 90°C to obtain a catalyst precursor powder, reduce the catalyst precursor in a H2 environment at 500°C for 4h, and obtain a highly dispersed, high-acid concentration molecular sieve-loaded Ni catalyst after cooling, and name it 4 # .

[0115] Comparative Example 7

[0116] The preparation method of the catalyst comprises the following steps:

[0117] 3.794 g of nickel nitrate hexahydrate was dissolved in 100 mL of deionized water to form a first mixed solution. 500 mg of HY molecular sieve with a silicon-aluminum ratio of 20 was placed in 25 mL of deionized water to form a suspension, and 8.7 mL of the first mixed solution was added and stirred for 30 min, then evaporated to dryness at 90 ° C to obtain a catalyst precursor powder, and the catalyst precursor was reduced in a H2 environment at 500 ° C for 4 h, and after cooling, a molecular sieve-supported Ni catalyst was obtained, which was named Comparative 4. # .

[0118] Example 5

[0119] The preparation method of the catalyst is basically the same as that of Example 1, except that triamine citrate is replaced by ethylenediaminetetraacetic acid.

[0120] The conditions for the hydrodeoxygenation of the catalytic substrates of the catalysts of Examples 1 to 5 and Comparative Examples 1 to 7 are shown in Table 1 below, and the obtained products and their yields are shown in Table 1 below:

[0121] Table 1

[0122]

[0123]

[0124] The basic principles of the present application are described above in conjunction with specific embodiments. However, it should be noted that the advantages, strengths, effects, etc. mentioned in the present application are only examples and not limitations, and it cannot be considered that these advantages, strengths, effects, etc. are required by each embodiment of the present application. In addition, the specific details disclosed above are only for the purpose of illustration and ease of understanding, not for limitation, and the above details do not limit the present application to being implemented by adopting the above specific details.

[0125] The above description has been given for the purpose of illustration and description. In addition, this description is not intended to limit the embodiments of the present application to the forms disclosed herein. Although multiple example aspects and embodiments have been discussed above, those skilled in the art will recognize certain variations, modifications, changes, additions and sub-combinations thereof.

Claims

1. A catalyst, characterized in that include: Nickel particles; A molecular sieve, wherein the nickel particles are supported on the molecular sieve; Based on the same mass of the catalyst and pure molecular sieve, the acid concentration of the catalyst is higher than that of the pure molecular sieve.

2. The catalyst according to claim 1, characterized in that Based on the same mass of the catalyst and the pure molecular sieve, the ratio of the acid concentration of the catalyst to the acid concentration of the pure molecular sieve is greater than 1 and less than or equal to 2; Preferably, the silicon to aluminum ratio of the molecular sieve is 5 to 300; Preferably, the molecular sieve comprises at least one of HZSM-5, HY and Hβ molecular sieves.

3. The catalyst according to claim 1, characterized in that The particle size of the nickel particles is 3 to 7 nm; Preferably, the content of the nickel particles is 5-40 wt % based on the total mass of the catalyst.

4. A method for preparing the catalyst according to any one of 1 to 3, characterized in that: include: Adding the auxiliary agent and the nickel salt solution to water to obtain a first mixed solution; placing the molecular sieve in a solution containing aqueous ammonia, and then performing a first drying treatment to obtain a first solid; The first solid is mixed with the first mixed solution, and then subjected to a second drying process to obtain a second solid; The second solid is calcined in a reducing atmosphere to obtain the catalyst.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the auxiliary agent to the nickel salt is greater than 0 and less than or equal to 5; Preferably, the auxiliary agent includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and triamine citrate; Preferably, the nickel salt includes at least one of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate.

6. The preparation method according to claim 4, characterized in that: Placing the molecular sieve in a solution containing aqueous ammonia comprises: The molecular sieve is placed in water, the pH of the mixed system is adjusted to 9.0-12.0 using aqueous ammonia, and the mixture is mixed under stirring for 1-10 hours; Preferably, the temperature of the first drying process is 60-100°C.

7. The preparation method according to claim 4, characterized in that: The mixing of the first solid with the first mixed solution comprises: placing the first solid in water to obtain a suspension; adding the first mixed solution into the suspension; Preferably, the second drying process comprises evaporation.

8. The preparation method according to claim 4, characterized in that: The step of calcining the second solid in a reducing atmosphere comprises: placing the second solid in a hydrogen atmosphere and calcining at a temperature of 400-700° C.

9. Use of the catalyst according to any one of claims 1 to 3, characterized in that: The catalyst is used to hydrodeoxygenate oxygen-containing organic matter, and / or the catalyst is used to hydrogenate unsaturated hydrocarbons.

10. The use according to claim 9, characterized in that Using the catalyst to hydrodeoxygenate oxygen-containing organic matter satisfies at least one of the following conditions: The mass ratio of the catalyst to the reaction substrate is 1 to 50 wt%; The reaction pressure is 1-5 MPa; The reaction temperature is 100 to 300°C; and The reaction time is 0.5 to 24 hours; And / or, the use of the catalyst to hydrogenate unsaturated hydrocarbons satisfies at least one of the following conditions: The mass ratio of the catalyst to the reaction substrate is 1 to 50 wt%; The reaction pressure is 1-5 MPa; The reaction temperature is 100 to 300°C; and The reaction time is 0.5 to 24 hours; Preferably, the oxygen-containing organic matter includes at least one of aliphatic oxygen-containing organic matter and aromatic oxygen-containing organic matter.

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