An amine-modified bimetallic supported catalyst, a preparation method and application thereof in oil synthesis of aviation oil

Abstract

The application discloses an amine-modified bimetallic supported catalyst, a preparation method thereof and application of the catalyst in oil and fat synthesis aviation oil, and belongs to the field of biomass liquid fuel. The preparation method of the amine-modified bimetallic supported catalyst comprises the following steps: mixing a nickel source, a molybdenum source, citric acid and an amine substance, adding ethanol to prepare a solution, then adding SAPO-11 molecular sieve into the solution, stirring uniformly to obtain a reaction liquid; stirring the reaction liquid at 40-60 DEG C, then stirring at 80 DEG C until ethanol is completely evaporated, and drying the reaction liquid in an oven to obtain a catalyst precursor; calcining the catalyst precursor to obtain the amine-modified bimetallic supported catalyst NiO-MoO3@N / SAPO-11. The catalyst NiO-MoO3@N / SAPO-11 is used for oil and fat synthesis aviation oil, and pre-reduction and pre-sulfuration are not needed; the catalyst has high catalytic activity for oil and fat hydrodeoxygenation reaction, good anti-carbon deposition performance, high selectivity for aviation oil n-alkane product, and can replace current sulfuration state NiMo hydrodeoxygenation catalyst.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of biomass liquid fuel, and particularly relates to an amine-modified bimetallic supported catalyst, a preparation method and application thereof in oil synthesis of aviation oil. BACKGROUND

[0002] With the continuous development of science and technology, the rapid development of global aviation industry leads to a sharp increase in fuel demand, and greenhouse gas emissions show an increasing trend year by year. Under the traction of the carbon peak and carbon neutralization target, biomass-derived bioaviation fuel has an absolute carbon emission advantage over traditional petroleum-based aviation kerosene, and thus has attracted widespread attention. At present, there are not many mature technologies for preparing bioaviation fuel from biomass resources, and the oil synthesis of bioaviation fuel through hydrodeoxygenation is one of them. The main raw materials of this method are natural oils (fatty acids, triglycerides) and waste oils, such as Jatropha oil, camilina oil, and restaurant waste oil. These oil raw materials are deoxygenated by decarboxylation-decarbonylation to remove oxygen in the form of CO2 or CO, or by hydrodeoxygenation to remove oxygen in the form of H2O, to prepare chain alkanes with carbon atom number in the range of 14-22, and then isomerization and selective cracking are performed to isomerize n-alkanes to isoalkanes, and selectively crack C 14 ~C 22 alkanes to C 16 alkanes, to obtain bioaviation fuel products meeting the requirements of aviation oil.

[0003] In the two-step bioaviation fuel preparation route of deoxygenation followed by isomerization, the isomerization of n-alkanes in the second step is a mature technology in petroleum processing, which can be directly used for reference. Therefore, efficient deoxygenation is the key to the preparation of bioaviation fuel from oil raw materials. One of the most important factors for efficient deoxygenation is the hydrodeoxygenation bifunctional catalyst. At present, noble metal catalysts are the most efficient catalysts for hydrodeoxygenation reactions. However, their expensive cost and low reserves limit their industrial application. Among non-noble metal catalysts, CoMo or NiMo catalysts supported on Al2O3 or SiO2 are most widely used, with a reaction pressure of 2-15 MPa and a reaction temperature of 200-500 DEG C. However, this type of catalyst needs to be pre-reduced, pre-sulfided, and a certain amount of sulfiding agent needs to be continuously added to the reaction system to maintain the activity of the catalyst. The introduction of the sulfiding agent makes the oil product contain sulfides. One of the important defects of this technical route is that sulfur-free bioaviation fuel is converted into a sulfur-containing product after deoxygenation refining, which is not conducive to industrial application.

[0004] In order to meet the large-scale bioaviation fuel industry, it is still the main task of current scientific and technological workers to develop cheap, high-activity and green catalysts. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide an amine-modified bimetallic supported catalyst, a preparation method and its application in oil synthesis aviation oil, which solves the problems in the prior art.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A preparation method of an amine-modified bimetallic supported catalyst, comprising the following steps:

[0008] Mixing a nickel source, a molybdenum source, citric acid and an amine substance and adding ethanol to prepare a solution, then adding SAPO-11 molecular sieve to the solution, stirring uniformly to obtain a reaction liquid;

[0009] Stirring the reaction liquid at 40-60℃, then stirring at 80℃ until all ethanol is evaporated, and drying in an oven to obtain a catalyst precursor;

[0010] Calcining the precursor to obtain an amine-modified bimetallic supported catalyst NiO-MoO3@N / SAPO-11.

[0011] Further, the nickel source is nickel acetate, the molybdenum source is ammonium heptamolybdate, and the amine substance is melamine.

[0012] Further, the nickel acetate is 200-600 parts by mass, the ammonium heptamolybdate is 7 parts, the citric acid is 72 parts, the melamine is 60-115 parts, and the SAPO-11 molecular sieve is 50-120 parts.

[0013] Further, the oven drying temperature is 100℃.

[0014] Further, the precursor calcination is calcining the precursor in a muffle furnace at a temperature of 500℃ with a heating rate of 10℃ / min for 5h.

[0015] An amine-modified bimetallic supported catalyst prepared by the above preparation method.

[0016] The application of the above amine-modified bimetallic supported catalyst in oil synthesis aviation oil.

[0017] Further, the steps of oil synthesis aviation oil are:

[0018] Step 1: adding oil, amine-modified bimetallic supported catalyst and n-hexane solvent into a reaction kettle and sealing it;

[0019] Step 2: flushing hydrogen into the reaction kettle and heating, replacing the air in the reaction with hydrogen, and finally closing the outlet valve;

[0020] Step 3: After the reactor is cooled to room temperature, the liquid product is obtained, which is aviation oil.

[0021] Further, the oil is methyl palmitate, palmitic acid or palm oil.

[0022] Further, the mass ratio of the oil and the catalyst is 5:1, the hydrogen pressure is 1-5 Mpa, and the heating temperature is 240-320 DEG C.

[0023] The beneficial effects of the present application are:

[0024] The present application discloses an in-situ reducible amine modified bimetallic supported non-sulfided catalyst NiO-MoO3@N / SAPO-11, which is simple to synthesize, easy to control conditions, low in cost, does not need pre-reduction and pre-sulfurization when used, has high catalytic activity and good carbon deposition resistance for oil hydrogenation deoxidation reaction, has high aviation oil n-alkane product selectivity, and is expected to replace the current sulfided NiMo hydrogenation deoxidation catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed in the embodiments or the prior art description will be briefly introduced below, and obviously, other drawings can be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0026] Figure 1 is the in-situ Py-IR spectrum of the catalyst prepared in Example 1 and Comparative Examples 1-3 of the present application;

[0027] Figure 2 is the N1s high-resolution spectrum of the NiO-MoO3@N / SAPO-11 catalyst of the present application. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application, and obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0029] Example 1

[0030] A preparation method of an amine modified bimetallic supported catalyst comprises the following steps:

[0031] S1, 4 g of nickel acetate, 0.07 g of ammonium heptamolybdate and 0.72 g of citric acid were added into a beaker, poured into 79 g of anhydrous ethanol, and stirred uniformly with a glass rod to obtain a mixed solution, wherein the atomic ratio of Ni:Mo was 40:1;

[0032] S2, 0.84 g of SAPO-11 molecular sieve carrier and 0.95 g of melamine were weighed and added into the above mixed solution respectively and placed in a 60°C water bath for continuous stirring for 4 h, and then stirred in an 80°C water bath until the ethanol was completely volatilized to obtain a solid;

[0033] S3, the obtained solid was placed in a 100°C oven for drying overnight to obtain a catalyst precursor; then the precursor was calcined in a muffle furnace at a temperature of 500°C at a temperature rising rate of 10°C / min for 5 h to obtain a NiO-MoO3@N / SAPO-11 catalyst, the mass fraction of NiO loading was about 40%, and the mass fraction of pyridine N loading was about 3.5%, and the pyridine N was a nitrogen atom formed by melamine in the calcination process which could provide Lewis acid sites.

[0034] Example 2

[0035] A preparation method of an amine-modified bimetallic supported catalyst comprises the following steps:

[0036] S1, 4 g of nickel acetate, 0.07 g of ammonium heptamolybdate and 0.72 g of citric acid were added into a beaker, poured into 79 g of anhydrous ethanol, and stirred uniformly with a glass rod to obtain a mixed solution, wherein the atomic ratio of Ni:Mo was 40:1;

[0037] S2, 0.84 g of SAPO-11 molecular sieve carrier and 0.95 g of melamine were weighed and added into the above mixed solution respectively and placed in a 60°C water bath for continuous stirring for 4 h, and then stirred in an 80°C water bath until the ethanol was completely volatilized to obtain a solid;

[0038] S3, the obtained solid was placed in a 100°C oven for drying overnight to obtain a catalyst precursor; then the precursor was calcined in a muffle furnace at a temperature of 500°C at a temperature rising rate of 10°C / min for 5 h to obtain a NiO-MoO3@N / SAPO-11 catalyst, the mass fraction of NiO loading was about 40%, and the mass fraction of pyridine N loading was about 3.5%, and the pyridine N was a nitrogen atom formed by melamine in the calcination process which could provide Lewis acid sites.

[0039] Example 3

[0040] A preparation method of an amine-modified bimetallic supported catalyst comprises the following steps:

[0041] S1, 2 g of nickel acetate, 0.07 g of ammonium heptamolybdate and 0.72 g of citric acid were added into a beaker, poured into 79 g of anhydrous ethanol, and stirred uniformly with a glass rod to obtain a mixed solution, wherein the atomic ratio of Ni:Mo was 20:1;

[0042] S2, 1.2 g of SAPO-11 molecular sieve carrier and 1.15 g of melamine were weighed into the above mixed solution respectively and placed in a 60°C water bath for continuous stirring for 4 h, and then stirred in an 80°C water bath until the ethanol was completely volatilized to obtain a solid;

[0043] S3, the obtained solid was placed in a 100°C oven for drying overnight to obtain a catalyst precursor; then the precursor was calcined in a muffle furnace at a temperature of 500°C at a heating rate of 10°C / min for 5 h to obtain the L-NiO-MoO3@N / SAPO-11 catalyst, wherein the mass fraction of NiO loading was about 20%, and the mass fraction of pyridine N loading was about 4.2%.

[0044] Comparative Example 1

[0045] The preparation steps of the NiO / SAPO-11 catalyst are as follows:

[0046] S1, 4 g of nickel acetate and 0.72 g of citric acid were added into a beaker, poured into 79 g of anhydrous ethanol, and stirred uniformly with a glass rod to obtain a mixed solution;

[0047] S2, 0.84 g of SAPO-11 molecular sieve carrier was weighed into the above mixed solution and placed in a 60°C water bath for continuous stirring for 4 h, and then stirred in an 80°C water bath until the ethanol was completely volatilized to obtain a solid; S3, the obtained solid was placed in a 100°C oven for drying overnight to obtain a catalyst precursor; then the precursor was calcined in a muffle furnace at a temperature of 500°C at a heating rate of 10°C / min for 5 h to obtain the NiO@SAPO-11 catalyst.

[0048] Comparative Example 2

[0049] The preparation steps of the MoO3 / SAPO-11 catalyst are as follows:

[0050] S1, 0.7 g of ammonium heptamolybdate and 0.72 g of citric acid were added into a beaker, poured into 79 g of anhydrous ethanol, and stirred uniformly with a glass rod to obtain a mixed solution;

[0051] S2, 0.84 g of SAPO-11 molecular sieve carrier and 0.95 g of melamine were weighed into the above mixed solution respectively and placed in a 60°C water bath for continuous stirring for 4 h, and then stirred in an 80°C water bath until the ethanol was completely volatilized to obtain a solid;

[0052] S3, the obtained solid is placed in a 100℃ oven and dried overnight to obtain the catalyst precursor; then the precursor is calcined in a muffle furnace at a temperature of 500℃ for 5h at a heating rate of 10℃ / min to obtain the MoO3@SAPO-11 catalyst.

[0053] Comparative Example 3

[0054] The preparation steps of the NiO-MoO3 / SAPO-11 catalyst are as follows:

[0055] S1. Add 4g of nickel acetate, 0.7g of ammonium heptamolybdate and 0.72g of citric acid to a beaker, pour in 79g of anhydrous ethanol, and stir with a glass rod to obtain a mixed solution.

[0056] S2, Weigh 0.84g of SAPO-11 molecular sieve support and add it to the above mixed solution and place it in a 60℃ water bath and continue stirring for 4h. Then stir in an 80℃ water bath until all the ethanol has evaporated to obtain a solid.

[0057] S3, the obtained solid is placed in an oven at 100℃ and dried overnight to obtain the catalyst precursor; then the precursor is calcined in a muffle furnace at 500℃ for 5h at a heating rate of 10℃ / min to obtain the NiO-MoO3@SAPO-11 catalyst.

[0058] The number of different types of acidic sites in the five catalysts prepared in Example 1 and Comparative Examples 1-3 was determined by in-situ Py-IR spectroscopy, and the results are as follows: Figure 1 As shown in Table 1, it can be seen that after introducing nitrogen to modify the catalyst, the NiO-MoO3@N / SAPO-11 catalyst has a 1450 cm⁻¹ chromium content. -1 The significantly increased Lev acid peak indicates an increase in the amount of Lev acid. During hydrodeoxygenation, Lev acid can accept electron pairs from oxygen atoms in fat molecules, thereby activating the carbon-oxygen bond and adjacent carbon atoms. α -C β The purpose is to promote the deoxygenation reaction by bonding bonds.

[0059] Table 1. Determination of the number of different types of acid sites in five catalysts.

[0060]

[0061] Example 4

[0062] The catalytic performance of the four catalysts prepared in Examples 1-3 and Comparative Examples 1-3 was tested, and the steps included:

[0063] Step 1: Add 0.5g methyl palmitate, 0.1g catalyst and 50mL n-hexane solvent to a 100mL high-temperature and high-pressure reactor and seal it.

[0064] Step 2: Replace the air in the reaction system with hydrogen, then close the outlet valve, purge with hydrogen to 4 MPa, and heat to 300℃ (heating rate of 5℃ / min) for 6 hours;

[0065] Step 3: After the reaction vessel has cooled to room temperature, a sample is taken, and the liquid product is quantitatively calculated using gas chromatography (GC). The results are shown in Table 2.

[0066] Table 2. Catalytic effects of six catalysts on the hydrodeoxygenation conversion of methyl palmitate.

[0067]

[0068] [a] The selectivity ratio of pentadecane to hexadecane.

[0069] Compared with catalysts without nitrogen modification, NiO-MoO3@N / SAPO-11 showed higher feed conversion and C content. 8-16 Alkane yield, C 15 With C 16 The selectivity for all alkanes was significantly improved. Table 2 also shows that in the products of the NiO-MoO3@N / SAPO-11 catalyst, C... 15 / C 16 The selectivity ratio is much higher than that of the NiO-MoO3 / SAPO-11 catalyst, and increases with increasing N content. This is because the amine-modified catalyst contains pyridine nitrogen with lone pairs of electrons (…). Figure 2 An increase in the amount of Lewis acid catalyst can promote the decarboxylation of hexadecanoic acid and produce more pentadecane.

[0070] Examples 5-22 are provided below to investigate the operating conditions, conversion rate, yield, and selectivity of NiO-MoO3@N / SAPO-11 catalyst in the preparation of jet fuel by hydrodeoxygenation of grease; the relevant parameters and results are shown in Table 3.

[0071] Example 5

[0072] Example 5 follows the same procedure as Example 4, but the reaction temperature is 220°C, yielding the hydrodeoxygenation product C8-C. 16 The product yield was 7.37%, with the main product being C. 15+16 Selectivity: 9.25%.

[0073] Example 6

[0074] Example 6 follows the same procedure as Example 4, but the reaction temperature is 240°C, yielding the hydrodeoxygenation product C8-C. 16 The product yield was 13.74%, with the main product being C. 15+16 Selectivity: 19.04%.

[0075] Example 7

[0076] Example 7 was carried out as in Example 4, but the reaction temperature was 260 °C, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 40.52%, and the main product was C 15+16 The selectivity was 64.70%.

[0077] Example 8

[0078] Example 8 was carried out as in Example 4, but the reaction temperature was 280 °C, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 64.35%, and the main product was C 15+16 The selectivity was 81.53%.

[0079] Example 9

[0080] Example 9 was carried out as in Example 4, but the hydrogen pressure was 1 MPa, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 30.56%, and the main product was C 15+16 The selectivity was 27.24%.

[0081] Example 10

[0082] Example 10 was carried out as in Example 4, but the hydrogen pressure was 2 MPa, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 41.81%, and the main product was C 15+16 The selectivity was 36.91%.

[0083] Example 11

[0084] Example 11 was carried out as in Example 4, but the hydrogen pressure was 3 MPa, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 60 24%, and the main product was C 15+16 The selectivity was 62.56%.

[0085] Example 12

[0086] Example 12 was carried out as in Example 4, but the hydrogen pressure was 5 MPa, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 65.30%, and the main product was C 15+16 The selectivity was 78.02%.

[0087] Example 13

[0088] Example 13 was carried out as in Example 4, but the mass ratio of methyl palmitate to catalyst was 1:1, and the hydrodeoxygenated product C8-C 16 The mass yield of the product was 73.87%, and the main product was C 15+16Selectivity 46.18%.

[0089] Example 14

[0090] Example 14 was operated as in Example 4, but the mass ratio of methyl palmitate to catalyst was 3:1, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 66.41%, and the main product was C8-Ci0. 15+16 Selectivity 52.37%.

[0091] Example 15

[0092] Example 15 was operated as in Example 4, but the mass ratio of methyl palmitate to catalyst was 7:1, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 50.25%, and the main product was C8-Ci0. 15+16 Selectivity 52.55%.

[0093] Example 16

[0094] Example 16 was operated as in Example 4, but the mass ratio of methyl palmitate to catalyst was 9:1, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 45.82%, and the main product was C8-Ci0. 15+16 Selectivity 48.67%.

[0095] Example 17

[0096] Example 17 was operated as in Example 4, but the reaction time was 1 hour, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 37.56%, and the main product was C8-Ci0. 15+16 Selectivity 24.16%.

[0097] Example 18

[0098] Example 18 was operated as in Example 4, but the reaction time was 2 hours, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 45.10%, and the main product was C8-Ci0. 15+16 Selectivity 33.81%.

[0099] Example 19

[0100] Example 19 was operated as in Example 4, but the reaction time was 3 hours, and the hydrogenated deoxygenated product C8-Ci0was obtained. 16 The mass yield of product was 47.35%, and the main product was C8-Ci0. 15+16 Selectivity 48.42%.

[0101] Example 20

[0102] Example 20 follows the same procedure as Example 4, but the reaction time is 4 hours, yielding the hydrodeoxygenation product C8-C. 16 The product yield was 56.02%, with the main product being C. 15+16 Selectivity: 55.24%.

[0103] Example 21

[0104] Example 21 follows the same procedure as Example 4, but the reaction time is 5 hours, yielding the hydrodeoxygenation product C8-C. 16 The product yield was 65.23%, with the main product being C. 15+16 Selectivity: 58.49%.

[0105] Example 22

[0106] Example 22 follows the same procedure as Example 4, but the reaction time is 8 hours, yielding the hydrodeoxygenation product C8-C. 16 The product yield was 66.03%, with the main product being C. 15+16 Selectivity: 69.50%.

[0107] Table 3. Conversion characteristics of NiO-MoO3@N / SAPO-11 to methyl palmitate under different operating conditions.

[0108]

[0109] From Examples 5-22 and Table 3, we can obtain:

[0110] The conversion rate of methyl palmitate increases rapidly when the temperature exceeds 260℃. However, at a reaction temperature of 220℃, the conversion rate is only around 20%, affecting aviation fuel component C. 8-16 The yield of alkanes is less than 10%. At 220°C and 240°C, the main products are hexadecyl alcohol and hexadecanoic acid. When the temperature reaches 280°C, hexadecyl alcohol and hexadecanoic acid are completely converted to alkanes, and the methyl ester conversion rate is close to 100%. At 280°C, C... 15+16 The selectivity for alkanes reached a maximum of 81.53%, at which point C 15 / C 16 The selectivity ratio was 19.28, indicating that the NiO-MoO3@N / SAPO-11 catalyst exhibits higher activity for C-C bond cleavage than for CO bond cleavage, with decarboxylation being the dominant reaction. When the temperature increased to 300℃, C... 15 / C 16 It has decreased slightly.

[0111] Initial hydrogen pressure and the mass ratio of methyl palmitate to catalyst have a significant impact on methyl palmitate conversion, as well as the yield and selectivity of jet fuel. Optimal hydrodeoxygenation can be achieved when the H2 pressure exceeds 4 MPa and the mass ratio of methyl palmitate to catalyst is 5:1.

[0112] The conversion of methyl palmitate showed a growing trend in the range of reaction time studied. When the reaction time was extended from 1 h to 5 h, the conversion of methyl palmitate increased from 67% to 99%, and when the reaction time was more than 5 h, the conversion of methyl palmitate was basically stable, and the selectivity of hydrocarbons was basically stable. 8-16 The yield and selectivity of alkanes reached a maximum at 6 h.

[0113] In order to study the catalytic ability of the catalyst to the real complex substrate raw material, the following examples are proposed:

[0114] Example 23

[0115] 0.5 g of palm oil (composition see Table 4), 0.1 g of NiO-MoO3@N / SAPO-11 catalyst and 50 mL of n-hexane solvent were added into a 100 mL high-temperature and high-pressure reaction kettle and sealed, then the air in the reaction system was replaced with hydrogen, and finally the outlet valve was closed, hydrogen was filled to 4 MPa, and heated to 300°C for 6 h. After the reaction kettle was cooled to room temperature, the sample was taken for GC quantitative calculation of the liquid product.

[0116] Table 4. Fatty acid composition of palm oil

[0117]

[0118] C x:y : x is the number of carbon atoms of the fatty acid, y is the number of double bonds on the carbon chain.

[0119] Table 5 Conversion and selectivity results calculation table under different substrate conditions

[0120]

[0121] Palm oil is the largest plant oil variety in the world in terms of production, mainly as glycerides of palmitic acid and oleic acid, and also contains a small amount of fatty acids with different carbon chain lengths. As can be seen from Table 5, NiO-MoO3@N / SAPO-11 is also suitable for complex palm oil raw materials with high selectivity of hydrocarbon components.

[0122] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0123] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above-mentioned embodiments, and the above-mentioned embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for preparing an amine-modified bimetallic supported catalyst, characterized in that, Includes the following steps: Nickel source, molybdenum source, citric acid and amines are mixed and ethanol is added to prepare a solution. Then SAPO-11 molecular sieve is added to the solution and stirred evenly to obtain the reaction solution. The reaction solution was stirred at 40–60°C, and then stirred at 80°C until all the ethanol evaporated. The solution was then dried in an oven to obtain the catalyst precursor. The precursor is calcined to obtain the amine-modified bimetallic supported catalyst NiO-MoO3@N / SAPO-11.

2. The method for preparing an amine-modified bimetallic supported catalyst according to claim 1, characterized in that, The nickel source is nickel acetate, the molybdenum source is ammonium heptamolybdate, and the amine is melamine.

3. The method for preparing an amine-modified bimetallic supported catalyst according to claim 2, characterized in that, By weight, the nickel acetate is 200-600 parts, the ammonium heptamolybdate is 7 parts, the citric acid is 72 parts, the melamine is 60-115 parts, and the SAPO-11 molecular sieve is 50-120 parts.

4. The method for preparing an amine-modified bimetallic supported catalyst according to claim 3, characterized in that, The drying temperature in the oven is 100℃.

5. The method for preparing an amine-modified bimetallic supported catalyst according to claim 3, characterized in that, The precursor calcination was carried out in a muffle furnace at a temperature of 500°C for 5 h with a heating rate of 10°C / min.

6. An amine-modified bimetallic supported catalyst, characterized in that, Prepared using the preparation method described in any one of claims 1-5.

7. The application of the amine-modified bimetallic supported catalyst according to claim 6 in the synthesis of jet fuel from oils and fats.

8. The application according to claim 7, characterized in that, The steps involved in synthesizing aviation fuel from oils: Step 1: Add the oil, amine-modified bimetallic supported catalyst, and n-hexane solvent to the reactor and seal it; Step 2: Pour hydrogen into the reactor and heat it to replace the air in the reaction vessel with hydrogen. Finally, close the outlet valve. Step 3: After the reactor cools to room temperature, the liquid product obtained is aviation fuel.

9. The application according to claim 8, characterized in that, The oil is methyl palmitate, palmitic acid, or palm oil.

10. The application according to claim 8, characterized in that, The mass ratio of the oil to the catalyst is 5:1, the hydrogen pressure is 1-5 MPa, and the heating temperature is 240-320℃.

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