Method for preparing alpha-olefin from triglyceride compound

Abstract

The invention provides a method for preparing alpha-olefin from a triglyceride compound, and relates to the technical field of organic synthesis. According to the method provided by the invention, in a solvent environment, a hydrogen-containing atmosphere and at 50-300 DEG C, a triglyceride compound I reacts under the catalysis of a NiCu bimetallic catalyst to generate alpha-olefin II-1, alpha-olefin II-2 and alpha-olefin II-3. According to the method provided by the invention, the triglyceride compound is adopted as a reaction substrate, the alpha-olefin compound can be efficiently synthesized, the reaction is green and efficient, the atom utilization rate is high, and no pollution is caused.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing alpha-olefins from triglyceride compounds. Background Art

[0002] In recent years, the direct conversion of syngas (a mixture of CO and H2) from renewable biomass, abundant natural gas and coal into olefins has attracted increasing research interest. Fischer-Tropsch synthesis is a classic reaction for converting syngas into clean hydrocarbon fuels and high value-added chemicals, but the α-olefin products prepared are complex and have low selectivity for single products. Direct catalytic hydrogenation and decarbonylation of fatty acid triglycerides to produce α-olefins is a promising approach. However, due to the complex structure of triesters and the inert chemical properties of the ester group, there are few studies on them as substrates, mainly focusing on fatty acids. Since natural vegetable oils basically exist in the form of triglycerides, the use of fatty acid triglycerides to prepare α-olefins can greatly improve the convenience and applicability of α-olefin synthesis. Summary of the invention

[0003] The object of the present invention is to provide a method for preparing α-olefins from triglyceride compounds, which uses triglyceride compounds as reaction substrates to efficiently synthesize α-olefin compounds, and the reaction is green and efficient, with high atomic utilization and no pollution.

[0004] The present invention provides a method for preparing α-olefin from triglyceride compounds, comprising: in a solvent environment, a hydrogen-containing atmosphere, and at 50° C. to 300° C., a triglyceride compound I is reacted under the catalysis of a NiCu bimetallic catalyst to generate α-olefin II-1, α-olefin II-2, and α-olefin II-3; ; Wherein, R1, R2, and R3 are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, cyano, nitro, carboxyl, aromatic ring, or furan ring.

[0005] Optionally, the solvent environment includes n-hexane, cyclohexane, n-octane, n-heptane, n-decane, cyclopentane or tetrahydrofuran.

[0006] Optionally, the hydrogen concentration in the hydrogen-containing atmosphere is 10%-100%.

[0007] Optionally, the pressure of the hydrogen-containing atmosphere is 1 MPa-5 MPa.

[0008] Optionally, the triglyceride compound I is reacted under the catalysis of a NiCu bimetallic catalyst for 0.1 h-10 h.

[0009] Optionally, the particle size of the NiCu bimetallic catalyst is 1-100 nm.

[0010] Optionally, the NiCu bimetallic catalyst comprises a catalytic carrier and active nickel and active copper loaded thereon, and the loading amounts of the active nickel and the active copper on the catalytic carrier are independently 0.1 wt%-50 wt%.

[0011] Optionally, the preparation method of the NiCu bimetallic catalyst comprises: impregnating a catalyst carrier in a mixed solution containing a nickel salt and a copper salt and evaporating the solution to dryness, calcining the solution and reducing the solution in a reducing atmosphere to obtain the NiCu bimetallic catalyst.

[0012] Optionally, the catalytic carrier includes Hβ molecular sieve, SiO2, C, HZSM-5, Al2O3, ZrO2 or MOF.

[0013] Optionally, the specific surface area of ​​the catalytic carrier is 100 m 2 / g-2000m 2 / g.

[0014] Optionally, the nickel salt includes nickel chloride, nickel nitrate or nickel sulfate.

[0015] Optionally, the copper salt includes copper chloride, copper nitrate or copper sulfate.

[0016] Optionally, the preparation method of the NiCu bimetallic catalyst comprises the following steps: dispersing the catalyst carrier in the mixed solution and impregnating it to obtain a mixed suspension; evaporating the mixed suspension and then crushing it to obtain a catalytic precursor; calcining and oxidizing the catalytic precursor in an oxidizing atmosphere to obtain a catalytic intermediate; and calcining and reducing the catalytic intermediate in a reducing atmosphere to obtain a NiCu bimetallic catalyst.

[0017] Alternatively, the catalytic support is dispersed in the mixed suspension under mechanical mixing, such as stirring, shaking or ultrasound.

[0018] Optionally, the mixed suspension is evaporated to dryness at 100°C-150°C.

[0019] Optionally, the temperatures of calcination oxidation and calcination reduction are independently 350°C-450°C.

[0020] Optionally, the flow rates of the oxidizing atmosphere and the reducing atmosphere are independently 1 mL / min-150 mL / min.

[0021] Optionally, the duration of calcination oxidation and calcination reduction is independently 1 h to 10 h.

[0022] Optionally, the triglyceride compound I includes one of valeric acid triglyceride, caproic acid triglyceride, heptanoic acid triglyceride, caprylic acid triglyceride, nonanoic acid triglyceride, capric acid triglyceride, undecanoic acid triglyceride, lauric acid triglyceride, palmitic acid triglyceride, stearic acid triglyceride, oleic acid triglyceride, linoleic acid triglyceride, 1,3-dioctanoic acid-2-decanoic acid triglyceride, 1,3-diheptanoic acid-2-octanoic acid triglyceride, and 1,3-oleic acid-2-palmitic acid triglyceride.

[0023] Optionally, the mass ratio of the triglyceride compound I to the NiCu bimetallic catalyst is (0.01-1000):1.

[0024] Optionally, the mass concentration of the triglyceride compound I in the solvent environment is 0.001%-50%. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A chemical reaction formula for preparing α-olefins from a triglyceride compound provided by the present invention; Figure 2 Schematic diagram of the technical route for preparing α-olefins from triglyceride compounds; Figure 3 Schematic diagram of the reaction mechanism of converting triglyceride compounds into α-olefins on the surface of a bimetallic catalyst; Figure 4 The figure is a flow chart of the preparation method of NiCu bimetallic catalyst in some embodiments of the present invention. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with general skills in the field to which the present invention belongs.

[0027] See also Figure 1 The present invention provides a method for preparing α-olefins from triglyceride compounds, comprising: in a solvent environment, a hydrogen-containing atmosphere, and at 50°C-300°C, triglyceride compound I is reacted under the catalysis of a NiCu bimetallic catalyst to produce α-olefin II-1, α-olefin II-2, and α-olefin II-3; ; Wherein, R1, R2, and R3 are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, cyano, nitro, carboxyl, aromatic ring, or furan ring.

[0028] In fact, see Figure 2 In the reaction process, triglyceride compound I is first hydrogenated to fatty acid, then decarbonylated to obtain fatty aldehyde, and further hydrogenated in a hydrogen-containing atmosphere to form fatty alcohol, and finally the fatty alcohol removes a molecule of water to obtain α-olefin compound. For details, see Figure 3 From the reaction path of converting triglyceride compound I to α-olefin compound, it can be seen that triglyceride compound I is first hydrogenated to fatty acid on the Ni surface, and then the fatty acid is decarbonylated to obtain fatty aldehyde and CO at the Ni-Cu interface. Then the carbonyl group of fatty aldehyde is adsorbed by Ni-Cu and catalyzed to hydrogenate and dehydrate to obtain α-olefin.

[0029] In some embodiments, the solvent environment used includes n-hexane, cyclohexane, n-octane, n-heptane, n-decane, cyclopentane or tetrahydrofuran. In fact, when selecting the solvent environment, an organic solvent commonly used in the art can be selected, which is necessary not to chemically react with triglyceride compound I and other substances. In addition, by conducting the preparation reaction in a solvent environment, it is beneficial for triglyceride compound I to fully contact with the NiCu bimetallic catalyst.

[0030] In some embodiments, the concentration of hydrogen in the hydrogen-containing atmosphere during the reaction is 10%-100%. In fact, when triglyceride compound I generates fatty alcohol on the surface of NiCu bimetallic catalyst, hydrogen is required to participate in the reaction, and the hydrogen content is positively correlated with the reaction rate to a certain extent. Specifically, when the concentration of hydrogen in the hydrogen-containing atmosphere is less than 100%, the hydrogen-containing atmosphere may also include a non-oxidizing carrier gas, such as an inert gas such as nitrogen, argon, helium, etc.

[0031] In fact, since the concentration of hydrogen decreases after participating in the reaction during the reaction, a certain amount of hydrogen can be added to the reaction environment as the reaction progresses to maintain a stable hydrogen concentration. In some embodiments, the pressure of the hydrogen-containing atmosphere during the reaction is 1MPa-5MPa, and maintaining the pressure environment is conducive to promoting the forward progress of the preparation reaction.

[0032] In some embodiments, the triglyceride compound I is reacted for 0.1h-10h under the catalysis of the NiCu bimetallic catalyst. In fact, the triglyceride compound I used includes valeric acid triglyceride, caproic acid triglyceride, heptanoic acid triglyceride, caprylic acid triglyceride, nonanoic acid triglyceride, capric acid triglyceride, undecanoic acid triglyceride, lauric acid triglyceride, palmitic acid triglyceride, stearic acid triglyceride, oleic acid triglyceride, linoleic acid triglyceride, 1,3-dioctanoic acid-2-capric acid triglyceride, 1,3-dicaprylic acid-2-lauric acid triglyceride, 1,3-dioleic acid-2-palmitic acid triglyceride. Therefore, when facing reaction substrates with different structural formulas, different reaction times are required when the reaction is complete.

[0033] In some embodiments, the mass ratio of triglyceride compound I to NiCu bimetallic catalyst is (0.01-1000): 1. In fact, by adjusting the amount ratio of reactants to catalysts, it is beneficial to promote the triglyceride compound I to fully contact with the bimetallic catalyst in the solvent environment, which is beneficial to the reaction at the surface Ni-Cu bimetallic interface. Specifically, the mass concentration of triglyceride compound I in the solvent environment is 0.001%-50%.

[0034] Specifically, the NiCu bimetallic catalyst used includes a catalytic carrier and active nickel and active copper loaded thereon. By using the catalytic carrier for loading, it is beneficial to increase the loading amount of active nickel and active copper, and at the same time, it can provide an anchoring effect for the active nickel and active copper, and can increase the specific surface area of ​​the bimetallic catalyst, which is beneficial to promote the contact between Ni-Cu and triglyceride compound I.

[0035] Furthermore, the loading amounts of active nickel and active copper on the catalyst carrier are independently 0.1wt%-50wt%. In fact, by adjusting the loading amounts of active nickel and active copper on the catalyst carrier, it is beneficial to adjust the morphology and distribution of the Ni-Cu bimetallic interface formed on the surface of the catalyst carrier.

[0036] In some embodiments, the preparation method of the NiCu bimetallic catalyst includes: impregnating the catalyst carrier in a mixed solution containing a nickel salt and a copper salt, evaporating the solution, calcining the solution, and reducing the solution in a reducing atmosphere to obtain the NiCu bimetallic catalyst. In fact, the solvent impregnation method is conducive to the uniform attachment of the nickel salt and the copper salt to the surface of the catalyst carrier, and after calcination, the nickel salt and the copper salt can not only be sintered and fixed, but also an oxidized coating can be formed, and then active nickel and active copper can be obtained after reduction in a reducing atmosphere.

[0037] In some embodiments, the catalytic carrier used includes Hβ molecular sieve, SiO2, HZSM-5, C, Al2O3, ZrO2 or MOF, and the specific surface area of ​​the catalytic carrier used is 50m 2 / g-3000m 2 / g. In practice, the nickel salt used includes nickel chloride, nickel nitrate or nickel sulfate, and the copper salt used includes copper chloride, copper nitrate or copper sulfate.

[0038] In some embodiments, see Figure 4 , a method for preparing a NiCu bimetallic catalyst comprises the following steps: S1. dispersing the catalyst carrier in the mixed solution and immersing it in the mixed suspension; S2, evaporating the mixed suspension to dryness and then crushing it to obtain a catalytic precursor; S3, calcining and oxidizing the catalytic precursor in an oxidizing atmosphere to obtain a catalytic intermediate; S4. The catalytic intermediate is calcined and reduced in a reducing atmosphere to obtain a NiCu bimetallic catalyst.

[0039] In some embodiments, the catalyst carrier is dispersed in the mixed solution under mechanical mixing, which is conducive to the uniform distribution of nickel salt and copper salt in the catalyst carrier. Specifically, mechanical mixing includes stirring, oscillation or ultrasound. In addition, the mixed suspension can be evaporated at 100°C-150°C, and the temperature of calcination oxidation and calcination reduction is independently controlled to be 350°C-450°C, the duration of calcination oxidation and calcination reduction is independently controlled to be 1h-10h, and the flow rate of oxidizing atmosphere and reducing atmosphere is independently controlled to be 1mL / min-150mL / min. In addition, the particle size of the prepared NiCu bimetallic catalyst is 1nm-100nm.

[0040] Preparation Example

[0041] This preparation example provides a method for preparing a NiCu bimetallic catalyst, comprising the following steps: S1. Dissolve cupric chloride dihydrate and nickel chloride dihydrate in 10 mL of ultrapure water by stirring to obtain a mixed solution, then put the catalyst support into the mixed suspension, and stir at room temperature at a speed of 100 rpm for 12 h to obtain a mixed suspension; S2, placing the mixed suspension in an oven at 110° C. and drying for 10 h, and then crushing to obtain a catalytic precursor; S3, placing the catalytic precursor in a tubular furnace, and calcining it at 400° C. and 80 mL / min of air for 4 h to obtain a catalytic intermediate; S4. The gas in the tube furnace was changed to 80 mL / min of hydrogen and the mixture was calcined at 400° C. for 4 h and then cooled to room temperature with the furnace to obtain a NiCu bimetallic catalyst in the form of black powder.

[0042] The NiCu bimetallic catalyst prepared in the preparation example is used for the preparation of α-olefins in Examples 1 to 13 and Comparative Examples 1 to 3, and the NiCu bimetallic catalyst is expressed as aNibCu / catalytic carrier, for example 0.1Ni0.1Cu / Hβ, which means that Hβ is used as the catalytic carrier, and the content of active nickel on the catalytic carrier is 0.1 and the content of active copper is 0.1.

[0043] At the same time, the yield of the reaction products of Examples 1 to 13 and Comparative Examples 1 to 3 was detected, wherein the quantitative analysis was performed using a gas chromatograph Agilent 7890A series (FID detector, Agilent HP-5 chromatographic column: 30m*32um*0.25um), and the qualitative analysis was performed using a gas mass spectrometer Thermoscientific TRACE 1310 (HP-5 capillary chromatographic column 30m*320μm*0.25μm).

[0044] Example 1

[0045] This Example 1 provides a method for preparing 1-pentene from valeric acid triglyceride, comprising: adding 100 mg of valeric acid triglyceride, 10 mg of a bimetallic catalyst (0.1Ni0.1Cu / Hβ), and 10 mL of n-hexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixture in the reactor and heating it to 50° C. for reaction for 10 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-pentene in the product to be 65%.

[0046] Example 2

[0047] This Example 2 provides a method for preparing 1-octene from caprylic acid triglyceride, comprising: adding 100 mg caprylic acid triglyceride, 0.1 mg bimetallic catalyst (50Ni50Cu / Hβ), and 10 mL cyclohexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 0.1 MPa, stirring the mixed material in the reactor and heating it to 300° C. for reaction for 0.1 h, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-octene in the product, which was 91%.

[0048] Example 3

[0049] This Example 3 provides a method for preparing 1-decene from capric triglyceride, comprising: adding 100 mg of capric triglyceride, 40 mg of a bimetallic catalyst (15Ni4Cu / Hβ), and 10 mL of cyclooctane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixture in the reactor and heating it to 180° C. for reaction for 2 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-decene in the product to be 85%.

[0050] Example 4

[0051] This Example 4 provides a method for preparing 1-myrcene from lauric acid triglyceride, comprising: adding 100 mg of lauric acid triglyceride, 200 mg of a bimetallic catalyst (20Ni15Cu / Hβ), and 10 mL of tetrahydrofuran into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 5 MPa, stirring the mixture in the reactor and heating it to 300° C. for reaction for 8 hours, cooling the reactor to room temperature in an ice-water bath, collecting an organic phase, and detecting that the yield of 1-myrcene in the product is 83%.

[0052] Example 5

[0053] This Example 5 provides a method for preparing 1-octadecene from linoleic acid triglyceride, comprising: adding 100 mg of linoleic acid triglyceride, 10 g of a bimetallic catalyst (40Ni40Cu / Hβ), and 10 mL of n-octane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 0.1 MPa, stirring the mixture in the reactor and heating it to 300° C. for reaction for 0.1 h, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-octadecene in the product to be 72%.

[0054] Example 6

[0055] This Example 6 provides a method for preparing 1-octadecene from stearic acid triglyceride, comprising: adding 100 mg of stearic acid triglyceride, 0.1 mg of a bimetallic catalyst (15Ni4Cu / SiO2), and 1 mL of n-octane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixture in the reactor and heating it to 150°C for reaction for 3 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-octadecene in the product to be 82%.

[0056] Example 7

[0057] This Example 7 provides a method for preparing 1-undecene from undecanoic acid triglyceride, comprising: adding 100 mg of undecanoic acid triglyceride, 100 mg of a bimetallic catalyst (25Ni4Cu / Al2O3), and 10 mL of cyclohexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixture in the reactor and heating it to 180°C for reaction for 2.5 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-undecene in the product to be 71%.

[0058] Example 8

[0059] This Example 8 provides a method for preparing 1-hexene from caproic acid triglyceride, comprising: adding 100 mg of caproic acid triglyceride, 40 mg of a bimetallic catalyst (30Ni15Cu / C), and 10 mL of n-heptane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 0.5 MPa, stirring the mixture in the reactor and heating it to 300° C. for reaction for 10 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-hexene in the product, which was 86%.

[0060] Example 9

[0061] This Example 9 provides a method for preparing 1-hexadecene from palmitic acid triglyceride, comprising: adding 1 g of palmitic acid triglyceride, 1 mg of a bimetallic catalyst (9Ni4Cu / Hβ), and 10 mL of cyclopentane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 2 MPa, stirring the mixture in the reactor and heating it to 260° C. for reaction for 4 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-hexadecene in the product to be 89%.

[0062] Example 10

[0063] This Example 10 provides a method for preparing 1-octadecene from oleic acid triglyceride, comprising: adding 100 mg of oleic acid triglyceride, 50 mg of a bimetallic catalyst (15Ni10Cu / Hβ), and 10 mL of n-heptane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 5 MPa, stirring the mixture in the reactor and heating it to 240° C. for reaction for 2 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-octadecene in the product to be 98%.

[0064] Embodiment 11

[0065] This Example 11 provides a method for preparing 1-octene and 1-decene from 1,3-dioctanoic acid-2-decanoic acid triglyceride, comprising: adding 100 mg of 1,3-dioctanoic acid-2-decanoic acid triglyceride, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of cyclohexane into a 50 mL reactor and then sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 4 MPa, stirring the mixed material in the reactor and heating it to 240° C. for reaction for 10 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yields of 1-octene and 1-decene in the product, respectively, were 55% and 28%, respectively.

[0066] Example 12

[0067] This Example 12 provides a method for preparing 1-heptene and 1-octene from 1,3-diheptanoic acid-2-octanoic acid triglyceride, comprising: adding 100 mg of 1,3-diheptanoic acid-2-octanoic acid triglyceride, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of cyclohexane into a 50 mL reactor and then sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 5 MPa, stirring the mixed material in the reactor and heating it to 240° C. for reaction for 12 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yields of 1-heptene and 1-octene in the product, respectively.

[0068] Embodiment 13

[0069] This Example 13 provides a method for preparing 1-octadecene and 1-hexadecene from 1,3-oleo-2-palmitoyl triglyceride, comprising: adding 100 mg of 1,3-oleo-2-palmitoyl triglyceride, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of n-hexane into a 50 mL reactor and then sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 5 MPa, stirring the mixed material in the reactor and heating it to 240°C for reaction for 12 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yields of 1-octadecene and 1-hexadecene in the product were 63% and 32%, respectively.

[0070] Comparative Example 1

[0071] This comparative example 1 provides a method for preparing 1-octene from n-octanoic acid, comprising: adding 100 mg of n-octanoic acid, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of n-hexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixed material in the reactor and heating it to 240° C. for reaction for 8 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase for detection, and finding that the yield of 1-octene in the product was 51%, and the yield of octane was 45%.

[0072] Comparative Example 2

[0073] This comparative example 2 provides a method for preparing 1-decene from n-decanoic acid, comprising: adding 100 mg of n-decanoic acid, 10 mg of a bimetallic catalyst (10Ni5Cu / HZSM-5), and 10 mL of n-hexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the air pressure in the reactor to 3 MPa, stirring the mixed material in the reactor and heating it to 240° C. for reaction for 8 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-decene in the product to be 63%, and the yield of octane to be 35%.

[0074] Comparative Example 3

[0075] Comparative Example 3 provides a method for preparing 1-tetradecene from myristic acid, comprising: adding 100 mg of myristic acid, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of n-hexane into a 50 mL reactor, sealing the reactor, introducing hydrogen to adjust the pressure in the reactor to 3 MPa, stirring the mixture in the reactor and heating it to 240° C. for reaction for 8 hours, cooling the reactor to room temperature in an ice-water bath, collecting the organic phase, and detecting the yield of 1-tetradecene in the product to be 32%, and the yield of tetradecane to be 63%.

[0076] Although the embodiments of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as described in the claims. Moreover, the present invention described herein may have other embodiments and may be implemented or realized in a variety of ways.

Claims

1. A method for preparing α-olefins from triglyceride compounds, characterized in that: include: In a solvent environment, hydrogen-containing atmosphere, and 50°C-300°C, triglyceride compound I reacts with a NiCu bimetallic catalyst to generate α-olefin II-1, α-olefin II-2, and α-olefin II-3; ； Wherein, R1, R2, and R3 are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, cyano, nitro, carboxyl, aromatic ring, or furan ring.

2. The method according to claim 1, characterized in that The solvent environment includes n-hexane, cyclohexane, n-octane, n-heptane, n-decane, cyclopentane or tetrahydrofuran; and / or, the hydrogen concentration in the hydrogen-containing atmosphere is 10%-100%; and / or, the pressure of the hydrogen-containing atmosphere is 1MPa-5MPa; and / or, the triglyceride compound I is reacted for 0.1h-10h under the catalysis of the NiCu bimetallic catalyst; and / or, the particle size of the NiCu bimetallic catalyst is 1-100nm.

3. The method according to claim 1, characterized in that The NiCu bimetallic catalyst comprises a catalytic carrier and active nickel and active copper loaded thereon, and the loading amounts of the active nickel and the active copper on the catalytic carrier are independently 0.1 wt%-50 wt%.

4. The method according to claim 1 or 3, characterized in that: The preparation method of the NiCu bimetallic catalyst comprises: impregnating a catalyst carrier in a mixed solution containing a nickel salt and a copper salt, evaporating the solution to dryness, calcining the solution, and reducing the solution in a reducing atmosphere to obtain the NiCu bimetallic catalyst.

5. The method according to claim 4, characterized in that The catalytic carrier comprises Hβ molecular sieve, SiO2, HZSM-5, Al2O3, C, ZrO2 or MOF; and / or the specific surface area of ​​the catalytic carrier is 100m 2 / g-2000m 2 / g; and / or, the nickel salt includes nickel chloride, nickel nitrate or nickel sulfate; and / or, the copper salt includes copper chloride, copper nitrate or copper sulfate.

6. The method according to claim 4, characterized in that The preparation method of the NiCu bimetallic catalyst comprises the following steps: dispersing a catalyst carrier in a mixed solution and impregnating the mixed suspension to obtain a mixed suspension; evaporating the mixed suspension to dryness and then crushing the mixed suspension to obtain a catalyst precursor; calcining and oxidizing the catalyst precursor in an oxidizing atmosphere to obtain a catalyst intermediate; and calcining and reducing the catalyst intermediate in a reducing atmosphere to obtain a NiCu bimetallic catalyst.

7. The method according to claim 6, characterized in that The catalytic carrier is dispersed in the mixed suspension under mechanical mixing, and the mechanical mixing includes stirring, oscillation or ultrasound; and / or, the mixed suspension is evaporated to dryness at 100°C-150°C; and / or, the temperature of calcination oxidation and calcination reduction are independently 350°C-450°C; and / or, the flow rate of oxidizing atmosphere and reducing atmosphere are independently 1mL / min-150mL / min; and / or, the duration of calcination oxidation and calcination reduction are independently 1h-10h.

8. The method according to claim 1, characterized in that The triglyceride compound I includes one of valeric acid triglyceride, caproic acid triglyceride, heptanoic acid triglyceride, caprylic acid triglyceride, nonanoic acid triglyceride, capric acid triglyceride, undecanoic acid triglyceride, lauric acid triglyceride, palmitic acid triglyceride, stearic acid triglyceride, oleic acid triglyceride, linoleic acid triglyceride, 1,3-dioctanoic acid-2-decanoic acid triglyceride, 1,3-diheptanoic acid-2-octanoic acid triglyceride, and 1,3-oleic acid-2-palmitic acid triglyceride.

9. The method according to claim 1, characterized in that: The mass ratio of the triglyceride compound I to the NiCu bimetallic catalyst is (0.01-1000):1; and / or, the mass concentration of the triglyceride compound I in the solvent environment is 0.001%-50%.

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