Method for preparing α-olefin from triglyceride compound

Abstract

The present invention provides a method for preparing α-olefins from triglyceride compounds, which relates to the technical field of organic synthesis. The method provided by the present invention is carried out in a solvent environment, a hydrogen-containing atmosphere, and at 50°C - 300°C. Under the catalysis of a NiCu bimetallic catalyst, triglyceride compound I reacts to generate α-olefin II-1, α-olefin II-2, and α-olefin II-3. The method provided by the present invention uses triglyceride compounds as reaction substrates, can efficiently synthesize α-olefin compounds, and the reaction is green and efficient, with high atom utilization rate and no pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a method for preparing α-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 prepared α-olefin products are complex and the selectivity of single products is low. The direct catalytic hydrodecarbonylation of fatty acid triglycerides to produce α-olefins is a promising approach. However, due to the complex structure of tri-esters and the inert chemical properties of ester groups, there are few studies using them as substrates, mainly focusing on fatty acids. Since natural vegetable oils basically exist in the form of triglycerides, using fatty acid triglycerides to prepare α-olefins can greatly improve the synthesis convenience and application of α-olefins. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for preparing α-olefins from triglyceride compounds. By using triglyceride compounds as reaction substrates, α-olefin compounds can be efficiently synthesized, and the reaction is green and efficient, with high atom utilization rate and no pollution.

[0004] A method for preparing α-olefins from triglyceride compounds provided by the present invention includes: in a solvent environment, a hydrogen-containing atmosphere, and at 50°C - 300°C, triglyceride compound I reacts under the catalysis of a NiCu bimetallic catalyst to generate α-olefin II-1, α-olefin II-2, and α-olefin II-3;

[0005] ;

[0006] Wherein, R1, R2, and R3 are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a cyano group, a nitro group, a carboxyl group, an aromatic ring, or a furan ring.

[0007] Optionally, the solvent environment includes n-hexane, cyclohexane, n-octane, n-heptane, n-decane, cyclopentane, or tetrahydrofuran.

[0008] Optionally, the hydrogen concentration in the hydrogen-containing atmosphere is 10% - 100%.

[0009] Optionally, the pressure of the hydrogen-containing atmosphere is 1 MPa - 5 MPa.

[0010] Optionally, triglyceride compound I reacts for 0.1 h - 10 h under the catalysis of the NiCu bimetallic catalyst.

[0011] Optionally, the particle size of the NiCu bimetallic catalyst is 1-100 nm.

[0012] Optionally, the NiCu bimetallic catalyst comprises a catalytic support and the active nickel and active copper supported thereon, and the loadings of the active nickel and the active copper on the catalytic support are independently 0.1 wt%-50 wt%.

[0013] Optionally, the method for preparing the NiCu bimetallic catalyst comprises: impregnating a catalytic support in a mixed solution containing nickel salt and copper salt, evaporating to dryness, calcining, and then reducing in a reducing atmosphere to obtain the NiCu bimetallic catalyst.

[0014] Optionally, the catalytic support comprises Hβ zeolite, SiO2, C, HZSM-5, Al2O3, ZrO2 or MOF.

[0015] Optionally, the specific surface area of the catalytic support is 100 m 2 / g - 2000 m 2 / g.

[0016] Optionally, the nickel salt comprises nickel chloride, nickel nitrate or nickel sulfate.

[0017] Optionally, the copper salt comprises copper chloride, copper nitrate or copper sulfate.

[0018] Optionally, the method for preparing the NiCu bimetallic catalyst comprises the following steps: dispersing a catalytic support in a mixed solution to obtain a mixed suspension; evaporating the mixed suspension to dryness and then pulverizing 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 the NiCu bimetallic catalyst.

[0019] Optionally, the catalytic support is dispersed in the mixed suspension under mechanical mixing, and the mechanical mixing includes stirring, oscillation or ultrasonic treatment.

[0020] Optionally, the mixed suspension is evaporated to dryness at 100°C - 150°C.

[0021] Optionally, the temperatures of the calcination oxidation and the calcination reduction are independently 350°C - 450°C.

[0022] Optionally, the flow rates of the oxidizing atmosphere and the reducing atmosphere are independently 1 mL / min - 150 mL / min.

[0023] Optionally, the durations of the calcination oxidation and the calcination reduction are independently 1 h - 10 h.

[0024] Optionally, the triglyceride compound I includes one of triglyceride pentanoate, triglyceride hexanoate, triglyceride heptanoate, triglyceride octanoate, triglyceride nonanoate, triglyceride decanoate, triglyceride undecanoate, triglyceride laurate, triglyceride palmitate, triglyceride stearate, triglyceride oleate, triglyceride linoleate, 1,3-dioctanoyl-2-decanoyl glycerol, 1,3-diheptanoyl-2-octanoyl glycerol, 1,3-oleoyl-2-palmitoyl glycerol.

[0025] Optionally, the mass ratio of the triglyceride compound I to the NiCu bimetallic catalyst is (0.01 - 1000):1.

[0026] Optionally, the mass concentration of the triglyceride compound I in the solvent environment is 0.001% - 50%. Description of the Drawings

[0027] Figure 1 It is a chemical reaction formula for preparing α-olefins from a triglyceride compound provided by the present invention;

[0028] Figure 2 It is a schematic diagram of the technical route for preparing α-olefins from triglyceride compounds;

[0029] Figure 3 It is a schematic diagram of the reaction mechanism for the conversion of triglyceride compounds to α-olefins on the surface of a bimetallic catalyst;

[0030] Figure 4 It is a flowchart of the preparation method of the NiCu bimetallic catalyst in some embodiments of the present invention. Detailed Embodiments

[0031] To make the objectives, 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. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein shall have the ordinary meaning as understood by those of ordinary skill in the art to which the present invention belongs.

[0032] See Figure 1 , the present invention provides a method for preparing α-olefins from triglyceride compounds, including: in a solvent environment, a hydrogen-containing atmosphere, and at 50°C - 300°C, the triglyceride compound I reacts under the catalysis of a NiCu bimetallic catalyst to generate α-olefin II-1, α-olefin II-2, and α-olefin II-3;

[0033] ;

[0034] Among them, R1, R2, and R3 are independently of each other a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a cyano group, a nitro group, a carboxyl group, an aromatic ring, or a furan ring.

[0035] Actually, referring to Figure 2 , during the reaction, triglyceride compound I is first hydrocracked into fatty acids, then decarbonylated to obtain fatty aldehydes, and further hydrogenated in a hydrogen-containing atmosphere to form fatty alcohols. Finally, the fatty alcohols are dehydrated by one molecule of water to obtain α-olefin compounds. Specifically, referring to Figure 3 , it can be seen from the reaction path of converting triglyceride compound I into α-olefin compounds that first, triglyceride compound I is hydrocracked into fatty acids on the surface of Ni, and the fatty acids are decarbonylated by the Ni-Cu interface to obtain fatty aldehydes and CO. Subsequently, the carbonyl group of the fatty aldehyde is adsorbed by Ni-Cu and catalytically hydrogenated and dehydrated to obtain α-olefins.

[0036] In some embodiments, the solvent environment used includes n-hexane, cyclohexane, n-octane, n-heptane, n-decane, cyclopentane, or tetrahydrofuran. Actually, when selecting the solvent environment, common organic solvents in the art can be used, provided that they do not chemically react with substances such as triglyceride compound I. In addition, by carrying out the preparation reaction in the solvent environment, it is beneficial for triglyceride compound I to come into full contact with the NiCu bimetallic catalyst.

[0037] In some embodiments, the hydrogen concentration in the hydrogen-containing atmosphere during the reaction is 10% - 100%. Actually, when triglyceride compound I generates fatty alcohols on the surface of the 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 hydrogen concentration in the hydrogen-containing atmosphere is less than 100%, the hydrogen-containing atmosphere may further include non-oxidizing carrier gases, such as inert gases like nitrogen, argon, and helium.

[0038] Actually, since the hydrogen concentration will decrease after hydrogen participates in the reaction during the reaction process, a certain amount of hydrogen can be replenished into the reaction environment as the reaction progresses to maintain the hydrogen concentration stable. In some embodiments, the pressure of the hydrogen-containing atmosphere during the reaction is 1 MPa - 5 MPa, and maintaining the pressure environment is beneficial for promoting the forward progress of the preparation reaction.

[0039] In some embodiments, the triglyceride compound I reacts for 0.1 h - 10 h under the catalysis of the NiCu bimetallic catalyst. In fact, the triglyceride compound I used includes one of triglyceride pentanoate, triglyceride hexanoate, triglyceride heptanoate, triglyceride octanoate, triglyceride nonanoate, triglyceride decanoate, triglyceride undecanoate, triglyceride laurate, triglyceride palmitate, triglyceride stearate, triglyceride oleate, triglyceride linoleate, 1,3 - dioctanoyl - 2 - decanoyl glycerol, 1,3 - didecanoyl - 2 - lauroyl glycerol, 1,3 - dioleoyl - 2 - palmitoyl glycerol. Therefore, when facing reaction substrates with different structural formulas, different reaction durations are required when the reaction is complete.

[0040] In some embodiments, the mass ratio of the triglyceride compound I to the NiCu bimetallic catalyst is (0.01 - 1000):1. In fact, by adjusting the dosage ratio of the reactant to the catalyst, it is beneficial to promote the full contact of the triglyceride compound I with the bimetallic catalyst in the solvent environment, and thus beneficial to the reaction occurring at the surface Ni - Cu bimetallic interface. Specifically, the mass concentration of the triglyceride compound I in the solvent environment is 0.001% - 50%.

[0041] Specifically, the NiCu bimetallic catalyst used includes a catalytic support and the active nickel and active copper supported thereon. By using the catalytic support for loading, it is beneficial to increase the loading amount of the active nickel and active copper, and at the same time can provide an anchoring effect for the active nickel and active copper, and can increase the specific surface area of the bimetallic catalyst, thus being beneficial to promoting the contact between Ni - Cu and the triglyceride compound I.

[0042] Furthermore, the loading amounts of the active nickel and active copper on the catalytic support are independently 0.1 wt% - 50 wt%. In fact, by adjusting the loading amounts of the active nickel and active copper on the catalytic support, it is beneficial to adjust the morphology and distribution of the Ni - Cu bimetallic interface formed on the surface of the catalytic support.

[0043] In some embodiments, the preparation method of the NiCu bimetallic catalyst includes: impregnating the catalytic support in a mixed solution dissolved with nickel salt and copper salt, evaporating to dryness, calcining, and then reducing in a reducing atmosphere to obtain the NiCu bimetallic catalyst. In fact, through the solvent impregnation method, it is beneficial for the nickel salt and copper salt to uniformly adhere to the surface of the catalytic support, and after calcination, not only can sintering and fixation be carried out, but also an oxide coating can be formed, and then active nickel and active copper can be obtained after reduction in a reducing atmosphere.

[0044] In some embodiments, the catalytic support used includes Hβ zeolite, SiO2, HZSM - 5, C, Al2O3, ZrO2 or MOF. In addition, the specific surface area of the catalytic support used is 50 m 2 / g - 3000m 2 / g. Actually, the nickel salts used include nickel chloride, nickel nitrate or nickel sulfate, and the copper salts used include copper chloride, copper nitrate or copper sulfate.

[0045] In some embodiments, referring to Figure 4 , a method for preparing a NiCu bimetallic catalyst includes the following steps:

[0046] S1. Disperse the catalytic support in a mixed solution for impregnation to obtain a mixed suspension;

[0047] S2. Evaporate the mixed suspension to dryness and then crush it to obtain a catalytic precursor;

[0048] S3. Calcinate and oxidize the catalytic precursor in an oxidizing atmosphere to obtain a catalytic intermediate;

[0049] S4. Calcinate and reduce the catalytic intermediate in a reducing atmosphere to obtain a NiCu bimetallic catalyst.

[0050] In some embodiments, disperse the catalytic support in the mixed solution under mechanical mixing, which is beneficial to the uniform distribution of nickel salts and copper salts in the catalytic support. Specifically, the mechanical mixing includes stirring, oscillation or ultrasound. In addition, the mixed suspension can be evaporated to dryness at 100°C - 150°C, and the temperatures of calcination oxidation and calcination reduction are independently controlled to be 350°C - 450°C, the durations of calcination oxidation and calcination reduction are independently 1h - 10h, and the flow rates of the oxidizing atmosphere and the reducing atmosphere are independently 1mL / min - 150mL / min. In addition, the particle size of the prepared NiCu bimetallic catalyst is 1nm - 100nm.

[0051] Preparation Example

[0052] This preparation example provides a method for preparing a NiCu bimetallic catalyst, including the following steps:

[0053] S1. Stir and dissolve copper chloride dihydrate and nickel chloride dihydrate in 10 mL of ultrapure water to obtain a mixed solution, then put the catalytic support into the mixed suspension and stir at a speed of 100 rpm at room temperature for 12 h to obtain a mixed suspension;

[0054] S2. Place the mixed suspension in an oven at 110°C and dry it for 10 h, then crush it to obtain a catalytic precursor;

[0055] S3. Place the catalytic precursor in a tubular furnace and calcine it at 400°C under 80 mL / min of air for 4 h to obtain a catalytic intermediate;

[0056] S4. Convert the gas in the tubular furnace to 80 mL / min of hydrogen and calcine it at 400°C for 4 h, then cool it to room temperature with the furnace to obtain a NiCu bimetallic catalyst in the form of a black powder.

[0057] The NiCu bimetallic catalyst prepared in the preparation example was used for the preparation of α-olefins in Examples 1 to 13 and Comparative Examples 1 to 3, and the NiCu bimetallic catalyst was expressed as aNibCu / catalytic support. For example, 0.1Ni0.1Cu / Hβ indicates that Hβ was used as the catalytic support, and the content of active nickel on the catalytic support was 0.1 and the content of active copper was 0.1.

[0058] At the same time, the yields of the reaction products of Examples 1 to 13 and Comparative Examples 1 to 3 were detected. For quantitative analysis, an Agilent 7890A series gas chromatograph (FID detector, Agilent HP-5 chromatographic column: 30m * 32um * 0.25um) was used, and for qualitative analysis, a Thermoscientific TRACE1310 gas mass spectrometer (HP-5 capillary chromatographic column 30m * 320μm * 0.25μm) was used.

[0059] Example 1

[0060] Example 1 provided a method for preparing 1-pentene from triglyceride pentanoate, including: adding 100 mg of triglyceride pentanoate, 10 mg of bimetallic catalyst (0.1Ni0.1Cu / Hβ), and 10 mL of n-hexane into a 50 mL reaction kettle, then sealing the reaction kettle, introducing hydrogen to adjust the pressure in the reaction kettle to 3 MPa, stirring and heating the mixed materials in the reaction kettle to 50 °C for reaction for 10 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yield of 1-pentene in the product was 65%.

[0061] Example 2

[0062] Example 2 provided a method for preparing 1-octene from triglyceride octanoate, including: adding 100 mg of triglyceride octanoate, 0.1 mg of bimetallic catalyst (50Ni50Cu / Hβ), and 10 mL of cyclohexane into a 50 mL reaction kettle, then sealing the reaction kettle, introducing hydrogen to adjust the pressure in the reaction kettle to 0.1 MPa, stirring and heating the mixed materials in the reaction kettle to 300 °C for reaction for 0.1 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yield of 1-octene in the product was 91%.

[0063] Example 3

[0064] Example 3 provided a method for preparing 1-decene from triglyceride caprate, including: adding 100 mg of triglyceride caprate, 40 mg of bimetallic catalyst (15Ni4Cu / Hβ), and 10 mL of cyclooctane into a 50 mL reactor, then sealing the reactor, introducing hydrogen to adjust the internal pressure of the reactor to 3 MPa, stirring the mixed materials in the reactor and heating to 180 °C for reaction for 2 h, then performing an ice-water bath cooling on the reactor to room temperature, collecting the organic phase and detecting that the yield of 1-decene in its product was 85%.

[0065] Example 4

[0066] Example 4 provided a method for preparing 1-dodecene from triglyceride laurate, including: adding 100 mg of triglyceride laurate, 200 mg of bimetallic catalyst (20Ni15Cu / Hβ), and 10 mL of tetrahydrofuran into a 50 mL reactor, then sealing the reactor, introducing hydrogen to adjust the internal pressure of the reactor to 5 MPa, stirring the mixed materials in the reactor and heating to 300 °C for reaction for 8 h, then performing an ice-water bath cooling on the reactor to room temperature, collecting the organic phase and detecting that the yield of 1-dodecene in its product was 83%.

[0067] Example 5

[0068] Example 5 provided a method for preparing 1-octadecene from triglyceride linoleate, including: adding 100 mg of triglyceride linoleate, 10 g of bimetallic catalyst (40Ni40Cu / Hβ), and 10 mL of n-octane into a 50 mL reactor, then sealing the reactor, introducing hydrogen to adjust the internal pressure of the reactor to 0.1 MPa, stirring the mixed materials in the reactor and heating to 300 °C for reaction for 0.1 h, then performing an ice-water bath cooling on the reactor to room temperature, collecting the organic phase and detecting that the yield of 1-octadecene in its product was 72%.

[0069] Example 6

[0070] Example 6 provided a method for preparing 1-octadecene from triglyceride stearate, including: adding 100 mg of triglyceride stearate, 0.1 mg of bimetallic catalyst (15Ni4Cu / SiO2), and 1 mL of n-octane into a 50 mL reactor, then sealing the reactor, introducing hydrogen to adjust the internal pressure of the reactor to 3 MPa, stirring the mixed materials in the reactor and heating to 150 °C for reaction for 3 h, then performing an ice-water bath cooling on the reactor to room temperature, collecting the organic phase and detecting that the yield of 1-octadecene in its product was 82%.

[0071] Example 7

[0072] Example 7 of the present invention provides a method for preparing 1-undecene from triglyceride undecanoate, including: adding 100 mg of triglyceride undecanoate, 100 mg of a bimetallic catalyst (25Ni4Cu / Al2O3), and 10 mL of cyclohexane into a 50 mL reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 3 MPa, stirring the mixed materials in the reaction kettle and heating to 180 °C for reaction for 2.5 h, then cooling the reaction kettle in an ice-water bath to room temperature, collecting the organic phase and detecting that the yield of 1-undecene in its product is 71%.

[0073] Example 8

[0074] Example 8 of the present invention provides a method for preparing 1-hexene from triglyceride hexanoate, including: adding 100 mg of triglyceride hexanoate, 40 mg of a bimetallic catalyst (30Ni15Cu / C), and 10 mL of n-heptane into a 50 mL reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 0.5 MPa, stirring the mixed materials in the reaction kettle and heating to 300 °C for reaction for 10 h, then cooling the reaction kettle in an ice-water bath to room temperature, collecting the organic phase and detecting that the yield of 1-hexene in its product is 86%.

[0075] Example 9

[0076] Example 9 of the present invention provides a method for preparing 1-hexadecene from triglyceride palmitate, including: adding 1 g of triglyceride palmitate, 1 mg of a bimetallic catalyst (9Ni4Cu / Hβ), and 10 mL of cyclopentane into a 50 mL reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 2 MPa, stirring the mixed materials in the reaction kettle and heating to 260 °C for reaction for 4 h, then cooling the reaction kettle in an ice-water bath to room temperature, collecting the organic phase and detecting that the yield of 1-hexadecene in its product is 89%.

[0077] Example 10

[0078] Example 10 of the present invention provides a method for preparing 1-octadecene from triglyceride oleate, including: adding 100 mg of triglyceride oleate, 50 mg of a bimetallic catalyst (15Ni10Cu / Hβ), and 10 mL of n-heptane into a 50 mL reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 5 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 2 h, then cooling the reaction kettle in an ice-water bath to room temperature, collecting the organic phase and detecting that the yield of 1-octadecene in its product is 98%.

[0079] Example 11

[0080] Example 11 provides a method for preparing 1-octene and 1-decene from 1,3-dioctanoyl-2-decanoyl glycerol tristearate, which includes: adding 100 mg of 1,3-dioctanoyl-2-decanoyl glycerol tristearate, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of cyclohexane into a 50 mL reaction kettle, then sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 4 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 10 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yields of 1-octene and 1-decene in the product are 55% and 28% respectively.

[0081] Example 12

[0082] Example 12 provides a method for preparing 1-heptene and 1-octene from 1,3-dihaptoyl-2-octanoyl glycerol tristearate, which includes: adding 100 mg of 1,3-dihaptoyl-2-octanoyl glycerol tristearate, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of cyclohexane into a 50 mL reaction kettle, then sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 5 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 12 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yields of 1-heptene and 1-octene in the product are 51% and 24% respectively.

[0083] Example 13

[0084] Example 13 provides a method for preparing 1-octadecene and 1-hexadecene from 1,3-oleoyl-2-palmitoyl glycerol tristearate, which includes: adding 100 mg of 1,3-oleoyl-2-palmitoyl glycerol tristearate, 10 mg of a bimetallic catalyst (10Ni10Cu / HZSM-5), and 10 mL of n-hexane into a 50 mL reaction kettle, then sealing the reaction kettle, introducing hydrogen to adjust the air pressure in the reaction kettle to 5 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 12 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yields of 1-octadecene and 1-hexadecene in the product are 63% and 32% respectively.

[0085] Comparative Example 1

[0086] Comparative Example 1 provided a method for preparing 1-octene from n-octanoic acid, including: 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 reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the pressure in the reaction kettle to 3 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 8 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yield of 1-octene in the product was 51% and the yield of octane was 45%.

[0087] Comparative Example 2

[0088] Comparative Example 2 provided a method for preparing 1-decene from n-decanoic acid, including: 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 reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the pressure in the reaction kettle to 3 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 8 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yield of 1-decene in the product was 63% and the yield of octane was 35%.

[0089] Comparative Example 3

[0090] Comparative Example 3 provided a method for preparing 1-tetradecene from myristic acid, including: 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 reaction kettle, sealing the reaction kettle, introducing hydrogen to adjust the pressure in the reaction kettle to 3 MPa, stirring the mixed materials in the reaction kettle and heating to 240 °C for reaction for 8 h, then cooling the reaction kettle to room temperature by ice-water bath, collecting the organic phase and detecting that the yield of 1-tetradecene in the product was 32% and the yield of tetradecane was 63%.

[0091] Although the embodiments of the present invention have been described in detail above, it is obvious to those skilled in the art that various modifications and changes can be made to these embodiments. However, it should be understood that such modifications and changes all fall within the scope and spirit of the present invention described in the claims. Moreover, the present invention described herein can have other embodiments and can be implemented or realized in various 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 alkyl groups; 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 0.1wt%-50wt%; the particle size of the NiCu bimetallic catalyst is 1nm-100nm; the preparation method of the NiCu bimetallic catalyst comprises: 2 / g-2000m 2 / g of catalytic carrier is dispersed in a mixed solution containing nickel salt and copper salt and impregnated to obtain a mixed suspension; the mixed suspension is evaporated to dryness and then crushed to obtain a catalytic precursor; the catalytic precursor is calcined and oxidized in an oxidizing atmosphere to obtain a catalytic intermediate; the catalytic intermediate is calcined and reduced in a reducing atmosphere to obtain a NiCu bimetallic catalyst; the catalytic carrier is Hβ molecular sieve, SiO2, HZSM-5, Al2O3, C or ZrO2.

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.

3. The method according to claim 1, characterized in that The hydrogen concentration in the hydrogen-containing atmosphere is 10%-100%.

4. The method according to claim 1, characterized in that: The pressure of the hydrogen-containing atmosphere is 1 MPa-5 MPa.

5. The method according to claim 1, characterized in that Triglyceride compound Ⅰ reacts for 0.1h-10h under the catalysis of NiCu bimetallic catalyst.

6. The method according to claim 1, characterized in that The nickel salt includes nickel chloride, nickel nitrate or nickel sulfate.

7. The method according to claim 1, characterized in that The copper salt includes copper chloride, copper nitrate or copper sulfate.

8. The method according to claim 1, characterized in that The catalyst support is dispersed in the mixed suspension under mechanical mixing, which includes stirring, shaking or ultrasound.

9. The method according to claim 1, characterized in that: The mixed suspension was evaporated to dryness at 100°C-150°C.

10. The method according to claim 1, characterized in that The temperatures for calcination oxidation and calcination reduction are independently 350°C to 450°C.

11. The method according to claim 1, characterized in that: The flow rates of the oxidizing atmosphere and the reducing atmosphere are independently 1 mL / min to 150 mL / min.

12. The method according to claim 1, characterized in that The duration of the calcination oxidation and the calcination reduction is independently 1 h to 10 h.

13. 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, 1,3-dioctanoic acid-2-decanoic acid triglyceride, and 1,3-diheptanoic acid-2-octanoic acid triglyceride.

14. 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.

15. The method according to claim 1, characterized in that The mass concentration of the triglyceride compound I in the solvent environment is 0.001%-50%.

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