CN111233603B - Method for preparing alkane by hydrogenation and photocatalysis of decarboxylation of fatty acid - Google Patents

Method for preparing alkane by hydrogenation and photocatalysis of decarboxylation of fatty acid Download PDF

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CN111233603B
CN111233603B CN201811432120.3A CN201811432120A CN111233603B CN 111233603 B CN111233603 B CN 111233603B CN 201811432120 A CN201811432120 A CN 201811432120A CN 111233603 B CN111233603 B CN 111233603B
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tio
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hydrogenation
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王峰
黄志鹏
张超锋
韩建宇
高著衍
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to a method for preparing alkane by hydrogenating and photocatalytic decarboxylation of fatty acid. The method converts fatty acid into alkane by a one-pot method through series steps of hydrogenation and photocatalytic decarboxylation in the presence of hydrogen, a catalyst and a solvent. The catalyst used is titanium dioxide modified on the surface of metal. The reaction process is as follows: mixing fatty acid, solvent and catalyst, placing them into quartz reactor, replacing the atmosphere in the reactor with low-pressure hydrogen (less than or equal to 0.5 MPa), sealing, stirring at a certain temp. (20-100 deg.C) under the condition of no light addition for a certain period of time to make hydrogenation reaction, then making decarboxylation reaction under the irradiation of external light source to obtain the invented product. The method can realize the high-efficiency conversion of the fatty acid under mild conditions, and the yield of the alkane can reach 96 percent. The catalyst after reaction is easy to separate from the reaction system and can be recycled for many times. The obtained alkane can be used for replacing the traditional fossil diesel and aviation kerosene.

Description

Method for preparing alkane by hydrogenation and photocatalysis of decarboxylation of fatty acid
Technical Field
The invention relates to a preparation method of a hydrocarbon compound, in particular to a method for preparing long-chain alkane by hydrogenation photocatalytic decarboxylation of fatty acid.
Technical Field
With the rapid development of society, the demand of energy is also increasing dramatically, but at present, the society mainly depends on limited fossil energy, and environmental pollution and CO are brought in the refining and using process 2 The emission and the like, so that renewable clean energy is developed, and the current energy and environmental pollution problems can be effectively relieved by reducing the dependence on fossil energy. Wherein renewable biomass resources are transferred toThe gasification into liquid fuel has become a research hotspot in the field of energy.
The oil and fat refining and paper industry currently produces a large amount of fatty acid by-products, which are mainly mixtures of unsaturated fatty acids, and therefore these fatty acid mixtures available in large amounts are considered as ideal raw materials for the production of green alkanes. Through the catalytic deoxidation process, fatty acid can be directly converted into straight-chain alkane of C12-C20, and the alkane can be used as the main component of fossil diesel oil, and can be used as fuel for replacing the fossil diesel oil through partial isomerization process. At present, the catalytic deoxidation process of fatty acid mostly needs higher reaction temperature (more than or equal to 250 ℃) and reaction pressure (more than or equal to 2 MPa). Moreover, many processes require the use of high pressure hydrogen for the hydrodeoxygenation of fatty acids, which requires the consumption of large amounts of hydrogen. The photocatalysis process can use light as the driving force of the reaction, and avoids the use of harsh reaction conditions such as high temperature and high pressure. Document CN107556152A discloses a method of photocatalytic decarboxylation for the conversion of higher fatty acids into alkanes, which converts in a nitrogen atmosphere with a low alkane yield of only 46%, and which has no substrate universality, limited to the catalytic conversion of saturated fatty acids.
Based on the above, although some progress has been made in the preparation of alkanes from fatty acids, there are still drawbacks, such as: the reaction temperature is high, the hydrogen pressure or the reaction pressure is high, the conversion efficiency is low, the substrate universality of the fatty acid is not strong, and the like, so that the development of a new method for preparing the long-chain alkane at low temperature, low pressure and constant temperature with high activity and high selectivity has scientific research significance and industrial application value.
Disclosure of Invention
The significance of the invention is to overcome the defects of the prior art for preparing alkane from fatty acid, such as: the method has the advantages of harsh reaction conditions, low conversion efficiency, limited substrate universality and the like, and under mild reaction conditions, fatty acid is converted into long-chain alkane through series steps of hydrogenation and photocatalytic decarboxylation by a one-pot method. The fatty acid mixture of various oil refining and paper industry by-products can realize high-efficiency conversion, and the alkane yield is 50-96%. The catalyst has high activity and good stability, and can be recycled for multiple times through simple separation and cleaning.
The preparation of long-chain alkane by the decarboxylation of hydrogenated photocatalytic fatty acid is realized by the following scheme. Mixing fatty acid, catalyst and solvent, placing the mixture into a quartz reactor, replacing the atmosphere in the reactor with hydrogen, sealing the reactor, stirring the mixture for a period of time at a certain temperature without adding light to perform hydrogenation reaction, then irradiating the mixture for a period of time at a certain temperature by using an external light source to perform decarboxylation reaction to generate an alkane product, and detecting the product by chromatography.
Wherein the fatty acid is one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid, rapeseed oil fatty acid, corn oil fatty acid, palm oil fatty acid and tall oil fatty acid; the concentration of the fatty acid in the initial reaction system is 2-20 g/L; the catalyst is titanium dioxide modified on the surface of metal, wherein the titanium dioxide is TiO 2 -A (anatase phase TiO) 2 )、TiO 2 -R (rutile phase TiO) 2 )、TiO 2 (P25); the metal in the titanium dioxide modified on the metal surface is one or more of Pt, pd, ru, au, ag and Ni; the loading of the metal is 0.1-10.0wt% (based on the mass of the carrier); the solvent is one or more of ethyl acetate, 1, 2-dichloroethane, dichloromethane, acetonitrile and trifluorotoluene; the hydrogen pressure is 0.1-0.5 MPa; the temperature of the hydrogenation reaction is 20-100 ℃, and the hydrogenation time is 10 min-4 h; the external light source is one or more of LED (with the central wavelength of 365nm, 18W), a xenon lamp (300W) and a high-pressure mercury lamp; the decarboxylation reaction temperature is 15-40 ℃, and the decarboxylation reaction time is 30 min-24 h.
Preferably, the method comprises the following steps: the fatty acid is preferably one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid, rapeseed oil fatty acid and palm oil fatty acid; the concentration of the fatty acid in the initial reaction system is preferably 5-15 g/L; the catalyst is titanium dioxide with a modified metal surface, wherein the titanium dioxide is preferably TiO 2 -A (anatase phase TiO) 2 )、TiO 2 One or two of (P25); in titanium dioxide modified with metal surfaceThe metal(s) is preferably one or more of Pt, pd, ru and Au; the loading of the metal is preferably from 0.1 to 5.0 wt.% (based on the mass of the support); the solvent is preferably one or more of dichloromethane, acetonitrile and trifluorotoluene; the hydrogen pressure is preferably 0.1-0.3 MPa; the temperature of the hydrogenation reaction is preferably 20-60 ℃, and the hydrogenation time is preferably 30 min-2 h; the external light source is preferably one or two of an LED (with the central wavelength of 365nm, 18W) and a xenon lamp (300W); the decarboxylation reaction temperature is preferably 15-30 ℃, and the decarboxylation reaction time is preferably 1-12 h.
The best is as follows: the optimal fatty acid is one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid and palm oil fatty acid; the optimal concentration of the fatty acid in the initial reaction system is 5-10 g/L; the catalyst is titanium dioxide modified on the surface of metal, wherein the best titanium dioxide is TiO 2 (P25); the optimal metal in the titanium dioxide modified by the metal surface is one or two of Pt and Pd; the optimal loading amount of the surface modified metal is 0.5-2.0 wt% (based on the mass of the carrier); the optimal solvent is one or two of acetonitrile and benzotrifluoride; the optimal pressure of the hydrogen is 0.1-0.15 MPa; the optimal temperature of the hydrogenation reaction is 20-40 ℃, and the optimal hydrogenation time is 1-2 h; the optimal external light source is an LED (the central wavelength is 365nm, and the central wavelength is 18W); the optimal temperature of the decarboxylation reaction is 20-30 ℃, and the optimal time of the decarboxylation reaction is 1-9 h.
The reaction process is shown as formula 1 by taking the hydrogenation and photocatalytic decarboxylation of linoleic acid as an example. In a hydrogen atmosphere, linoleic acid firstly undergoes a hydrogenation reaction on a titanium dioxide catalyst modified by a metal surface to be converted into corresponding saturated octadecanoic acid, then is oxidized by a photoproduction hole under the illumination condition, is decarboxylated to generate an alkyl radical, and then is subjected to photogeneration electron reduction to obtain a proton dissociated by carboxylic acid, which is taken as active hydrogen and then is combined with the alkyl radical to generate an alkane product. The consumption of hydrogen during the photocatalytic decarboxylation is very small. Meanwhile, the reaction process is carried out under the mild condition and the hydrogen pressure condition, so that hydrocracking and byproduct CO are avoided 2 Hydrogenation, etc. ofA side reaction that consumes hydrogen. Thus, no additional hydrogen is consumed during the reaction, except for the hydrogen consumed by hydrogenation of the substrate double bonds.
Figure BDA0001882848270000031
The reaction process of the hydrogenation photocatalytic decarboxylation of linoleic acid of formula 1
Compared with the existing method for preparing alkane by decarboxylation of fatty acid, the method has the following advantages:
1. the yield of alkane products is high and can reach 96 percent;
2. the reaction conditions are mild (the temperature is less than or equal to 100 ℃, and the hydrogen pressure is less than or equal to 0.5 MPa), so that harsh reaction conditions such as high temperature and high pressure are avoided;
3. the substrate has wide application range, and different unsaturated fatty acids including various oil refining and paper industry by-product fatty acid mixtures can be efficiently converted into alkane products;
4. the method has low hydrogen consumption;
5. the catalyst has high activity, good stability, easy separation and repeated recycling.
Drawings
FIG. 1 is a gas chromatogram of the product of example 25;
FIG. 2 is a gas chromatogram of the product of example 28.
Detailed Description
In order to further illustrate the present invention in detail, several specific examples are given below, but the present invention is not limited to these examples.
Example 1
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by chromatography, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 95%.
Example 2
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Pd/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 81%.
Example 3
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Ru/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 60 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 76%.
Example 4
1.5mL of an acetonitrile solution of linoleic acid (concentration: 10 g/L) and Au/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 60 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 72%.
Example 5
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Ag/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 100 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 68%.
Example 6
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Ni/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, the atmosphere in the reaction tube was replaced with hydrogen (0.1 MPa), sealed, stirred at 80 ℃ for 1 hour, and then LED (center wavelength)365nm, 18W) for 2.0h at 25 ℃, and the product mass spectrum is consistent with the standard spectrum by chromatographic detection, and the yield of heptadecane is 65%.
Example 7
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 10mg of-A (1 wt%), replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring for 1h at the temperature of 25 ℃, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 81%.
Example 8
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 10mg of-R (1 wt%), replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1.5h, then reacting for 5.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by a chromatogram, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 55%.
Example 9
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Pt/TiO are respectively added into a quartz reaction tube 2 (0.1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 3.0h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by a chromatographic method, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 55%.
Example 10
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 (0.5 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 2.0h, then reacting under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, wherein the reaction temperature is 25 ℃, the product is detected by a chromatogram, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 78%.
Example 11
In the quartz reverse direction1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Pt/TiO are respectively added into the reaction tube 2 (5 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 0.5h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 94%.
Example 12
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 (10 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 20min, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by chromatography, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 95%.
Example 13
1.5mL of linoleic acid acetonitrile solution (concentration of 2 g/L) and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 30min, then reacting for 1.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 92%.
Example 14
1.5mL of linoleic acid in acetonitrile (20 g/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 3h, then reacting for 3.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 93%.
Example 15
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, the atmosphere in the reaction tube was replaced with hydrogen (0.3 MPa), the reaction tube was sealed, stirred at 25 ℃ for 1 hour, and then reacted under irradiation of an LED (center wavelength 365nm, 18W) for 2.0 hours, and the reaction was carried outThe temperature is 25 ℃, the product is detected by chromatography, the mass spectrum of the product is consistent with the standard spectrum, and the yield of the heptadecane is 95%.
Example 16
1.5mL of linoleic acid acetonitrile solution (with the concentration of 10 g/L) and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.5 MPa), sealing, stirring at 25 ℃ for 30min, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 96%.
Example 17
1.5mL of ethyl acetate solution of linoleic acid (10 g/L in concentration) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by chromatography, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 54%.
Example 18
1.5mL of a 1, 2-dichloroethane solution of linoleic acid (10 g/L in concentration) and 1.5mL of Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (center wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 61%.
Example 19
1.5mL of a dichloromethane solution of linoleic acid (10 g/L in concentration) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (center wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 61%.
Example 20
Respectively adding sub-substances into quartz reaction tubesOleic acid in trifluorotoluene (10 g/L) 1.5mL and Pt/TiO 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 75%.
Example 21
1.5mL of linoleic acid acetonitrile solution (with a concentration of 10 g/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of a high-pressure mercury lamp, wherein the reaction temperature is 40 ℃, the product is detected by a chromatograph, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 78%.
Example 22
30mL of an acetonitrile solution of linoleic acid (10 g/L in concentration) and 30mL of Pt/TiO were added to a 100mL Schlenk reaction flask 2 (1 wt%) 200mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring for 4h at the temperature of 25 ℃, then reacting for 10h under the irradiation of a xenon lamp (300W), wherein the reaction temperature is 40 ℃, the product is detected by a chromatograph, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 82%.
Example 23
1.5mL of an acetonitrile solution (with the concentration of 10 g/L) of oleic acid and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the product is detected by chromatography, the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 94%.
Example 24
1.5mL of palmitoleic acid acetonitrile solution (with the concentration of 10 g/L) and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring at 25 deg.C for 1h, then reacting for 30min under the irradiation of LED (center wavelength 365nm, 18W), the reaction temperature is 25 deg.C, detecting the product by chromatography, and obtaining the productThe mass spectrum is consistent with the standard spectrum, and the yield of the pentadecane is 92 percent.
Example 25
1.5mL of acetonitrile solution (concentration of 10 g/L) of soybean oil fatty acid and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.2 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is detected by chromatography, the mass spectrum of the product is consistent with that of a standard spectrum, the product is paraffin such as pentadecane, heptadecane and nonadecane, and the total yield is 92%.
Example 26
1.5mL of an acetonitrile solution (concentration of 10 g/L) of rapeseed oil fatty acid and 1.5mL of Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.2 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is detected by chromatography, the mass spectrum of the product is consistent with that of a standard spectrum, the product is long paraffin such as pentadecane, heptadecane and nonadecane, and the total yield is 86%.
Example 27
1.5mL of acetonitrile solution (with the concentration of 10 g/L) of corn oil fatty acid and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.2 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is detected by chromatography, the mass spectrum of the product is consistent with that of a standard spectrum, the product is paraffin such as pentadecane, heptadecane and nonadecane, and the total yield is 78%.
Example 28
1.5mL of a tall oil fatty acid acetonitrile solution (10 g/L in concentration) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.2 MPa), sealing, stirring at 25 deg.C for 1h, then reacting for 30min under the irradiation of LED (central wavelength 365nm, 18W), the reaction temperature is 25 deg.C, detecting the product by chromatography, the mass spectrum of the product is consistent with that of the standard spectrum, and the product is pentadecane, heptadecaneParaffins such as alkane and nonadecane in a total yield of 83%.
Example 29
1.5mL of acetonitrile solution (with the concentration of 10 g/L) of palm oil fatty acid and Pt/TiO are respectively added into a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.2 MPa), sealing, stirring at 25 ℃ for 1h, then reacting for 30min under the irradiation of an LED (central wavelength 365nm, 18W), wherein the reaction temperature is 25 ℃, the mass spectrum of the product is detected by chromatography, the mass spectrum of the product is consistent with that of a standard spectrum, the product is paraffin such as pentadecane, heptadecane and nonadecane, and the total yield is 89%.

Claims (4)

1. A method for preparing alkane by hydrogenation and photocatalytic decarboxylation of fatty acid is characterized in that:
mixing fatty acid, a catalyst and a solvent, putting the mixture into a quartz reactor, replacing the atmosphere in the reactor with hydrogen, sealing the reactor, stirring the mixture under the condition of no light addition to carry out hydrogenation reaction, and then irradiating the mixture by an external light source to carry out decarboxylation reaction to generate alkane;
the fatty acid is one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid, rapeseed oil fatty acid, corn oil fatty acid, palm oil fatty acid and tall oil fatty acid;
the catalyst is titanium dioxide modified on the surface of metal;
the hydrogen pressure is 0.1-0.5 MPa;
the temperature of the hydrogenation reaction is 20 DEG 0 C~100 0 And C, the hydrogenation time is 10 min-4 h.
2. The method of claim 1, wherein:
the concentration of the fatty acid in an initial reaction system is 2-20 g/L;
the titanium dioxide is TiO 2 -A、TiO 2 -R、TiO 2 One or more of P25; the metal in the titanium dioxide modified on the metal surface is one or more of Pt, pd, ru, au, ag and Ni; the loading of the metal based on the mass of the carrier is 0.1- 10.0 wt%；
The solvent is one or more of ethyl acetate, 1, 2-dichloroethane, dichloromethane, acetonitrile and trifluorotoluene;
the additional light source is an 18W LED, wherein the central wavelength is 365nm, one or more of a 300W xenon lamp and a high-pressure mercury lamp;
the decarboxylation reaction temperature is 15 DEG 0 C ~ 40 0 And C, the decarboxylation reaction time is 30 min-24 h.
3. A method according to claim 1 or 2, characterized in that:
the fatty acid is one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid, rapeseed oil fatty acid and palm oil fatty acid;
the concentration of the fatty acid in an initial reaction system is 5-15 g/L;
the catalyst is titanium dioxide modified on the surface of metal, wherein the titanium dioxide is TiO 2 -A、TiO 2 One or two of P25; the metal in the titanium dioxide modified on the metal surface is one or more of Pt, pd, ru and Au; the loading amount of the metal based on the mass of the carrier is 0.1-5.0 wt%;
the solvent is one or more of dichloromethane, acetonitrile and trifluorotoluene;
the hydrogen pressure is 0.1-0.3 MPa;
the temperature of the hydrogenation reaction is 20 DEG 0 C~60 0 C, the hydrogenation time is 30 min-2 h;
the external light source is preferably an 18W LED, wherein the center wavelength is 365nm, 300W xenon lamps or both;
the decarboxylation reaction temperature is 15 DEG 0 C ~ 30 0 And C, the decarboxylation reaction time is 1-12 h.
4. A method as claimed in claim 3, characterized in that:
the fatty acid is one or more of palmitoleic acid, oleic acid, linoleic acid, soybean oil fatty acid and palm oil fatty acid;
the concentration of the fatty acid in an initial reaction system is 5-10 g/L;
the catalyst is titanium dioxide modified on the surface of metal, wherein the titanium dioxide is TiO 2 P25; the metal in the titanium dioxide modified on the metal surface is one or two of Pt and Pd; the loading amount of the surface-modified metal based on the mass of the carrier is 0.5-2.0 wt%;
the solvent is one or two of acetonitrile and benzotrifluoride;
the hydrogen pressure is 0.1-0.15 MPa;
the temperature of the hydrogenation reaction is 20 DEG 0 C~40 0 C, the hydrogenation time is 1-2 h;
the external light source is an 18W LED, wherein the central wavelength is 365 nm;
the temperature of the decarboxylation reaction is 20 DEG 0 C ~ 30 0 And C, the decarboxylation reaction time is 1-9 h.
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