CN111233604B - Method for preparing alkane by decarboxylation of fatty acid under photocatalysis - Google Patents
Method for preparing alkane by decarboxylation of fatty acid under photocatalysis Download PDFInfo
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Abstract
The invention relates to a method for preparing alkane by decarboxylation of fatty acid under photocatalysis. The method prepares the alkane by the photocatalytic decarboxylation of different fatty acids in the presence of hydrogen, a catalyst and a solvent. The catalyst used is titanium dioxide and titanium dioxide modified by metal surface. The reaction process is as follows: mixing fatty acid, solvent and catalyst, placing them into quartz reactor, replacing the atmosphere in the reactor with hydrogen gas, sealing, stirring, and making reaction under the irradiation of external light source. The method can realize the high-efficiency conversion of fatty acid under the mild condition of room temperature (15-40 ℃) and low hydrogen pressure (less than or equal to 0.5 MPa), and the yield of alkane can reach 94 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 oil and aviation kerosene.
Description
Technical Field
The invention relates to a preparation method of a hydrocarbon compound, in particular to a method for preparing alkane by decarboxylation of fatty acid under photocatalysis.
Background
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. Among them, the conversion of renewable biomass resources into liquid fuels has become a research hotspot in the energy field.
In biomass resources, fatty acid is considered to be an ideal raw material for preparing renewable alkane fuel due to the characteristics of long carbon chain structure, low price, inedibility, easy obtaining and the like. 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. Catalytic decarboxylation can avoid the use of hydrogen, but compared with hydrodeoxygenation processes, alkane products have lower selectivity and higher reaction temperature. 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 for converting higher fatty acids into alkanes by photocatalytic decarboxylation, the method converts in a nitrogen atmosphere, the alkane yield is low and is only 46%, and the system has no substrate universality and is 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 and the like, and realizes the efficient preparation of long-chain alkane by the decarboxylation of the photocatalytic fatty acid under very mild reaction conditions (room temperature and low-pressure hydrogen). High conversion efficiency can be realized for various saturated and unsaturated fatty acids, and the alkane yield is 55-94%. The catalyst has high activity and good stability, and can be recycled for multiple times through simple separation and cleaning.
The preparation of alkane by the decarboxylation of the fatty acid under the photocatalysis of the invention is realized by the following scheme. Catalyzing fatty acidMixing the solvent and the agent, placing the mixture into a quartz reactor, replacing the atmosphere in the reactor with hydrogen, sealing, stirring, reacting for a certain time at a certain temperature under the irradiation of an external light source, and detecting the product by chromatography, wherein the product is long-chain alkane. Wherein the fatty acid is one or more of caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid and behenic acid; the concentration of the fatty acid in the initial reaction system is 0.01-0.10 mol/L; the catalyst is titanium dioxide and 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 semiconductor oxide modified on the metal surface is one or more of Pt, pd, ru, au, ag, cu and Ni; the loading amount of the metal is 0.1-10.0 wt% (based on the mass of the carrier); the solvent is one or more of water, ethyl acetate, 1,2-dichloroethane, dichloromethane, acetonitrile and trifluorotoluene; the hydrogen pressure is 0.1-0.5MPa; the external light source is one or more of LED (central wavelength 365nm, 18W), xenon lamp (300W) and high-pressure mercury lamp; the reaction temperature is 15-40 ℃, and the reaction time is 0.5-24 h.
Preferably, the method comprises the following steps: the fatty acid is one or more of n-decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid and eicosanoic acid; the concentration of the fatty acid in the initial reaction system is 0.02-0.5mol/L; the catalyst is titanium dioxide and titanium dioxide modified on the surface of metal, wherein the titanium dioxide is TiO 2 -A (anatase phase TiO) 2 )、TiO 2 (P25) one or two; the metal in the titanium dioxide modified on the metal surface is one or more of Pt, pd, ru, au and Ag; the loading amount of the metal is 0.1-5.0 wt% (based on the mass of the carrier); the solvent is one or more of dichloromethane, acetonitrile and trifluorotoluene; the hydrogen pressure is 0.1-0.3 MPa; the external light source is one or two of an LED (with the central wavelength of 365nm, 18W) and a xenon lamp (300W); the reaction temperature is 2The reaction time is 1.0 to 12 hours at the temperature of between 0 and 30 ℃.
The best is as follows: the concentration of the fatty acid in the initial reaction system is 0.03-0.5mol/L; the fatty acid is one or more of dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid and oleic acid; the catalyst is titanium dioxide and titanium dioxide modified on the surface of metal, wherein the titanium dioxide is TiO 2 (P25); the metal in the titanium dioxide modified by the metal surface comprises one or two of Pt and Pd; the loading of the surface-modified metal is 0.5 to 2.0wt% (based on the mass of the support); the solvent is one or two of acetonitrile and benzotrifluoride; the hydrogen pressure is 0.1-0.15MPa; the external light source is an LED (central wavelength 365nm, 18W).
Taking the photocatalytic decarboxylation of dodecanoic acid as an example, the route for generating undecane is shown as formula 1. Under the irradiation of light, the semiconductor is excited to oxidize, and photo-generated electrons and holes are generated. The dodecanoic acid is dissociated and adsorbed on the surface of the titanium dioxide, and then is subjected to decarboxylation by hole oxidation to generate an alkyl radical, and photo-generated electrons can migrate to the loaded metal to reduce protons dissociated from the carboxylic acid. The alkyl radical combines with hydrogen to produce an alkane, and the interaction of the catalyst with the hydrogen facilitates this process. In this process, the amount of hydrogen consumed by the interaction between hydrogen and the catalyst is small.
In the decarboxylation process of the unsaturated fatty acid, due to the interaction between hydrogen and a catalyst, the unsaturated fatty acid can generate a double bond hydrogenation reaction during decarboxylation, so that the generation of double bond attack induced polymerization caused by alkane radicals is reduced to a certain extent. In addition, because the reaction is carried out under the condition of room temperature and low pressure hydrogen, hydrocracking and by-product CO can not occur 2 Hydrogen consumption side reactions such as hydrogenation. Thus, the photocatalytic decarboxylation process is a low hydrogenAnd (4) a consuming process.
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 94 percent;
2. the reaction condition is mild, harsh reaction conditions such as high temperature and high pressure are avoided, and the conversion can be realized at room temperature (15-40 ℃) and low hydrogen pressure (less than or equal to 0.5 MPa);
3. the substrate has wide application range, and different saturated and unsaturated fatty acids can be efficiently converted into alkane products;
4. the hydrogen consumption of the method is low;
5. the catalyst has high activity, good stability, easy separation and repeated recycling.
Drawings
FIG. 1 is a gas-mass spectrum of the product of example 1, wherein FIG. 1 (a) is a chromatogram and FIG. 1 (b) is a mass spectrum of the product with a retention time of 11.4 min;
FIG. 2 is a gas-mass spectrum of the product of example 31, wherein FIG. 2 (a) is a chromatogram and FIG. 2 (b) is a mass spectrum of the product with a retention time of 9.1 min.
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
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube, respectively 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 93%.
Example 2
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pd/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, the atmosphere in the reaction tube was replaced with hydrogen (0.1 MPa), the reaction tube was sealed, stirred, and the reaction temperature was adjustedAnd (3) reacting for 2.0h under the irradiation of an LED (with the central wavelength of 365nm and the central wavelength of 18W) at 25 ℃, detecting a product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of the heptadecane is 81%.
Example 3
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Au/TiO were added to a quartz reaction tube, respectively 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 76%.
Example 4
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Ag/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, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 68%.
Example 5
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Ru/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, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 74%.
Example 6
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Cu/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, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 58%.
Example 7
Acetonitrile (1.5 mL) and octadecanoic acid (0.05 mmol) (concentrated solution) were added to a quartz reaction tubeDegree of 0.033 mol/L) and Ni/TiO 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 63%.
Example 8
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 83%.
Example 9
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ for 5.0h under the irradiation of an LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 56%.
Example 10
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube, respectively 2 (0.1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 4.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 55%.
Example 11
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 83%.
Example 12
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube 2 (2 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 94%.
Example 13
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube 2 (5 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 91%.
Example 14
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 93%.
Example 15
Acetonitrile 1.5mL, octadecanoic acid 0.02mmol (concentration 0.013 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 1.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 88%.
Example 16
Acetonitrile 1.5mL, octadecanoic acid 0.15mmol (concentration 0.10 mol/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 (0.1 MPa), the reaction tube was sealed and stirred at a reaction temperature of 25 ℃ in an LED (center wavelength)365nm, 18W) for 8.0h, detecting the product by chromatography, wherein the mass spectrogram of the product is consistent with the standard spectrogram, and the yield of the heptadecane is 88%.
Example 17
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube, respectively 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.3 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 93%.
Example 18
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.5 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 94%.
Example 19
In a quartz reaction tube, ethyl acetate 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 56%.
Example 20
1,2-dichloroethane 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 60%.
Example 21
Into a quartz reaction tube, 1.5mL of methylene chloride and 0.05mmol (concentrated) of octadecanoic acid were addedDegree of 0.033 mol/L) and Pt/TiO 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 63%.
Example 22
Into a quartz reaction tube, 1.5mL of trifluorotoluene, 0.05mmol (concentration: 0.033 mol/L) of octadecanoic acid and Pt/TiO were added 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 72%.
Example 23
Acetonitrile 1.5mL, octadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 40 ℃ for 0.5h under the irradiation of a high-pressure mercury lamp, and detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 76%.
Example 24
Into a 100mL Schlenk reaction flask, 30.0mL of acetonitrile, 1.0mmol (concentration: 0.033 mol/L) of octadecanoic acid and Pt/TiO were added 2 (1 wt%) 200mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), stirring, reacting at 40 ℃ for 9.0h under the irradiation of a xenon lamp (300W), continuously and slowly introducing hydrogen to purge in the reaction process, detecting the product by chromatography after the reaction, wherein the mass spectrogram of the product is consistent with the standard spectrogram, and the yield of heptadecane is 80%.
Example 25
Into a 100mL Schlenk reaction flask, 30.0mL of acetonitrile, 1.0mmol (concentration: 0.033 mol/L) of octadecanoic acid and Pt/TiO were added 2 200mg of-A (1 wt%), replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), stirring, reacting at 40 ℃ for 12.0h under the irradiation of a xenon lamp (300W), continuously and slowly introducing hydrogen to purge in the reaction process, detecting the product by chromatography after the reaction, and obtaining a mass spectrogram of the productThe heptadecane yield was 71% in accordance with the standard spectrum.
Example 26
Acetonitrile 1.5mL, n-octanoic acid 0.10mmol (concentration 0.067 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of the n-heptane is 81%.
Example 27
In a quartz reaction tube, acetonitrile 1.5mL, n-decanoic acid 0.075mmol (concentration of 0.05 mol/L) and Pt/TiO were added 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of the n-nonane is 86%.
Example 28
Into a quartz reaction tube, acetonitrile 1.5mL, dodecanoic acid 0.075mmol (concentration of 0.05 mol/L) and Pt/TiO were added 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of undecane is 93%.
Example 29
Acetonitrile (1.5 mL), tetradecanoic acid (0.05 mmol, concentration: 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of tridecane is 91%.
Example 30
Acetonitrile 1.5mL, pentadecanoic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube 2 (1 wt%) 10mg, and the atmosphere in the reaction tube was replaced with hydrogen (0.1)MPa), sealing, stirring, reacting at 25 ℃ for 2.0h under the irradiation of an LED (central wavelength 365nm, 18W), detecting a product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of tetradecane is 91%.
Example 31
Acetonitrile 1.5mL, hexadecanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of pentadecane is 92%.
Example 32
Acetonitrile 1.5mL, eicosanoic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 ℃ under the irradiation of an LED (central wavelength 365nm, 18W) for 2.0h, detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of the nonadecane is 93%.
Example 33
Acetonitrile 1.5mL, behenic acid 0.05mmol (concentration 0.033 mol/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, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heneicosane is 91%.
Example 34
Acetonitrile 1.5mL, oleic acid 0.05mmol (concentration 0.033 mol/L) and Pt/TiO were added to a quartz reaction tube, respectively 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 90%.
Example 35
In the quartz reaction tube, the reaction tube is provided with a quartz reaction tube,adding acetonitrile 1.5mL, linoleic acid 0.05mmol (concentration is 0.033 mol/L) and Pt/TiO respectively 2 (1 wt%) 10mg, replacing the atmosphere in the reaction tube with hydrogen (0.1 MPa), sealing, stirring, reacting at 25 deg.C for 2.0h under the irradiation of LED (central wavelength 365nm, 18W), detecting the product by chromatography, wherein the mass spectrum of the product is consistent with the standard spectrum, and the yield of heptadecane is 70%.
Claims (4)
1. A method for preparing alkane by decarboxylation of fatty acid under photocatalysis 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 reactor, and reacting the reactor under the irradiation of an external light source;
the catalyst is titanium dioxide and titanium dioxide modified on the surface of metal;
the hydrogen pressure is 0.1-0.5MPa;
the reaction temperature is 15 deg.C 0 C ~ 40 0 And C, the reaction time is 0.5 h-24 h.
2. The method of claim 1, wherein:
the fatty acid is one or more of caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid and behenic acid;
the concentration of the fatty acid in the initial reaction system is 0.01-0.10 mol/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 by the metal surface is one or more of Pt, pd, ru, au, ag, cu and Ni; the loading amount of the metal based on the mass of the carrier is 0.1-10.0 wt%;
the solvent is one or more of water, ethyl acetate, 1,2-dichloroethane, dichloromethane, acetonitrile and trifluorotoluene;
the external light source is 18W LED with center wavelength of 365nm, 300W xenon lamp or high-pressure mercury lamp.
3. A method according to claim 1 or 2, characterized in that:
the fatty acid is one or more of n-decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid and eicosanoic acid;
the concentration of the fatty acid in the initial reaction system is 0.02-0.5mol/L;
the catalyst is titanium dioxide and 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, au and Ag; 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 external light source is an 18W LED, and the center wavelength of the external light source is one or two of 365nm and 300W xenon lamps;
the reaction temperature is 20 DEG C 0 C ~ 30 0 And C, the reaction time is 1.0 h-12 h.
4. A method according to claim 3, characterized by:
the fatty acid is one or more of dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid and oleic acid;
the concentration of the fatty acid in the initial reaction system is 0.03-0.5mol/L;
the catalyst is titanium dioxide and 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 0.1-0.15MPa;
the additional light source is an 18W LED, and the center wavelength of the additional light source is 365 nm.
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| CN108067237A (en) * | 2017-11-21 | 2018-05-25 | 浙江大学 | A kind of catalyst and its application that long chain alkane is prepared for unsaturated fat acid decarboxylation |
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| CN105130738A (en) * | 2015-07-23 | 2015-12-09 | 厦门大学 | Method of preparing alkanes through decarbonylation of fatty acid |
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