CN113004953B - Method for preparing biological aviation fuel by using coconut oil - Google Patents
Method for preparing biological aviation fuel by using coconut oil Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a method for preparing biological aviation fuel by coconut oil, which comprises the steps of taking coconut pure oil as a raw material, firstly mixing the coconut pure oil with diethylene glycol monobutyl ether, then adding the mixture into a high-flux microwave reactor, and then adding a modified solid catalyst and methanol for esterification reaction; transferring the mixture into a hydrogenation reaction device, replenishing the modified solid catalyst for the first time, and continuously introducing hydrogen to perform hydrodeoxygenation reaction; transferring to obtain an isomerization reaction device, adding the modified solid catalyst for the second time, and continuously introducing hydrogen to perform an isomerization reaction; then distilling, collecting the distillate between 140 ℃ and 300 ℃, and finally transferring the distillate to a refined filtering device for cleaning treatment. The biological aviation fuel provided by the invention does not contain sulfur and aromatic hydrocarbon, can be directly used as aviation kerosene and high-quality diesel oil, and has the advantages of good thermal oxidation stability, good low-temperature performance, high cleanliness and environmental friendliness.
Description
Technical Field
The invention relates to a method for preparing biological aviation fuel by using coconut oil, belonging to the technical field of biological aviation fuel.
Background
With the rising of international oil prices, the increasing concern on the environment and the consumption of existing petroleum resources, all major airlines also vigorously develop novel biological aviation fuels, wherein the raw materials with development prospects are jatropha oil, rapeseed oil, camelina oil, microalgae oil and the like. Aviation fuels must meet very stringent international standards, with chemical compositions mainly of hydrocarbons with carbon chain lengths in the range C8-C16, mainly alkanes, cycloalkanes and aromatics and small amounts of olefins, with strict limits on the content of aromatics and olefins. At present, the preparation method of the biological aviation fuel which is researched more abroad mainly comprises a two-stage hydrogenation process, so that fatty acid and triglyceride in raw oil are converted into hydrocarbon components with smaller molecules, thereby obtaining the biological aviation fuel.
Coconut meat and coconut water are contained in coconut of coconut palm family, the coconut meat contains 60-65% of coconut oil, the oil content is extremely high, the coconut meat is an important tropical woody oil crop and has extremely high economic value, the coconut oil contains 20% of free fatty acid, 2% of linoleic acid, 7% of palmitic acid, 9% of caprylic acid, 5% of cerotic acid, 10% of capric acid, 2% of oleic acid and 45% of lauric acid, and the coconut oil contains more straight chain or branched chain alkane olefin of which the carbon chain is a medium chain (C8-C12). Therefore, the coconut oil serving as the biological aviation fuel raw material has great development potential and is an important way for reducing carbon emission and realizing the goal of green sustainable development in the aviation industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing biological aviation fuel by using coconut oil, the biological aviation fuel does not contain sulfur and aromatic hydrocarbon, can be directly used as aviation kerosene and high-quality diesel oil, and has the advantages of good thermal oxidation stability, good low-temperature performance, high cleanliness and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for preparing biological aviation fuel by using coconut oil comprises the following steps:
s1, esterification: firstly, adding pure coconut oil into a solvent I to be dissolved and uniformly mixed, transferring the mixture to a high-flux microwave reaction device, adding a modified solid catalyst and methanol, stirring the mixture for esterification reaction at the stirring speed of 350-750 r/min and the microwave power of 250-600W at the microwave temperature of 45-65 ℃ for 120-180 min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, supplementing a modified solid catalyst for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 1.2-6.2 MPa, the reaction temperature is 175-365 ℃, and the reaction time is 180-260 min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, supplementing a modified solid catalyst for the second time, continuously introducing hydrogen into the liquid, and carrying out an isomerization reaction at a hydrogen pressure of 1.5-5.5 MPa, a reaction temperature of 185-330 ℃ and a reaction time of 180-260 min to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
The modified solid catalyst is prepared from a carrier zeolite molecular sieve and an active component of ferric oxide-silicon oxide-copper sulfate.
Preferably, the zeolite molecular sieve is one of a Y-type zeolite molecular sieve, a ZSM-5 zeolite molecular sieve or a ZSM-11 zeolite molecular sieve.
Preferably, the modified solid catalyst is prepared by the steps of:
(1) adding a zeolite molecular sieve and polyethylene glycol into an aqueous solution containing silica sol, stirring for 3-6 h at the rotating speed of 1500-2500 r/min, adding ferric oxide, heating to 45-65 ℃, continuing stirring for 15-20 h, drying, and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring for 1.5-3 h at the speed of 800-1200 r/min to obtain a transparent solution B;
(3) and (3) soaking the solid A in the transparent solution B, stirring for 2-3 h at 300-500 r/min, drying at 45-60 ℃, and calcining at 490-530 ℃ to obtain the modified solid catalyst.
Preferably, the modified solid catalyst takes the mass of the zeolite molecular sieve as a reference, the content of the ferric oxide is 3-14.8% of the mass of the zeolite molecular sieve, the content of the copper sulfate is 0.8-5.6% of the mass of the zeolite molecular sieve, and the content of the silicon oxide is 0.4-10.5% of the mass of the zeolite molecular sieve.
In the step S1, the solvent I is diethylene glycol monobutyl ether, and the weight of the diethylene glycol monobutyl ether is 3.5-11.5 times of that of the coconut pure oil.
Wherein, in step S1, the weight ratio of coconut pure oil to methanol is 1: 0.22-0.44.
Wherein, in step S1, the weight of the modified solid catalyst is 0.05-0.26% of the weight of the coconut pure oil.
In step S2, the weight of the modified solid catalyst added for the first time is 0.008-0.037% of the weight of the pure coconut oil.
In step S3, the weight of the modified solid catalyst added for the second time is 0.005-0.023% of the weight of the pure coconut oil.
The invention has the beneficial effects that: the method for preparing the biological aviation fuel by using the coconut oil has high alkane yield, and can be directly used as aviation kerosene and high-quality diesel oil; the biological aviation fuel does not contain sulfur and aromatic hydrocarbon, has good thermal oxidation stability, good low-temperature performance, high cleanliness and environmental protection; the modified solid catalyst has excellent catalytic effect on the preparation of the biological aviation fuel by the coconut oil, improves the conversion rate of the reaction and the selectivity of a target product, and has good quality of the product; the modified solid catalyst is prepared by taking one of a Y-type zeolite molecular sieve, a ZSM-5 zeolite molecular sieve or a ZSM-11 zeolite molecular sieve as a carrier and ferric oxide-silicon oxide-copper sulfate as an active component, can be continuously used in esterification reaction, hydrodeoxygenation and isomerization reaction processes, and has high catalyst utilization rate.
Detailed Description
In order to more clearly and completely illustrate the present invention, the following examples are given by way of illustration of the present invention, and are not intended to limit the present invention.
Example 1 preparation of modified solid catalyst
The preparation method of the modified solid catalyst comprises the following steps:
(1) adding 1.5g of Y-type zeolite molecular sieve and 0.035g of polyethylene glycol into an aqueous solution containing silica sol, wherein the content of silicon oxide is 0.4% of the mass of the zeolite molecular sieve, stirring for 3h at the rotating speed of 2500r/min, adding ferric oxide, wherein the content of the ferric oxide is 3% of the mass of the zeolite molecular sieve, heating to 65 ℃, continuing stirring for 20h, drying and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring at 1200r/min for 1.5h, wherein the content of copper sulfate is 0.8% of the mass of the zeolite molecular sieve, to obtain transparent solution B;
(3) and (3) soaking the solid A in the transparent solution B, stirring for 2h at 500r/min, drying at 60 ℃, and calcining at 530 ℃ to obtain the modified solid catalyst marked with the symbol (i).
Example 2 preparation of modified solid catalyst
The preparation method of the modified solid catalyst comprises the following steps:
(1) adding 1g of ZSM-5 zeolite molecular sieve and 0.03g of polyethylene glycol into an aqueous solution containing silica sol, wherein the content of silicon oxide is 5% of the mass of the zeolite molecular sieve, stirring for 5 hours at a rotating speed of 2000r/min, adding ferric oxide, wherein the content of the ferric oxide is 9% of the mass of the zeolite molecular sieve, heating to 55 ℃, continuing stirring for 18 hours, and then drying and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring at 1000r/min for 2h, wherein the content of copper sulfate is 3% of the mass of the zeolite molecular sieve, to obtain transparent solution B;
(3) and (3) soaking the solid A in the transparent solution B, stirring for 2.5h at 400r/min, drying at 50 ℃, and calcining at 510 ℃ to obtain a modified solid catalyst marked with a symbol (II).
Example 3 preparation of modified solid catalyst
The preparation of the modified solid catalyst comprises the following steps:
(1) adding 0.8g of ZSM-11 zeolite molecular sieve and 0.028g of polyethylene glycol into an aqueous solution containing silica sol, wherein the content of silicon oxide is 10.5 percent of the mass of the zeolite molecular sieve, stirring for 6 hours at the rotating speed of 1500r/min, adding ferric oxide, wherein the content of the ferric oxide is 14.8 percent of the mass of the zeolite molecular sieve, heating to 45 ℃, continuously stirring for 15 hours, and then drying and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring at 800r/min for 3h, wherein the content of copper sulfate is 5.6% of the mass of the zeolite molecular sieve, to obtain transparent solution B;
(3) and (3) soaking the solid A in the transparent solution B, stirring for 2-3 h at 300r/min, drying at 45 ℃, and calcining at 490 ℃ to obtain the modified solid catalyst marked by the symbol (c).
The modified solid catalysts prepared in the above examples 1, 2 and 3 were marked with the symbols (i), (ii) and (iii), and then used in the examples 4 to 8, respectively, to prepare bio-aviation fuels.
Example 4 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, adding 100g of coconut pure oil into 350g of diethylene glycol monobutyl ether to dissolve and mix uniformly, transferring the coconut pure oil into a high-flux microwave reaction device, adding 0.05g of modified solid catalyst marked as I and 22g of methanol, stirring the mixture to perform esterification reaction, wherein the stirring speed is 350r/min, the microwave power is 250W, the microwave temperature is 45 ℃, and the reaction time is 180min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.008g of a first-time modified solid catalyst, continuously introducing hydrogen into the liquid, and carrying out a hydrodeoxygenation reaction, wherein the hydrogen pressure is 1.2MPa, the reaction temperature is 175 ℃, and the reaction time is 260min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B into an isomerization reaction device, supplementing 0.005g of modified solid catalyst marked with the symbol I for the second time, continuously introducing hydrogen into the liquid, and carrying out isomerization reaction under the hydrogen pressure of 1.5MPa at the reaction temperature of 185 ℃ for 260min to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Example 5 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, adding 100g of coconut pure oil into 750g of diethylene glycol monobutyl ether to dissolve and mix uniformly, transferring the coconut pure oil into a high-flux microwave reaction device, adding 0.16g of modified solid catalyst marked with the second symbol and 33g of methanol, stirring the mixture to perform esterification reaction, wherein the stirring speed is 550r/min, the microwave power is 450W, the microwave temperature is 55 ℃, and the reaction time is 150min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.023g of a modified solid catalyst marked with a second mark for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 3.5MPa, the reaction temperature is 270 ℃, and the reaction time is 220min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, adding 0.014g of modified solid catalyst marked with the second sign II for the second time, continuously introducing hydrogen into the liquid for isomerization reaction, wherein the pressure of the hydrogen is 3.5MPa, the reaction temperature is 250 ℃, and the reaction time is 220min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Example 6 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, adding 100g of coconut pure oil into 1150g of diethylene glycol monobutyl ether, dissolving and uniformly mixing, transferring the coconut pure oil into a high-flux microwave reaction device, adding 0.26g of modified solid catalyst marked with the third sign and 44g of methanol, stirring the mixture for esterification reaction at the stirring speed of 750r/min and the microwave power of 600W at the microwave temperature of 65 ℃ for 120min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.037g of modified solid catalyst marked with the third symbol for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 6.2MPa, the reaction temperature is 365 ℃, and the reaction time is 180min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, supplementing 0.023g of the modified solid catalyst marked with the third symbol for the second time, continuously introducing hydrogen into the liquid to perform an isomerization reaction, wherein the pressure of the hydrogen is 5.5MPa, the reaction temperature is 330 ℃, and the reaction time is 180min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Example 7 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, adding 150g of coconut pure oil into 1350g of diethylene glycol monobutyl ether, dissolving and uniformly mixing, then transferring the coconut pure oil into a high-flux microwave reaction device, adding 0.3g of modified solid catalyst marked with a character I and 55g of methanol, stirring for esterification reaction, wherein the stirring speed is 600r/min, the microwave power is 500W, the microwave temperature is 60 ℃, and the reaction time is 140min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.015g of modified solid catalyst marked with the reference number I for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 5MPa, the reaction temperature is 300 ℃, and the reaction time is 200min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, adding 0.015g of modified solid catalyst marked with the symbol I for the second time, continuously introducing hydrogen into the liquid, and carrying out an isomerization reaction, wherein the pressure of the hydrogen is 5MPa, the reaction temperature is 300 ℃, and the reaction time is 200min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Example 8 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, 200g of coconut pure oil is added into 1000g of diethylene glycol monobutyl ether to be dissolved and uniformly mixed, then the mixture is transferred into a high-flux microwave reaction device, 0.17g of modified solid catalyst marked as I and 56g of methanol are added, and the mixture is stirred for esterification reaction, wherein the stirring speed is 450r/min, the microwave power is 300W, the microwave temperature is 50 ℃, and the reaction time is 160min, so that a liquid mixture A is obtained;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.04g of modified solid catalyst marked with the number I for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 2.5MPa, the reaction temperature is 220 ℃, and the reaction time is 240min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, adding 0.038g of the modified solid catalyst marked with the reference number I for the second time, continuously introducing hydrogen into the liquid for isomerization reaction, wherein the hydrogen pressure is 2.5MPa, the reaction temperature is 215 ℃, and the reaction time is 240min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Comparative example 1 preparation of modified solid catalyst
The preparation method of the modified solid catalyst comprises the following steps:
(1) adding 1g of A-type zeolite molecular sieve and 0.03g of polyethylene glycol into an aqueous solution containing silica sol, wherein the content of silicon oxide is 5% of the mass of the zeolite molecular sieve, stirring for 5h at the rotating speed of 2000r/min, adding ferric oxide, wherein the content of the ferric oxide is 9% of the mass of the zeolite molecular sieve, heating to 55 ℃, continuing stirring for 18h, and then drying and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring at 1000r/min for 2h, wherein the content of copper sulfate is 3% of the mass of the zeolite molecular sieve, to obtain transparent solution B;
(3) the solid A is dipped in the transparent solution B, stirred for 2.5h at 400r/min, dried at 50 ℃ and calcined at 510 ℃ to obtain the modified solid catalyst which is marked as the symbol (r).
The modified solid catalyst prepared in the comparative example 1 is correspondingly marked with a symbol (r) and is used for preparing the biological aviation fuel in the comparative example 2.
Comparative example 2 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, adding 100g of coconut pure oil into 800g of diethylene glycol monobutyl ether to dissolve and mix uniformly, transferring the coconut pure oil into a high-flux microwave reaction device, adding 0.18g of modified solid catalyst marked with a fourth mark and 35g of methanol, stirring the mixture to perform esterification reaction, wherein the stirring speed is 550r/min, the microwave power is 450W, the microwave temperature is 55 ℃, and the reaction time is 160min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, adding 0.02g of modified solid catalyst marked with the fourth label for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 280 ℃, and the reaction time is 200min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, adding 0.016g of the modified solid catalyst marked with the fourth mark for the second time, continuously introducing hydrogen into the liquid for isomerization reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 270 ℃, and the reaction time is 200min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Comparative example 3 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, esterification: firstly, mutually dissolving 100g of coconut pure oil and 35g of methanol, adding concentrated sulfuric acid as a catalyst, stirring for esterification reaction at the stirring speed of 550r/min and the reaction temperature of 55 ℃ for 160min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device filled with zeolite loaded nickel, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 280 ℃, and the reaction time is 200min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device filled with zeolite-loaded platinum, continuously introducing hydrogen into the liquid, and carrying out isomerization reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 270 ℃, and the reaction time is 200min, so as to obtain a liquid mixture C;
s4, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
Comparative example 4 preparation of a biological aviation Fuel
The preparation method of the biological aviation fuel comprises the following steps:
s1, hydrodeoxygenation reaction: adding 100g of coconut pure oil into a hydrogenation reaction device filled with zeolite-loaded nickel, continuously introducing hydrogen into liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 280 ℃, and the reaction time is 200min, so as to obtain a liquid mixture B;
s2, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device filled with zeolite-loaded platinum, continuously introducing hydrogen into the liquid, and carrying out isomerization reaction, wherein the hydrogen pressure is 4MPa, the reaction temperature is 270 ℃, and the reaction time is 200min, so as to obtain a liquid mixture C;
s3, distillation and refining: and transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment, and obtaining the biological aviation fuel.
The liquid mixture A, the liquid mixture B, the liquid mixture C and the biological aviation fuel generated in the process of preparing the biological aviation fuel by the above examples 4-8, the comparative examples 2, the comparative examples 3 and the comparative examples 4 are subjected to quantitative analysis by gas chromatography, and the conversion rate of coconut pure oil in the esterification reaction, the conversion rate of esters in the hydrodeoxygenation reaction and the isomerization reaction and the selectivity of hydrocarbon products and the content of C8-C16 alkane in the biological aviation fuel are analyzed, and the results are shown in the following table:
the results show that the method for preparing the biological aviation fuel by using the coconut oil has high alkane yield, namely the mixed alkane fuel of C8-C14 in the biological aviation fuel prepared in the embodiment 4-8 can be directly used as aviation kerosene and high-quality diesel oil; the modified solid catalyst has excellent catalytic effect on the preparation of the biological aviation fuel by the coconut oil, improves the conversion rate of the reaction and the selectivity of a target product, and has good quality of the product; the modified solid catalyst can be continuously used in the processes of esterification, hydrodeoxygenation and isomerization, and the utilization rate of the catalyst is high; the biological aviation fuel provided by the invention does not contain sulfur and aromatic hydrocarbon, and has the advantages of good thermal oxidation stability, good low-temperature performance, high cleanliness and environmental friendliness.
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention is described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the present invention can be modified or replaced with equivalents without departing from the spirit and scope of the present invention, and all modifications or partial replacements should be covered in the claims of the present invention.
Claims (8)
1. A method for preparing biological aviation fuel by using coconut oil is characterized by comprising the following steps:
s1, esterification: firstly, adding pure coconut oil into a solvent I to be dissolved and uniformly mixed, transferring the mixture to a high-flux microwave reaction device, adding a modified solid catalyst and methanol, stirring the mixture for esterification reaction at the stirring speed of 350-750 r/min and the microwave power of 250-600W at the microwave temperature of 45-65 ℃ for 120-180 min to obtain a liquid mixture A;
s2, hydrodeoxygenation reaction: cooling the liquid mixture A to 30-35 ℃, transferring the liquid mixture A to a hydrogenation reaction device, supplementing a modified solid catalyst for the first time, continuously introducing hydrogen into the liquid, and carrying out hydrodeoxygenation reaction, wherein the hydrogen pressure is 1.2-6.2 MPa, the reaction temperature is 175-365 ℃, and the reaction time is 180-260 min, so as to obtain a liquid mixture B;
s3, isomerization reaction: cooling the liquid mixture B to 40-45 ℃, transferring the liquid mixture B to an isomerization reaction device, supplementing a modified solid catalyst for the second time, continuously introducing hydrogen into the liquid, and carrying out an isomerization reaction at a hydrogen pressure of 1.5-5.5 MPa, a reaction temperature of 185-330 ℃ and a reaction time of 180-260 min to obtain a liquid mixture C;
s4, distillation and refining: transferring the liquid mixture C into a distillation device for distillation while the liquid mixture C is hot, collecting fractions at the temperature of 140-300 ℃, transferring the collected fractions to a refining and filtering device for cleaning treatment to obtain the biological aviation fuel;
the modified solid catalyst is prepared from a carrier zeolite molecular sieve and an active component of ferric oxide-silicon oxide-copper sulfate;
the zeolite molecular sieve is one of a Y-type zeolite molecular sieve, a ZSM-5 zeolite molecular sieve or a ZSM-11 zeolite molecular sieve.
2. The method for preparing biological aviation fuel by using coconut oil as claimed in claim 1, wherein the modified solid catalyst is prepared by the following steps:
(1) adding a zeolite molecular sieve and polyethylene glycol into an aqueous solution containing silica sol, stirring for 3-6 h at the rotating speed of 1500-2500 r/min, adding ferric oxide, heating to 45-65 ℃, continuing stirring for 15-20 h, drying, and roasting to obtain a solid A;
(2) mixing copper sulfate, water and ethanol, and stirring for 1.5-3 hours at 800-1200 r/min to obtain a transparent solution B;
(3) and (3) soaking the solid A in the transparent solution B, stirring for 2-3 h at 300-500 r/min, drying at 45-60 ℃, and calcining at 490-530 ℃ to obtain the modified solid catalyst.
3. The method for preparing the biological aviation fuel by using the coconut oil as the claim 1, wherein the modified solid catalyst is based on the mass of the zeolite molecular sieve, the content of the ferric oxide is 3-14.8% of the mass of the zeolite molecular sieve, the content of the copper sulfate is 0.8-5.6% of the mass of the zeolite molecular sieve, and the content of the silicon oxide is 0.4-10.5% of the mass of the zeolite molecular sieve.
4. The method for preparing biological aviation fuel by using coconut oil as claimed in claim 1, wherein in step S1, solvent I is diethylene glycol monobutyl ether, the weight of which is 3.5-11.5 times of that of coconut pure oil.
5. The method for preparing the biological aviation fuel by using the coconut oil as claimed in claim 1, wherein in the step S1, the weight ratio of the coconut pure oil to the methanol is 1: 0.22-0.44.
6. The method for preparing biological aviation fuel by using coconut oil as claimed in claim 1, wherein in step S1, the weight of the modified solid catalyst is 0.05-0.26% of the weight of the coconut pure oil.
7. The method for preparing the biological aviation fuel by using the coconut oil as claimed in claim 1, wherein in step S2, the weight of the modified solid catalyst is supplemented for the first time and is 0.008-0.037% of the weight of the pure coconut oil.
8. The method for preparing biological aviation fuel by using coconut oil as claimed in claim 1, wherein in step S3, the modified solid catalyst is supplemented for the second time, and the weight of the modified solid catalyst is 0.005-0.023% of the weight of the pure coconut oil.
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| CN104711012A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene |
| CN106492873A (en) * | 2016-11-22 | 2017-03-15 | 新奥生态环境治理有限公司 | A kind of catalyst for bio oil upgrading |
| CN107987868A (en) * | 2016-10-26 | 2018-05-04 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by stepwise deoxygenation of grease |
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| US8039682B2 (en) * | 2008-03-17 | 2011-10-18 | Uop Llc | Production of aviation fuel from renewable feedstocks |
| EP2655569A2 (en) * | 2010-12-20 | 2013-10-30 | Shell Oil Company | Process to produce biofuels from biomass |
| TW201347845A (en) * | 2012-03-13 | 2013-12-01 | Daiki Axis Co Ltd | Solid acid catalyst, method for manufacturing same, and method for manufacturing a fatty acid alkyl ester using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104711012A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Applications of hydrodeoxygenation catalyst in synthesis of renewable diesel fuel or aviation kerosene |
| CN107987868A (en) * | 2016-10-26 | 2018-05-04 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by stepwise deoxygenation of grease |
| CN106492873A (en) * | 2016-11-22 | 2017-03-15 | 新奥生态环境治理有限公司 | A kind of catalyst for bio oil upgrading |
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