CN109456838B - Method for producing biodiesel and glycerol triacetate - Google Patents
Method for producing biodiesel and glycerol triacetate Download PDFInfo
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
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Abstract
A method for producing biodiesel and glycerol triacetate comprises mixing oil, acetic acid and catalyst, preparing into catalytic reaction system, reacting at 120-250 deg.C for 0.2-10 hr, separating reaction product after reaction to obtain long-chain fatty acid and glycerol triacetate, and esterifying the separated long-chain fatty acid with methanol to obtain long-chain fatty acid methyl ester, i.e. biodiesel. The invention has the advantages of low production cost and no pollution.
Description
Technical Field
The invention belongs to the field of renewable resources, and relates to a method for producing biodiesel and glycerol triacetate.
Technical Field
The biodiesel is essentially an ester compound formed by long-chain fatty acid with carbon number of 16-22 and methanol or ethanol, which is obtained by catalytic ester exchange of waste grease and methanol or ethanol. Biodiesel is a typical green energy source, has the advantages of good environmental protection performance, good engine starting performance, good fuel performance and the like, and has wide raw material sources and reproducibility. The yield thereof rapidly increases on a global scale, and according to statistical data published by the global renewable energy network, the global biodiesel yield increases from 70.40 ten thousand tons in 2000 to 2648.80 ten thousand tons in 2015, and the annual composite growth rate is 27.36%. The biodiesel market in China really enters a vigorous development period from 2006. The by-product of 1 ton of glycerin is produced when 9 tons of biodiesel are produced by animal and vegetable oil, and the catalytic conversion of glycerin becomes an important process for relieving the cost pressure of biodiesel.
The triacetyl glycerine is an important chemical solvent, reagent and perfume fixative, the current production method is mainly obtained by catalytic esterification of glycerin, acetic acid and acetic anhydride, and also is prepared by dehydrochlorination of trichloroethane and acetic acid or glycerin and acetyl chloride, the production cost is high on the whole, and the problem of discharge of small-molecule toxic substances cannot be avoided in the whole production process.
Disclosure of Invention
The invention aims to provide a method for producing biodiesel and glycerol triacetate economically and efficiently, which has low production cost and no pollution.
The conventional preparation method of biodiesel and glycerol triacetate is that grease is catalyzed to perform ester exchange to generate long-chain fatty acid methyl ester and glycerol, the glycerol reacts with acetic acid to generate a mixture of glycerol monoacetate and glycerol diacetate, and the mixture of the glycerol monoacetate and the glycerol diacetate reacts with acetic anhydride to generate the glycerol triacetate. The key point of the process is that the esterification reaction of glycerol and acetic acid for producing glycerol triacetate is not completely carried out, high-cost acetic anhydride is needed to participate in the reaction, the process is complex, and the operation cost is high. This problem has two chemically essential causes: firstly, glycerol and acetic acid are subjected to dehydration esterification to form a reversible reaction, and the generated water seriously influences the reaction progress, so that the water generated in the reaction process is often required to be separated from the system in time, which is a great challenge for an acetic acid system completely miscible with water; secondly, the radius of the hydrogen atom on the hydroxyl group of the trifunctional molecule such as glycerol is far smaller than that of the acetyl group, and the hydrogen atom on the hydroxyl group of the glycerol molecule is gradually replaced by the acetyl group, so that the reaction steric effect is rapidly increased, the glycerol is difficult to be completely esterified with acetic acid through the conventional process, the reaction products are mainly mono-acetin and di-acetin, and a large amount of acetic anhydride is required to be added in order to improve the yield of the triacetin. Because the acetic anhydride participates in the reaction process and does not produce water, the limitation of reversible reaction is greatly relieved. However, acetic anhydride is usually prepared by cracking acetic acid at high temperature to form ketene, and ketene is synthesized through a series of processes, so that the cost of raw materials is high, and the process is complex.
The invention utilizes the direct reaction of animal and vegetable oil and acetic acid under the action of a catalyst to generate long-chain fatty acid and glycerol triacetate, which is an acyl exchange reaction process. The fatty acids in animal and vegetable oil are long-chain fatty acids with 16-22 carbon atoms, and have much larger steric hindrance than acetic acid and much larger corresponding intramolecular tension. Different from the esterification of glycerol to generate glycerol triacetate, the acetyl exchange reaction of animal and vegetable oil is a process of gradually reducing the tension in molecules and a process of gradually reducing the steric hindrance of catalytic reaction, so once acetic acid replaces a long-chain fatty acid to generate monoacetate oil, the further reaction is easier, and by analogy, the generation of glycerol triacetate is an advantageous product of the reaction. In addition, no water is produced during the reaction, and the produced long-chain fatty acid is insoluble in acetic acid and triacetin, so the reaction is not limited by the balance basically. The obtained long-chain fatty acid can be used for obtaining the biodiesel through a conventional methyl esterification process.
The invention specifically comprises the following steps:
(1) fully mixing grease, acetic acid and a catalyst to prepare a catalytic reaction system;
(2) reacting at the temperature of 120 ℃ and 250 ℃ for 0.2-10 hours, and separating reaction products after the reaction is finished to obtain long-chain fatty acid and glycerol triacetate;
(3) the separated long-chain fatty acid and methanol are subjected to esterification reaction to obtain long-chain fatty acid methyl ester, namely the biodiesel.
The grease in the step (1) is an ester compound formed by combining fatty acid and glycerol, and can be one or more of animal grease, vegetable grease and waste grease;
the acetic acid in the step (1) refers to glacial acetic acid or an aqueous solution of acetic acid, wherein the mass percentage concentration of the acetic acid in the aqueous solution of the acetic acid is more than 80%;
the catalyst in the step (1) is an acid-base catalyst, and the best catalyst is an organic acid-base catalyst such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, tri-tert-butyl ammonium hydroxide and the like, and an inorganic acid-base catalyst such as phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, sodium acetate, zinc acetate, potassium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, an acidic molecular sieve, an acidic resin, a basic resin or a heteropoly acid and the like.
The mass ratio of the acetic acid to the grease in the step (1) is 0.2-100: 1.
the mass ratio of the catalyst to the grease in the step (1) is 0.01-1: 1.
the long-chain fatty acid in the step (2) is a fatty acid with 16-22 carbon atoms.
The step (2) of separating the reaction product refers to:
firstly, when the catalyst in the step (1) is in a liquid state, the following process is adopted:
(a) filtering, or standing and layering or centrifugally separating the reaction product to obtain long-chain fatty acid and a mixed solution;
(b) heating the mixed solution to collect acetic acid to obtain a reaction mixture, wherein the mass ratio of the organic solvent to the animal and vegetable oil is 0.01-100: adding an organic solvent into the reaction mixture, uniformly mixing, filtering to obtain an organic solution and a catalyst, and evaporating to remove the organic solvent in the organic solution to obtain the glycerol triacetate.
The organic solvent is diethyl ether, chloroform, toluene or benzene.
Secondly, when the catalyst in the step (1) is a solid, the following process is adopted:
(a) heating the reaction product to 40-80 ℃, and filtering to obtain a solid catalyst and a mixed solution A;
(b) filtering or standing the mixed solution A at 0-35 ℃ for layering to obtain long-chain fatty acid and a mixed solution B;
(c) and distilling the mixed solution B to collect acetic acid and obtain glycerol triacetate.
The esterification reaction of the long-chain fatty acid and the methanol in the step (3) means that the methanol and the long-chain fatty acid react to generate long-chain fatty acid methyl ester under the action of an acid-base catalyst, wherein the acid-base catalyst is phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, aluminum chloride, zinc sulfate, sodium acetate, zinc acetate, potassium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, an acidic molecular sieve, heteropoly acid and the like;
the esterification reaction of the long-chain fatty acid and the methanol in the step (3) means that the reaction time is 10min-10h at the temperature of 140-: 1;
the biodiesel in the step (3) is obtained by the following separation process: for a homogeneous catalysis system, distilling to recover methanol, and filtering or centrifuging the remaining solution to obtain long-chain fatty acid methyl ester and a catalyst; for the catalytic system with the solid catalyst, the solid catalyst is firstly filtered and recovered, and then the methanol is distilled and recovered to obtain the biodiesel.
Compared with the prior art, the invention has the following advantages:
1. firstly, the grease and acetic acid are subjected to acyl exchange reaction to obtain glycerol triacetate, and then long-chain fatty acid is subjected to methyl esterification to obtain the biodiesel.
2. The triacetyl glycerine has high selectivity, and does not contain acetic acid and other esterification products of glycerine.
3. The method can obtain the glyceryl triacetate without using relatively expensive chemical reagents such as acetic anhydride and the like and a complex dehydration process, has the advantages of high efficiency, greenness, economy and the like, and has few byproducts.
4. The yield of the glycerol triacetate is more than 90 percent, and the yield of the biodiesel is more than 90 percent.
Drawings
FIG. 1 is an NMR carbon spectrum of glycerol triacetate.
FIG. 2 is an NMR hydrogen spectrum of glycerol triacetate.
FIG. 3 is a gas chromatogram (peaks 1, 2, 3 for analytical procedures with addition of ethanol, chloroform and internal standard methyl benzoate, peak (21.74) for triacetin).
FIG. 4 is an NMR hydrogen spectrum of stearic acid.
FIG. 5 is an NMR carbon spectrum of stearic acid.
Detailed Description
Example 1
Mixing 1.0g of glyceryl tristearate, 0.01g of phosphotungstic acid and 0.2g of glacial acetic acid, reacting for 10h at 120 ℃, filtering at 60 ℃ after the reaction is finished to obtain phosphotungstic acid insoluble in acetic acid, cooling the filtrate to 40 ℃, filtering precipitated fatty acid solid, distilling the filtrate under reduced pressure, recovering acetic acid, and obtaining the glyceryl triacetate (shown in attached figures 1, 2 and 3), wherein the conversion rate of the glyceryl tristearate is 100% and the molar yield of the glyceryl triacetate is 95% by analysis; adding 0.1g of methanol and 0.005g of phosphotungstic acid into the obtained fatty acid (shown in attached figures 4 and 5), reacting for 2 hours at 140 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the phosphotungstic acid from the liquid phase, filtering and recovering the phosphotungstic acid to obtain the liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 98 percent, and the content is 99.5 percent.
Example 2
Mixing 1.0g of tallow oil, 0.05g of benzenesulfonic acid and 100g of 80% acetic acid aqueous solution by mass percent, reacting for 8 hours at 140 ℃, filtering out precipitated fatty acid solid after the reaction is finished, carrying out reduced pressure distillation on the filtrate, recovering acetic acid, adding 0.01g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the oil to be 100%, and the molar yield of the glycerol triacetate to be 97%; adding 0.4g of methanol and 0.008g of phosphoric acid into the obtained fatty acid, reacting for 10 hours at 150 ℃, then distilling under reduced pressure to remove the methanol, standing and layering the phosphoric acid from the liquid phase to separate out, recovering the phosphoric acid to obtain a liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 96 percent, and the content is 99.2 percent.
Example 3
Mixing 1.0g of lard oil, 0.1g of p-toluenesulfonic acid and 80g of acetic acid aqueous solution with the mass percentage concentration of 90%, reacting for 4 hours at 160 ℃, filtering out precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 0.05g of organic solvent chloroform, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the oil to be 100%, and the molar yield of the glycerol triacetate to be 96%; adding 0.6g of methanol and 0.01g of phosphoric acid into the obtained fatty acid, reacting for 10h at 140 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the phosphoric acid from a liquid phase, filtering and recovering the phosphoric acid to obtain the liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 95 percent, and the content is 99.4 percent.
Example 4
Mixing 1.0g of mutton fat, 0.2g of dodecylbenzene sulfonic acid and 90g of acetic acid aqueous solution with the mass percentage concentration of 85%, reacting for 2 hours at 180 ℃, filtering out precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 0.1g of organic solvent toluene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the fat to be 100%, and obtaining the molar yield of the glycerol triacetate to be 99%; adding 0.8g of methanol and 0.04g of zinc chloride into the obtained fatty acid, reacting for 6 hours at 160 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the zinc chloride from a liquid phase, filtering and recovering the zinc chloride to obtain a liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 96 percent, and the content is 99.6 percent.
Example 5
Mixing 1.0g of palm oil, 0.5g of tri-tert-butyl ammonium hydroxide and 60g of acetic acid aqueous solution with the mass percent concentration of 95%, reacting at 220 ℃ for 0.6h, standing and layering separated fatty acid after the reaction is finished, distilling the liquid phase after the fatty acid is separated under reduced pressure, recovering acetic acid, adding 0.5g of organic solvent, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the grease to be 100%, and obtaining the molar yield of the glycerol triacetate to be 95%; adding 1g of methanol and 0.06g of sulfuric acid into the obtained fatty acid, reacting for 30min at 180 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the sulfuric acid from a liquid phase, filtering and recovering the sulfuric acid to obtain a liquid phase which is a biodiesel product, wherein the molar yield of the fatty acid methyl ester is 95% and the content is 99.0% through chromatographic analysis.
Example 6
Mixing 1.0g of illegal cooking oil, 0.8g of phosphoric acid and 0.4g of glacial acetic acid, reacting for 0.4h at 240 ℃, standing and layering separated fatty acid after the reaction is finished, distilling the liquid phase with the separated fatty acid under reduced pressure, recovering acetic acid, adding 1g of organic solvent methylbenzene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing that the conversion rate of the grease is 100%, and the molar yield of the glycerol triacetate is 96%; adding 1.5g of methanol and 0.08g of phosphotungstic acid into the obtained fatty acid, reacting for 10min at 200 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the phosphotungstic acid from a liquid phase, filtering and recovering the phosphotungstic acid to obtain a liquid phase which is a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 93 percent, and the content is 99.1 percent.
Example 7
Mixing 1.0g of hydrogenated oil, 1.0g of zinc chloride and 80g of acetic acid aqueous solution with the mass percent concentration of 80%, reacting for 0.2h at 250 ℃, filtering out precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 2g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the oil to be 100%, and obtaining the molar yield of the glycerol triacetate to be 98%; adding 2g of methanol and 0.1g of aluminum sulfate into the obtained fatty acid, reacting for 3 hours at 180 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating the aluminum sulfate from a liquid phase, filtering and recovering the aluminum sulfate to obtain the liquid phase as a biodiesel product, and analyzing by a chromatographic method, wherein the molar yield of the fatty acid methyl ester is 95 percent, and the content is 99.2 percent.
Example 8
Mixing 1.0g of glyceryl tristearate, 0.1g of sulfuric acid and 50g of an acetic acid aqueous solution with the mass percentage concentration of 90%, reacting for 8 hours at 120 ℃, filtering precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 5g of an organic solvent methylbenzene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain the glyceryl triacetate, analyzing that the conversion rate of the glyceryl tristearate is 100%, and the molar yield of the glyceryl triacetate is 95%; adding 4g of methanol and 0.01g of aluminum chloride into the obtained fatty acid, reacting for 1h at 150 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the aluminum chloride from a liquid phase, filtering and recovering the aluminum chloride to obtain a liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 96 percent, and the content is 99.4 percent.
Example 9
Mixing 1.0g of mixed grease of tristearin and mutton fat (the mass ratio is 1:1), 0.05g of aluminum sulfate and 40g of acetic acid aqueous solution with the mass percentage concentration of 85%, reacting for 4 hours at 140 ℃, filtering precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 10g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the grease to be 100%, and the molar yield of the glycerol triacetate to be 97%; adding 5g of methanol and 0.02g of zinc sulfate into the obtained fatty acid, reacting for 4 hours at 180 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the zinc sulfate from a liquid phase, filtering and recovering the zinc sulfate to obtain a liquid phase which is a biodiesel product, and performing chromatographic analysis to obtain the fatty acid methyl ester with the molar yield of 95 percent and the content of 99.3 percent.
Example 10
Mixing 1.0g of mixed grease of lard and beef tallow (the mass ratio is 1:3), 0.1g of sodium acetate and 10g of acetic acid aqueous solution with the mass percentage concentration of 95%, reacting at 120 ℃ for 6h, filtering precipitated fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 50g of organic solvent toluene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the grease after the analysis is 100%, and the molar yield of the glycerol triacetate is 95%; adding 6g of methanol and 0.05g of sodium acetate into the obtained fatty acid, reacting for 8 hours at 140 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the sodium acetate from a liquid phase, filtering and recovering the sodium acetate to obtain a liquid phase which is a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 98 percent, and the content is 99.6 percent.
Example 11
Mixing 1.0g of mixed oil of palm oil and hydrogenated oil (the mass ratio is 1:2), 0.2g of zinc acetate and 0.8g of glacial acetic acid, reacting for 8 hours at 120 ℃, standing and layering separated fatty acid after the reaction is finished, distilling the liquid phase after removing the fatty acid under reduced pressure, recovering the acetic acid, adding 80g of organic solvent chloroform, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling and removing the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the oil to be 100%, and the molar yield of the glycerol triacetate to be 97%; adding 8g of methanol and 0.08g of zinc acetate into the obtained fatty acid, reacting for 1.5h at 150 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the zinc acetate from the liquid phase, filtering and recovering the zinc acetate to obtain a liquid phase which is a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 96 percent, and the content is 99.2 percent.
Example 12
Mixing 1.0g of mixed grease of illegal cooking oil and beef tallow (the mass ratio is 1:1), 0.4g of potassium hydroxide and 1g of glacial acetic acid, reacting for 4 hours at 120 ℃, standing and layering separated fatty acid after the reaction is finished, carrying out reduced pressure distillation on a liquid phase after the fatty acid is removed, recovering acetic acid, adding 100g of organic solvent toluene, filtering to obtain an organic solution and a catalyst after the reaction, and distilling to remove the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the grease is 100% and the molar yield of the glycerol triacetate is 98% by analysis; adding 10g of methanol and 0.01g of potassium bisulfate into the obtained fatty acid, reacting for 40min at 160 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the potassium bisulfate from a liquid phase, filtering and recovering the potassium bisulfate to obtain the liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 95 percent, and the content is 99.0 percent.
Example 13
Mixing 1.0g of soybean oil, 0.6g of potassium bisulfate and 40g of acetic acid aqueous solution with the mass percentage concentration of 80%, reacting for 1h at 160 ℃, standing and layering separated fatty acid after the reaction is finished, carrying out reduced pressure distillation on a liquid phase after the fatty acid is removed, recovering acetic acid, adding 20g of organic solvent methylbenzene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the grease to be 100%, and the molar yield of the glycerol triacetate to be 97%; adding 2g of methanol and 0.02g of sodium carbonate into the obtained fatty acid, reacting for 8 hours at 160 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out the sodium carbonate from a liquid phase, filtering and recovering the sodium carbonate to obtain the liquid phase as a biodiesel product, and analyzing by a chromatographic method, wherein the molar yield of the fatty acid methyl ester is 92 percent, and the content is 99.4 percent.
Example 14
Mixing 1.0g of rapeseed oil, 0.02g of sodium carbonate and 2g of glacial acetic acid, reacting for 0.8h at 200 ℃, standing fatty acid separated by layers after the reaction is finished, carrying out reduced pressure distillation on a liquid phase after the fatty acid is removed, recovering acetic acid, adding 10g of organic solvent diethyl ether, filtering to obtain an organic solution and a catalyst after the reaction, and distilling to remove the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the oil is 100% and the molar yield of the glycerol triacetate is 95%; adding 5g of methanol and 0.04g of sodium bicarbonate into the obtained fatty acid, reacting for 10 hours at 150 ℃, then distilling under reduced pressure to remove methanol, simultaneously separating out the sodium bicarbonate from a liquid phase, filtering and recovering the sodium bicarbonate to obtain the liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 94 percent, and the content is 99.3 percent.
Example 15
Mixing 1.0g of peanut oil, 0.04g of sodium hydroxide and 20g of acetic acid aqueous solution with the mass percentage concentration of 90%, reacting for 0.6h at 220 ℃, standing and layering separated fatty acid after the reaction is finished, carrying out vacuum distillation on the liquid phase after the fatty acid is removed, recovering acetic acid, adding 5g of organic solvent methylbenzene, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glycerol triacetate, analyzing the conversion rate of the grease to be 100%, and obtaining the molar yield of the glycerol triacetate to be 95%; adding 6g of methanol and 0.06g of sodium hydroxide into the obtained fatty acid, reacting for 4h at 180 ℃, then distilling under reduced pressure to remove the methanol, simultaneously separating out catalyst solids from a liquid phase, filtering and recovering the catalyst to obtain a liquid phase which is a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 95%, and the content is 99.6%.
Example 16
Mixing 1.0g of lard and soybean mixed oil (the mass ratio is 1:3), 0.06g of zinc chloride and 8g of glacial acetic acid, reacting for 1h at 180 ℃, standing and layering separated fatty acid after the reaction is finished, carrying out vacuum distillation on the liquid phase after the fatty acid is removed, recovering acetic acid, adding 2g of organic solvent chloroform, filtering to obtain an organic solution and a catalyst after the reaction, and distilling to remove the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the oil is 100% and the molar yield of the glycerol triacetate is 99%; adding 4g of methanol and 0.08g of phosphotungstic acid into the obtained fatty acid, reacting for 5h at 140 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the phosphotungstic acid from a liquid phase, filtering and recovering the phosphotungstic acid to obtain a liquid phase as a biodiesel product, and performing chromatographic analysis to obtain the fatty acid methyl ester with the molar yield of 98 percent and the content of 99.6 percent.
Example 17
Mixing 1.0g of illegal cooking oil, 0.08g of phosphotungstic acid and 50g of acetic acid aqueous solution with the mass percentage concentration of 85%, reacting for 2 hours at 160 ℃, standing and layering separated fatty acid after the reaction is finished, carrying out reduced pressure distillation on a liquid phase after the fatty acid is removed, recovering acetic acid, adding 0.5g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling and removing the organic solvent to obtain glycerol triacetate, analyzing that the conversion rate of the grease is 100%, and the molar yield of the glycerol triacetate is 98%; 6g of methanol and 0.05g of zinc sulfate are added into the obtained fatty acid, the mixture reacts for 2 hours at the temperature of 150 ℃, then the methanol is removed by reduced pressure distillation, the zinc sulfate is separated out from the liquid phase, the zinc sulfate is recovered by filtration, the liquid phase is the biodiesel product, and the fatty acid methyl ester yield is 96 percent and the content is 99.4 percent by chromatographic analysis.
Example 18
Mixing 1.0g of mixed grease of illegal cooking oil and soybean oil (the mass ratio is 1:1), 0.3g of acidic resin D001 and 25g of glacial acetic acid, reacting for 6 hours at 120 ℃, filtering at 80 ℃ after the reaction is finished to obtain acidic resin, cooling filtrate to 35 ℃, standing for layering and separating out fatty acid, distilling the reaction liquid under reduced pressure, recovering acetic acid, and obtaining glycerol triacetate, wherein the conversion rate of the grease is 100% and the molar yield of the glycerol triacetate is 97% by analysis; adding 5g of methanol and 0.01g of ZMS-5 molecular sieve with the silicon-aluminum ratio of 50:1 into the obtained fatty acid, reacting for 4 hours at 150 ℃, then filtering and recovering the molecular sieve, distilling under reduced pressure to remove the methanol to obtain a liquid phase as a biodiesel product, and performing chromatographic analysis to obtain the fatty acid methyl ester with the molar yield of 92 percent and the content of 98.8 percent.
Example 19
Mixing 1.0g of glyceryl tristearate, 0.5g of a ZMS-5 molecular sieve with a silicon-aluminum ratio of 50:1 and 15g of an acetic acid aqueous solution with a mass percentage concentration of 95%, reacting at 180 ℃ for 1h, filtering at 50 ℃ after the reaction is finished to obtain the molecular sieve, cooling the filtrate to 30 ℃, filtering out precipitated fatty acid solid, distilling the filtrate under reduced pressure, recovering acetic acid, and obtaining the glyceryl triacetate, wherein the conversion rate of the glyceryl tristearate is 100% and the molar yield of the glyceryl triacetate is 96% by analysis; adding 2g of methanol and 0.08g of ZMS-5 molecular sieve with the silicon-aluminum ratio of 50:1 into the obtained fatty acid, reacting for 2 hours at 150 ℃, filtering and recovering the molecular sieve, then carrying out reduced pressure distillation to remove the methanol to obtain a liquid phase as a biodiesel product, and carrying out chromatographic analysis to obtain the fatty acid methyl ester with the molar yield of 96% and the content of 99.2%.
Example 20
Mixing 1.0g of glyceryl tristearate, 0.2g of alkaline resin D311 and 12g of glacial acetic acid, reacting at 140 ℃ for 4h, filtering at 45 ℃ after the reaction is finished to obtain alkaline resin, cooling the filtrate to 40 ℃, filtering precipitated fatty acid solid, distilling the filtrate under reduced pressure, recovering acetic acid, and obtaining glyceryl triacetate, wherein the conversion rate of the grease is 100% by analysis, and the molar yield of the glyceryl triacetate is 95%; adding 2g of methanol and 0.08g of phosphomolybdic acid into the obtained fatty acid, reacting for 4 hours at 140 ℃, then distilling under reduced pressure to remove methanol, simultaneously separating out phosphomolybdic acid from a liquid phase, filtering and recovering phosphomolybdic acid to obtain a liquid phase which is a biodiesel product, and analyzing by chromatography, wherein the molar yield of fatty acid methyl ester is 98 percent, and the content is 99.5 percent.
Example 21
Mixing 1.0g of mixed grease of illegal cooking oil and hydrogenated oil (the mass ratio is 1:1), 0.2g of phosphomolybdic acid and 10g of glacial acetic acid, reacting for 2 hours at 160 ℃, filtering at 50 ℃ after the reaction is finished to obtain phosphomolybdic acid insoluble in acetic acid, cooling the filtrate to 0 ℃, standing, layering and separating out fatty acid, distilling the filtrate under reduced pressure, recovering acetic acid, obtaining triacetin, analyzing that the conversion rate of the grease is 100 percent, and the molar yield of the triacetin is 98 percent; adding 2g of methanol and 0.06g of phosphotungstic acid into the obtained fatty acid, reacting for 2h at 160 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the phosphotungstic acid from a liquid phase, filtering and recovering the phosphotungstic acid to obtain a liquid phase as a biodiesel product, and analyzing by chromatography, wherein the molar yield of the fatty acid methyl ester is 94 percent, and the content is 99.2 percent.
Example 22
Mixing 1.0g of glyceryl tristearate, 0.5g of silicotungstic acid and 5g of an acetic acid aqueous solution with the mass percent concentration of 95%, reacting for 2 hours at 180 ℃, filtering precipitated fatty acid after the reaction is finished, carrying out reduced pressure distillation on the liquid phase after the fatty acid is removed, recovering acetic acid, adding 0.8g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, distilling to remove the organic solvent to obtain glyceryl triacetate, analyzing that the conversion rate of the glyceryl tristearate is 100%, and the molar yield of the glyceryl triacetate is 99%; adding 2g of methanol and 0.08g of phosphotungstic acid into the obtained fatty acid, reacting for 2h at 180 ℃, then distilling under reduced pressure to remove the methanol, simultaneously precipitating the phosphotungstic acid from a liquid phase, filtering and recovering the phosphotungstic acid to obtain a liquid phase which is a biodiesel product, and performing chromatographic analysis to obtain the fatty acid methyl ester with the molar yield of 98 percent and the content of 99.6 percent.
Claims (14)
1. A method for producing biodiesel and glycerol triacetate is characterized by comprising the following steps:
(1) fully mixing grease, acetic acid and a catalyst to prepare a catalytic reaction system;
(2) reacting at the temperature of 120 ℃ and 250 ℃ for 0.2-10 hours, and separating reaction products after the reaction is finished to obtain long-chain fatty acid and glycerol triacetate;
(3) the separated long-chain fatty acid and methanol are subjected to esterification reaction to obtain long-chain fatty acid methyl ester, namely the biodiesel.
2. The method for producing biodiesel and glycerol triacetate as in claim 1, wherein the fat in the step (1) is an ester compound formed by combining fatty acid and glycerol, and is one or more of animal fat, vegetable fat and waste fat.
3. The method for producing biodiesel and glycerol triacetate as in claim 1, wherein the acetic acid in the step (1) is glacial acetic acid or an aqueous solution of acetic acid, and the mass percentage concentration of acetic acid in the aqueous solution of acetic acid is more than 80%.
4. The method for producing biodiesel and glycerol triacetate as set forth in claim 1, wherein the catalyst in the step (1) is any one of an organic acid catalyst, an organic base catalyst, an inorganic acid catalyst and an inorganic base catalyst.
5. The method of claim 1, wherein the organic acid catalyst and the organic base catalyst are benzene sulfonic acid, p-toluene sulfonic acid, dodecyl benzene sulfonic acid, tri-tert-butyl ammonium hydroxide.
6. The process for producing biodiesel and glycerol triacetate as claimed in claim 1, wherein the inorganic acid catalyst and the inorganic base catalyst are phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, sodium acetate, zinc acetate, potassium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, acidic molecular sieves, acidic resins, basic resins, or heteropoly acids.
7. The method for producing biodiesel and glycerol triacetate as in claim 1, wherein the mass ratio of acetic acid to the fat in the step (1) is 0.2 to 100: 1.
8. the method for producing biodiesel and glycerol triacetate as in claim 1, wherein the mass ratio of the catalyst to the oil in the step (1) is 0.01 to 1: 1.
9. the method for producing biodiesel and glycerol triacetate as set forth in claim 1, wherein the long-chain fatty acid in the step (2) is a fatty acid having 16 to 22 carbon atoms.
10. The method for producing biodiesel and glycerol triacetate as set forth in claim 1, wherein the reaction product separated in the step (2) is:
when the catalyst in the step (1) is in a liquid state, the following process is adopted:
(a) filtering, or standing and layering or centrifugally separating the reaction product to obtain long-chain fatty acid and a mixed solution;
(b) heating the mixed solution to collect acetic acid to obtain a reaction mixture, wherein the mass ratio of the organic solvent to the animal and vegetable oil is 0.01-100: 1, adding an organic solvent into the reaction mixture, uniformly mixing, filtering to obtain an organic solution and a catalyst, and evaporating to remove the organic solvent in the organic solution to obtain glycerol triacetate;
secondly, when the catalyst in the step (1) is solid, the following process is adopted:
(a) heating the reaction product to 40-80 ℃, and filtering to obtain a solid catalyst and a mixed solution A;
(b) filtering or standing the mixed solution A at 0-35 ℃ for layering to obtain long-chain fatty acid and a mixed solution B;
(c) and distilling the mixed solution B to collect acetic acid and obtain glycerol triacetate.
11. The method for producing biodiesel and glycerol triacetate as in claim 10, wherein the organic solvent in the step (one) is ether, chloroform, toluene or benzene.
12. The method according to claim 1, wherein the acid-base catalyst for esterification of long-chain fatty acids with methanol is phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, aluminum chloride, zinc sulfate, sodium acetate, zinc acetate, potassium hydrogen sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, acidic molecular sieves or heteropolyacids.
13. The method for producing biodiesel and glycerol triacetate as in claim 1, wherein the esterification reaction of the long-chain fatty acid with methanol in the step (3) is carried out at 140-: 1.
14. the method for producing biodiesel and glycerol triacetate as set forth in claim 1, wherein the steps
(3) The biodiesel is obtained by the following separation process:
for a homogeneous catalysis system, distilling and recovering methanol, and filtering or centrifuging the remaining solution to obtain long-chain fatty acid methyl ester and a catalyst; for a catalytic system with the solid catalyst, the solid catalyst is firstly filtered and recovered, and then the methanol is distilled and recovered to obtain the biodiesel.
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| CN102226134A (en) * | 2011-05-12 | 2011-10-26 | 福建漳州鼎能生物科技有限公司 | Method for producing biodiesel by using waste oil |
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN105132189A (en) * | 2015-08-06 | 2015-12-09 | 天津大学 | Fine separation method of C18 series and C20-C22 series fatty acid methyl esters |
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| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN102226134A (en) * | 2011-05-12 | 2011-10-26 | 福建漳州鼎能生物科技有限公司 | Method for producing biodiesel by using waste oil |
| CN105132189A (en) * | 2015-08-06 | 2015-12-09 | 天津大学 | Fine separation method of C18 series and C20-C22 series fatty acid methyl esters |
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