CN109400469B - Method for producing long-chain fatty acid and glycerol triacetate from grease - Google Patents
Method for producing long-chain fatty acid and glycerol triacetate from grease Download PDFInfo
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- CN109400469B CN109400469B CN201811219581.2A CN201811219581A CN109400469B CN 109400469 B CN109400469 B CN 109400469B CN 201811219581 A CN201811219581 A CN 201811219581A CN 109400469 B CN109400469 B CN 109400469B
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Abstract
A process for preparing long-chain fatty acid and glyceryl triacetate from oil includes such steps as mixing oil, acetic acid and catalyst, preparing catalytic reaction system, reacting at 250 deg.C for 0.2-10 hr, and separating the reaction product to obtain long-chain fatty acid and glyceryl triacetate. The invention has the advantages of low cost, low energy consumption and no pollution.
Description
Technical Field
The invention relates to a method for producing long-chain fatty acid and glycerol triacetate from grease.
Technical Field
The long-chain fatty acid (the number of carbon atoms in the molecule is 16-22) is a biomass-based chemical product obtained by catalytic hydrolysis of grease, and is widely applied to the fields of petroleum, chemical industry and fine chemicals. At present, long-chain fatty acid and glycerol are mainly generated through acid-base catalytic hydrolysis, a large amount of water is needed in the hydrolysis process, after the reaction is finished, the remaining large amount of water and the glycerol obtained through hydrolysis are mixed and dissolved together, 1 ton of glycerol can be generated when 8 tons of long-chain fatty acid is produced by animal and vegetable oil, and the separation of the glycerol and the water which are completely mixed and dissolved is a high-energy-consumption process.
In addition, the glycerol triacetate is an important chemical solvent, reagent and fixative, the current production method is mainly obtained by catalytic esterification of glycerol, acetic acid and acetic anhydride, and is also prepared by dehydrochlorination of trichloroethane and acetic acid or glycerol and acetyl chloride, the production cost is high on the whole, and the problem of discharge of small-molecular toxic substances cannot be avoided in the whole production process. The invention relates to a method for producing long-chain fatty acid and glycerol triacetate by grease in one step, which is not found in reports through retrieval.
Disclosure of Invention
The invention aims to provide a method for producing long-chain fatty acid and glycerol triacetate from grease, which has low cost, low energy consumption and no pollution.
The conventional preparation method of long-chain fatty acid and glycerol triacetate is to generate long-chain fatty acid and glycerol by catalyzing and hydrolyzing grease, a large amount of water is needed in the hydrolysis process, after the reaction is finished, the water and the glycerol obtained by hydrolysis are mixed and dissolved together, and the long-chain fatty acid is suspended at the top of a system. Separating long chain fatty acid, and separating glycerol and water by distillation. And then 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 glycerol triacetate. The problems with this process are: firstly, the separation of glycerol from water is a highly energy-consuming process; secondly, the esterification reaction of glycerol and acetic acid to produce glycerol triacetate is not completely carried out, high-cost acetic anhydride is needed, the process is complex, and the operation cost is high. Aiming at the first problem, a more energy-saving catalytic reaction system needs to be designed, and the essential reason of the second problem is that the radius of a hydrogen atom on a hydroxyl group of a trifunctional group molecule such as glycerol is far smaller than that of an acetyl group, the steric effect of the reaction is rapidly increased along with the gradual replacement of the hydrogen atom on the hydroxyl group of the glycerol molecule by the acetyl group, so that the glycerol is difficult to be completely esterified with acetic acid through the conventional process, reaction products are mainly mono-acetin and di-acetin, a large amount of acetic anhydride is also needed to be added in order to improve the yield of the tri-acetin, and the limitation of reversible reaction is greatly relieved because the acetic anhydride participates in the reaction process and does not produce water. However, acetic anhydride is usually prepared by cracking acetic acid at high temperature to form ketene, and the ketene is synthesized through a series of processes, so that the cost of raw materials is high, and the process is complicated.
The invention utilizes the direct reaction of grease and acetic acid under the action of a catalyst to generate long-chain fatty acid and glycerol triacetate, which is an acyl exchange process. The fatty acid in the animal and vegetable oil is long-chain fatty acid, and compared with acetic acid, the steric hindrance of the fatty acid is much larger, and the corresponding intramolecular tension is also much larger. 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 monoacetic acid oil, the further reaction is easier, and by analogy, the generation of the glycerol triacetate is an advantageous product of the reaction. In addition, water is not generated in the reaction process, the generated stearic acid is not dissolved in acetic acid and triacetyl glycerine, the separation is easy, and the reaction is basically not limited by balance.
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.
The grease in the step (1) is an ester compound formed by combining long-chain 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) refers to homogeneous or heterogeneous acid-base catalyst, and essentially the reaction can be catalyzed by any acid-base catalyst.
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 separation of the reaction product in the step (2) means:
firstly, when the catalyst adopted 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, uniformly mixing the mixture and 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 adopted in the step (1) is solid, the following process is adopted:
(a) heating the reaction product to 40-80 ℃, and filtering to obtain a catalyst solid 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.
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 long-chain fatty acid by a one-step method.
2. The triacetyl glycerine has high selectivity, and does not contain acetic acid and other esterification products of glycerine.
3. The method has the advantages of high efficiency, greenness, economy and the like, and has few byproducts, the molar yield of the glycerol triacetate is over 95 percent, the molar yield of long-chain fatty acid is more than 95 percent, and the conversion rate of the grease is 100 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 and separating out long-chain fatty acid solid, distilling the filtrate under reduced pressure, recovering the 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% by analysis, the molar yield of the glyceryl triacetate is 95%, the long-chain fatty acids (shown in attached figures 4 and 5) are all octadecanoic fatty acids, and the yield is 100%.
Example 2
Mixing 1.0g of tallow oil, 0.05g of benzenesulfonic acid and 100g of 80 mass percent acetic acid aqueous solution, reacting for 8 hours at 140 ℃, filtering to separate out long-chain fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 0.01g of organic solvent diethyl ether, standing for 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%, the molar yield of the glycerol triacetate is 97%, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 98%.
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 for 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 oil is 100%, the molar yield of the glycerol triacetate is 96%, the long-chain fatty acids are all octadecanoic fatty acids, and the yield is 96%.
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 that the conversion rate of the fat is 100%, the molar yield of the glycerol triacetate is 99%, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 97%.
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 percentage concentration of 95%, reacting at 220 ℃ for 0.6h, centrifuging 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 and removing the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the glycerol triacetate is 95%, 40% of long-chain fatty acid is palmitic acid, the rest is octadecanoic fatty acid, and the total yield of the fatty acid is 98%.
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, carrying out reduced pressure distillation on a liquid phase after the fatty acid is separated, 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 triacetin, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the triacetin is 96%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 95%.
Example 7
Mixing 1.0g of hydrogenated oil, 1.0g of zinc chloride and 80g of acetic acid aqueous solution with the mass percentage concentration of 80%, reacting for 0.2h at 250 ℃, filtering out precipitated fatty acid solid after the reaction is finished, then carrying out reduced pressure distillation on the filtrate, 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 triacetin, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the triacetin is 98%, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 99%.
Example 8
Mixing 1.0g of glyceryl tristearate, 0.1g of sulfuric acid and 50g of 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 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%, the molar yield of the glyceryl triacetate is 95%, all long-chain fatty acids are eighteen-carbon fatty acids, and the yield is 99%.
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 and removing the organic solvent to obtain the triacetin, wherein the conversion rate of the grease is 100%, the molar yield of the triacetin is 97%, all long-chain fatty acids are eighteen-carbon fatty acids, and the yield is 98%.
Example 10
Mixing 1.0g of lard and tallow mixed grease (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 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%, the molar yield of the glycerol triacetate to be 95%, wherein all long-chain fatty acids are octadecanoic fatty acids, and the yield is 98%.
Example 11
Mixing 1.0g of mixed grease 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 for layering precipitated 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 80g of organic solvent chloroform, standing for layering to obtain an organic solution and a catalyst after the reaction, and distilling for removing the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the grease is 100%, the molar yield of the glycerol triacetate is 97%, the palmitic acid content in long-chain fatty acid is 15%, the rest is octadecanoic fatty acid, and the total yield of the fatty acid is 99%.
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 for layering precipitated 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, distilling to remove the organic solvent to obtain triacetin, analyzing the conversion rate of the grease to be 100%, the molar yield of the triacetin to be 98%, all long-chain fatty acids to be octadecanoic fatty acids, and the yield to be 96%.
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, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the glycerol triacetate is 97%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 95%.
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 for layering and separating out 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 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 triacetin, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the triacetin is 95%, the content of erucic acid in long-chain fatty acid is 25%, the rest is octadecanoic fatty acid, and the total yield of the fatty acid is 97%.
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 reduced pressure distillation on a 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, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the glycerol triacetate is 95%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 99%.
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 demixing the fatty acid after the reaction is finished, distilling the liquid phase after the fatty acid is removed under reduced pressure, 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 triacetin, wherein the conversion rate of the oil is 100 percent, the molar yield of the triacetin is 99 percent, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 97 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, and distilling and removing the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the grease is 100% by analysis, the molar yield of the glycerol triacetate is 98%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 96%.
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 triacetin, wherein the conversion rate of the grease is 100%, the molar yield of the triacetin is 97%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 98%.
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 20 ℃, 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% by analysis, the molar yield of the glyceryl triacetate is 96%, the long-chain fatty acids are all octadecanoic fatty acids, and the yield is 99%.
Example 20
Mixing 1.0g of tristearin, 0.2g of basic resin D311 and 12g of glacial acetic acid, reacting for 4 hours at 140 ℃, filtering at 45 ℃ after the reaction is finished to obtain basic resin, cooling the filtrate to 40 ℃, filtering precipitated fatty acid solid, distilling the filtrate under reduced pressure, recovering acetic acid, and obtaining the triacetin, wherein the conversion rate of the tristearin is 100% by analysis, the molar yield of the triacetin is 95%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 99%.
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 the acetic acid, and obtaining triacetin, wherein the conversion rate of the grease is 100%, the molar yield of the triacetin is 98%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 96%.
Example 22
Mixing 1.0g of glyceryl tristearate, 0.5g of silicotungstic acid and 5g of an acetic acid aqueous solution with the mass percentage concentration of 95%, reacting for 2 hours at 180 ℃, filtering precipitated 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 0.8g 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%, the molar yield of the glyceryl triacetate is 99%, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 100%.
Claims (16)
1. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
(1) fully mixing grease, acetic acid and a catalyst to prepare a catalytic reaction system, wherein the grease is an ester compound formed by combining long-chain fatty acid and glycerol and is one or more of animal grease, vegetable grease and waste grease;
(2) reacting at the temperature of 120-250 ℃ for 0.2-10 hours, and separating reaction products after the reaction is finished to obtain long-chain fatty acid and glycerol triacetate, wherein the long-chain fatty acid refers to fatty acid with 16-22 carbon atoms;
(3) the catalyst is one or more of zinc chloride, aluminum sulfate, sodium acetate, zinc acetate, ZSM-5 with Si/Al =50:1 and acidic resin D001.
2. The method for producing long-chain fatty acids and glycerol triacetate from fats and oils according to claim 1, wherein the acetic acid in the step (1) is glacial acetic acid or an aqueous solution of acetic acid, and the concentration of acetic acid in the aqueous solution of acetic acid is more than 80% by mass.
3. The method for producing long-chain fatty acids and glycerol triacetate from fats and oils according to claim 1, wherein the mass ratio of acetic acid to fats and oils in step (1) is 0.2 to 100: 1.
4. The method for producing long-chain fatty acids and glycerol triacetate from fats and oils according to claim 1, wherein the mass ratio of the catalyst to the fats and oils in the step (1) is 0.01 to 1: 1.
5. the method for producing long-chain fatty acids and glycerol triacetate from fats and oils according to claim 1, wherein the reaction product separated in the step (2) is:
when the catalyst adopted 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, uniformly mixing the mixture in the proportion of 1, standing for layering 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 adopted in the step (1) is solid, the following process is adopted:
(a) heating the reaction product to 40-80 ℃, and filtering to obtain a catalyst solid 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.
6. The method for producing long-chain fatty acids and glycerol triacetate as in claim 5, wherein the organic solvent in the step (a) is diethyl ether, chloroform, toluene or benzene.
7. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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 and separating out long-chain fatty acid solid, distilling the filtrate under reduced pressure, recovering the acetic acid, and obtaining the glyceryl triacetate, wherein the conversion rate of the glyceryl tristearate is 100% by analysis, the molar yield of the glyceryl triacetate is 95%, all the long-chain fatty acids are octadecanoic fatty acids, and the yield is 100%.
8. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
mixing 1.0g of beef 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 long-chain fatty acid solid after the reaction is finished, distilling the filtrate under reduced pressure, recovering acetic acid, adding 0.01g of organic solvent diethyl ether, standing for 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 oil is 100%, the molar yield of the glycerol triacetate is 97%, the long-chain fatty acids are all octadecanoic fatty acids, and the yield is 98%.
9. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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 for 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 oil is 100%, the molar yield of the glycerol triacetate is 96%, the long-chain fatty acids are all octadecanoic fatty acids, and the yield is 96%.
10. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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 that the conversion rate of the fat is 100%, the molar yield of the glycerol triacetate is 99%, the long-chain fatty acids are all eighteen-carbon fatty acids, and the yield is 97%.
11. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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, carrying out reduced pressure distillation on a liquid phase after the fatty acid is separated, 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 triacetin, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the triacetin is 96%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 95%.
12. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
mixing 1.0g of glyceryl tristearate, 0.1g of sulfuric acid and 50g of acetic acid aqueous solution with the mass percentage concentration of 90%, reacting for 8 hours at 120 ℃, filtering out precipitated fatty acid solid after the reaction is finished, then carrying out reduced pressure distillation on the filtrate, 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 the glyceryl triacetate, analyzing that the conversion rate of the glyceryl tristearate is 100%, the molar yield of the glyceryl triacetate is 95%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 99%.
13. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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, and distilling and removing the organic solvent to obtain glycerol triacetate, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the glycerol triacetate is 98%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 96%.
14. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
mixing 1.0g of mixed grease with 1:1 of illegal cooking oil and hydrogenated oil by mass ratio, 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 for layering to separate out fatty acid, distilling the filtrate under reduced pressure, recovering acetic acid, and obtaining glycerol triacetate, wherein the conversion rate of the grease is 100%, the molar yield of the glycerol triacetate is 98%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 96%.
15. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
mixing 1.0g of glyceryl tristearate, 0.5g of silicotungstic acid and 5g of acetic acid aqueous solution with the mass percentage concentration of 95%, reacting for 2 hours at 180 ℃, 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 0.8g of organic solvent diethyl ether, standing and layering to obtain an organic solution and a catalyst after the reaction, and distilling and removing the organic solvent to obtain glyceryl triacetate, wherein the conversion rate of the glyceryl tristearate is 100% by analysis, the molar yield of the glyceryl triacetate is 99%, all long-chain fatty acids are eighteen-carbon fatty acids, and the yield is 100%.
16. A method for producing long-chain fatty acid and glycerol triacetate from grease is characterized by comprising the following steps:
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, wherein the conversion rate of the analyzed grease is 100%, the molar yield of the glycerol triacetate is 97%, all long-chain fatty acids are octadecanoic fatty acids, and the yield is 95%.
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| "油脂水解生产脂肪酸工艺选择";刘春媚;《广东化工》;20140330;第41卷(第6期);第105页右栏2.1油脂水解生产工艺2.1常压水解 * |
| "环境友好催化剂催化合成三醋酸甘油酯";陶贤平;《精细石油化工进展》;20051128;第6卷(第11期);第29-31页 1.1-1.8 * |
| Lijuan Su等."The driving effect of substituent size changes on reaction: a novel reaction for direct production of triacetylglycerol from oils and fats".《Green Chem》.2020,第22卷第6345-6350页. * |
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