CN109456838A - A method of producing biodiesel and triacetyl glycerine - Google Patents
A method of producing biodiesel and triacetyl glycerine Download PDFInfo
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- CN109456838A CN109456838A CN201811219534.8A CN201811219534A CN109456838A CN 109456838 A CN109456838 A CN 109456838A CN 201811219534 A CN201811219534 A CN 201811219534A CN 109456838 A CN109456838 A CN 109456838A
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- C—CHEMISTRY; METALLURGY
- 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
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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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
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
A kind of biodiesel and the method for triacetyl glycerine of producing is to be sufficiently mixed grease, acetic acid and catalyst, it is made into catalystic converter system, it is reacted 0.2-10 hours at 120-250 DEG C, reaction product is separated after reaction, obtain long chain fatty acids and triacetyl glycerine, esterification occurs for isolated long chain fatty acids and methanol, obtains long chain fatty acids methyl esters i.e. biodiesel.The present invention has production cost low, free of contamination advantage.
Description
Technical field
The invention belongs to renewable resource fields, are related to a kind of method for producing biodiesel and triacetyl glycerine.
Technical background
Biodiesel is substantially to be by the carbon number that catalytic transesterification obtains with methanol or ethyl alcohol using waste grease
The ester type compound that the long chain fatty acids and methanol or ethyl alcohol of 16-22 are formed.Biodiesel is typical " green energy resource ", tool
Have the advantages that good environmental protection, startup performance of engine are good, fuel performance is good, raw material sources are extensive, and have renewable
Property.Therefore its yield rapid growth in the world, according to the statistical data that global renewable energy net is announced, whole world biology
Production of diesel oil risen to from 70.40 ten thousand tons of 2000 2015 2648.80 ten thousand tons, annual average compound growth rate 27.36%.
Booming period is actually entered from 2006 in the country, China biodiesel market.Animal and plant fat 9 tons of biologies of every production
Diesel oil, glycerol that will be 1 ton of by-product, and the catalyzed conversion of glycerol becomes the significant process for alleviating biodiesel cost pressure.
Triacetyl glycerine is a kind of important Chemical Solvents, reagent and fixastive, and current production method is mainly benefit
It is obtained with glycerol and acetic acid and acetic anhydride catalytic esterification, also useful trichloroethanes and acetic acid or glycerol and the dechlorination of acetyl group chlorine
Change hydrogen to be made, on the whole its high production cost, and unavoidably has the discharge of small molecule noxious material in all round process
Problem.
Summary of the invention
The object of the present invention is to provide a kind of production cost is low, free of contamination production biodiesel and economical and efficient production
The method of triacetyl glycerine.
The preparation method of conventional biodiesel and triacetyl glycerine is that grease catalytic transesterification generates long chain fatty acids
Methyl esters and glycerol, glycerol and acetic acid reaction generate the mixture of single triacetin and two acetoglycerides, and then single acetic acid is sweet
The mixture of grease and two acetoglycerides and acetic acid anhydride reactant generate triacetyl glycerine.The problem of this technique, key was
The esterification of glycerol and production of acetic acid triacetyl glycerine is not thorough, and high-cost acetic anhydride is needed to participate in reaction, and
And complex technical process, operating cost are high.There are two chemical nature reasons for this problem: first, glycerol is esterified with acetic acid dehydration is
One reversible reaction, the moisture content of generation seriously affects the carry out degree of reaction, therefore generally requires to generate in reaction process
Moisture content is separated from system in time, this is for being often huge challenge with the acetate system that water dissolves each other completely；Second,
The trifunctional molecule as glycerol, hydrogen atom radius is much smaller than acetyl group radius on hydroxyl, on glycerol molecule hydroxyl
Hydrogen atom gradually replaced by acetyl group, reaction steric effect rises rapidly so that glycerol be difficult by conventional technique with
Acetic acid is thoroughly esterified, reaction product often be mainly an acetoglyceride and two acetoglycerides, it is sweet in order to improve three acetic acid
The yield of grease needs to be added a large amount of acetic anhydride toward contact.Water is not produced since acetic anhydride participates in reaction process, is alleviated significantly
The limitation of reversible reaction.But acetic anhydride is usually to generate ketenes by pyrolytic cracking by acetic acid, ketenes is using one
Series of processes, which just synthesizes, to be made, and cost of material is higher, and technique is also more complex.
The present invention is directly reacted with acetic acid under the effect of the catalyst using animal and plant fat, generate long chain fatty acids with
Triacetyl glycerine, this is the reaction process of acyl group exchange.Fatty acid in animal and plant fat is all that carbon atom number is
The long chain fatty acids of 16-22, relative to acetic acid, its steric hindrance is much bigger, and corresponding molecule internal tension is also much bigger.With glyceride metaplasia
At triacetyl glycerine difference, the acetyl exchange reaction of animal and plant fat is the process that molecule internal tension is gradually reduced, and catalysis is anti-
The process that steric hindrance is gradually reduced is answered, once so after acetic acid replaces long chain fatty acids to generate single acetic acid grease, further
Reaction can be more easier, and so on, generate the predominant product that triacetyl glycerine is this reaction.In addition, during the reaction
Water will not be generated, the long chain fatty acids of generation do not dissolve in acetic acid and triacetyl glycerine, so the limit that reaction is not balanced substantially
System.Obtained long chain fatty acids can obtain biodiesel by conventional esterification technique.
The method specifically includes following steps:
(1) grease, acetic acid and catalyst are sufficiently mixed, are made into catalystic converter system；
(2) it is reacted 0.2-10 hours at 120-250 DEG C, separates reaction product after reaction, obtain long chain fatty acids
And triacetyl glycerine；
(3) esterification occurs for isolated long chain fatty acids and methanol, obtains the i.e. biological bavin of long chain fatty acids methyl esters
Oil.
Grease described in step (1) is the ester type compound that fatty acid and glycerol are bonded, can be animal fat,
One or more of vegetable fat, waste grease；
Acetic acid described in step (1) refers to the aqueous solution of glacial acetic acid or acetic acid, wherein in the aqueous solution of acetic acid acetic acid matter
It measures percent concentration and is greater than 80%；
Catalyst described in step (1) refers to that acid base catalysator, optimum catalyst are benzene sulfonic acid, p-methyl benzenesulfonic acid, dodecane
The organic acids and bases catalyst such as base benzene sulfonic acid, tri-tert ammonium hydroxide, phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, acetic acid
Sodium, zinc acetate, potassium acid sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, acidic molecular sieve, acidic resins, basic resin or miscellaneous
The inorganic acid alkalis catalyst such as polyacid.
The mass ratio of step (1) acetic acid and grease is 0.2-100:1.
The mass ratio of step (1) catalyst and grease is 0.01-1:1.
Long chain fatty acids described in step (2) refer to that carbon atom number is the fatty acid of 16-22.
Separation reaction product described in step (2) refers to:
One, for step (1) catalyst be liquid condition when, using following technique:
(a), reaction product is through filtering or stratification, or is centrifugally separating to obtain long chain fatty acids and mixed solution；
(b), mixed solution is heated and collects acetic acid, reaction mixture is obtained, by organic solvent and animal and plant fat quality
Than organic solvent being added in reaction mixture and is filtered after evenly mixing, organic solution and catalysis are obtained for 0.01-100:1
Agent, evaporation remove the organic solvent in organic solution, obtain triacetyl glycerine.
The organic solvent is ether, chloroform, toluene or benzene.
Two, when for step (1) catalyst, to be catalyst be solid, using following technique:
(a) reaction product filters after being heated to 40 DEG C -80 DEG C, obtains solid catalyst and mixed solution A；
(b) mixed solution A obtains long chain fatty acids and mixed solution B in 0-35 DEG C of filtering or stratification；
(c) mixed solution B is distilled and collects acetic acid, and obtain triacetyl glycerine.
Step (3) long chain fatty acids and methanol occur esterification and refer under acid base catalysator effect, methanol with
Long chain fatty acids reaction generates long chain fatty acids methyl esters, and acid base catalysator used is phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, sulfuric acid
Aluminium, aluminium chloride, zinc sulfate, sodium acetate, zinc acetate, potassium acid sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, acidic molecular sieve,
Heteropoly acid etc.；
Step (3) long chain fatty acids and methanol occur esterification and refer at 140-200 DEG C, and the reaction time is
The mass ratio of 10min-10h, methanol and long chain fatty acids is 0.1-2:1, and the mass ratio of catalyst and long chain fatty acids is
0.005-0.1:1；
Biodiesel described in step (3) is obtained by following separating technology: for homogeneous catalysis system, being distilled back
Methanol is received, remaining thing liquid filtering or centrifugation obtain long chain fatty acids methyl esters and catalyst；Solid catalyst is participated in
Solid catalyst is recovered by filtration in catalyst system first, is then distilled to recover methanol and obtains biodiesel.
Compared with the prior art the present invention has the advantages that
1, grease and acetic acid generation acyl group exchange reaction first obtains triacetyl glycerine, then long chain fatty acids methyl esters
Change obtains biodiesel.
2, the selectivity of triacetyl glycerine is high, other esterification products without acetic acid and glycerol.
3, three acetic acid can be obtained without using the dewatering process of the relatively expensive chemical reagent such as acetic anhydride and complexity
Glyceride, the method for the present invention have the advantages that efficient, green, economy etc., and by-product is few.
4, the yield of triacetyl glycerine is greater than 90%, while the yield of biodiesel is greater than 90%.
Detailed description of the invention
Fig. 1 is the NMR carbon spectrum of triacetyl glycerine.
Fig. 2 is the NMR hydrogen spectrum of triacetyl glycerine.
Fig. 3 is that (peak 1,2,3 is that analytic process adds ethyl alcohol, chloroform and internal standard compound methyl benzoate, peak to gas chromatogram
It (21.74) is triacetyl glycerine).
Fig. 4 is stearic NMR hydrogen spectrum.
Fig. 5 is stearic NMR carbon spectrum.
Specific embodiment
Embodiment 1
1.0g glyceryl tristearate, 0.01g phosphotungstic acid and 0.2g glacial acetic acid are mixed, 120 DEG C of reaction 10h have reacted
It is filtered at latter 60 DEG C, obtains the phosphotungstic acid insoluble in acetic acid, filtrate is cooled to 40 DEG C, filters the fatty-acid solid of precipitation, later
Filtrate decompression distillation, recovery of acetic acid, and obtain triacetyl glycerine (see attached drawing 1,2,3), through analyzing glyceryl tristearate
Conversion ratio be 100%, the molar yield 95% of triacetyl glycerine；It is added in obtained fatty acid (see attached Figure 4 and 5)
0.1g methanol and 0.005g phosphotungstic acid, 140 DEG C of reaction 2h, then vacuum distillation removes methanol, while phosphotungstic acid is analysed from liquid phase
Out, phosphotungstic acid is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid methyl ester molar yield
98%, content 99.5%.
Embodiment 2
The aqueous acetic acid that 1.0g butter grease, 0.05g benzene sulfonic acid and 100g mass percent concentration are 80% is mixed
It closing, 140 DEG C of reaction 8h filter the fatty-acid solid of precipitation after the reaction was completed, filtrate decompression distillation later, recovery of acetic acid,
0.01g organic solvent ether and stratification is added, the catalyst after obtaining organic solution and reaction is distilled off organic molten
Agent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield 97% of triacetyl glycerine；?
0.4g methanol and 0.008g phosphoric acid is added in obtained fatty acid, and 150 DEG C of reaction 10h, then vacuum distillation removes methanol, simultaneously
Phosphoric acid stratification from liquid phase is precipitated, and recycles phosphoric acid, obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid
Methyl esters molar yield 96%, content 99.2%.
Embodiment 3
The aqueous acetic acid that 1.0g lard grease, 0.1g p-methyl benzenesulfonic acid and 80g mass percent concentration are 90% is mixed
It closing, 160 DEG C of reaction 4h filter the fatty-acid solid of precipitation after the reaction was completed, filtrate decompression distillation later, recovery of acetic acid,
0.05g organic solvents, chloroform and stratification is added, the catalyst after obtaining organic solution and reaction is distilled off organic molten
Agent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield 96% of triacetyl glycerine；?
0.6g methanol and 0.01g phosphoric acid is added in obtained fatty acid, and 140 DEG C of reaction 10h, then vacuum distillation removes methanol, while phosphorus
Acid is precipitated from liquid phase, and phosphoric acid is recovered by filtration, and obtaining liquid phase is biodiesel oil product, and by chromatography, fatty acid methyl ester rubs
That yield 95%, content 99.4%.
Embodiment 4
The acetic acid for being 85% by 1.0g sheep oil grease, 0.2g dodecyl benzene sulfonic acid and 90g mass percent concentration is water-soluble
Liquid mixing, 180 DEG C of reaction 2h filter the fatty-acid solid of precipitation after the reaction was completed, and vinegar is recycled in filtrate decompression distillation later
0.1g organic solvent toluene and stratification is added in acid, and the catalyst after obtaining organic solution and reaction is distilled off organic
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield 99% of triacetyl glycerine；
0.8g methanol and 0.04g zinc chloride is added in obtained fatty acid, 160 DEG C of reaction 6h, then vacuum distillation removes methanol, together
When zinc chloride be precipitated from liquid phase, zinc chloride is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography, fat
Sour methyl esters molar yield 96%, content 99.6%.
Embodiment 5
The acetic acid for being 95% by 1.0g palm oil, 0.5g tri-tert ammonium hydroxide and 60g mass percent concentration is water-soluble
Liquid mixing, 220 DEG C of reaction 0.6h, after the reaction was completed, and the fatty acid that stratification is precipitated, the liquid phase decompression after separating fatty acid
0.5g organic solvent benzo stratification is added in distillation, recovery of acetic acid, the catalyst after obtaining organic solution and reaction, distillation
Organic solvent is removed, triacetyl glycerine is obtained, the conversion ratio for being analyzed grease is 100%, mole receipts of triacetyl glycerine
Rate 95%；1g methanol and 0.06g sulfuric acid is added in obtained fatty acid, 180 DEG C of reaction 30min, then vacuum distillation removes first
Alcohol, while sulfuric acid is precipitated from liquid phase, and sulfuric acid is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography, rouge
Fatty acid methyl esters molar yield 95%, content 99.0%.
Embodiment 6
1.0g gutter oil, 0.8g phosphoric acid and 0.4g glacial acetic acid are mixed, 240 DEG C of reaction 0.4h, after the reaction was completed, is stood
It is layered the fatty acid being precipitated, the liquid phase after separating fatty acid is evaporated under reduced pressure, recovery of acetic acid, and it is simultaneously quiet that 1g organic solvent toluene is added
Layering is set, the catalyst after obtaining organic solution and reaction is distilled off organic solvent, obtains triacetyl glycerine, through analyzing
The conversion ratio of grease is 100%, the molar yield 96% of triacetyl glycerine；Obtained fatty acid be added 1.5g methanol and
0.08g phosphotungstic acid, 200 DEG C of reaction 10min, then vacuum distillation removes methanol, while phosphotungstic acid is precipitated from liquid phase, filtering
Phosphotungstic acid is recycled, obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid methyl ester molar yield 93%, content
99.1%.
Embodiment 7
The aqueous acetic acid that 1.0g hydrogenated oil and fat, 1.0g zinc chloride and 80g mass percent concentration are 80% is mixed, 250
DEG C reaction 0.2h filters the fatty-acid solid of precipitation after the reaction was completed, and filtrate decompression later distillation, recovery of acetic acid is added
2g organic solvent ether and stratification, the catalyst after obtaining organic solution and reaction, are distilled off organic solvent, obtain
Triacetyl glycerine, the conversion ratio for being analyzed grease is 100%, the molar yield 98% of triacetyl glycerine；In obtained rouge
Fat acid is added 2g methanol and 0.1g aluminum sulfate, 180 DEG C of reaction 3h, then vacuum distillation removing methanol, while aluminum sulfate is from liquid phase
Middle precipitation, is recovered by filtration aluminum sulfate, and obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid methyl ester molar yield
95%, content 99.2%.
Embodiment 8
The aqueous acetic acid that 1.0g glyceryl tristearate, 0.1g sulfuric acid and 50g mass percent concentration are 90% is mixed
It closing, 120 DEG C of reaction 8h filter the fatty-acid solid of precipitation after the reaction was completed, filtrate decompression distillation later, recovery of acetic acid,
5g organic solvent toluene and stratification is added, organic solvent is distilled off in the catalyst after obtaining organic solution and reaction,
Triacetyl glycerine is obtained, the conversion ratio for being analyzed glyceryl tristearate is 100%, the molar yield of triacetyl glycerine
95%；4g methanol and 0.01g aluminium chloride is added in obtained fatty acid, 150 DEG C of reaction 1h, then vacuum distillation removes methanol,
Aluminium chloride is precipitated from liquid phase simultaneously, and aluminium chloride is recovered by filtration, and obtaining liquid phase is biodiesel oil product, by chromatography, rouge
Fatty acid methyl esters molar yield 96%, content 99.4%.
Embodiment 9
By 1.0g glyceryl tristearate and the compound lard (mass ratio 1:1) of sheep oil, 0.05g aluminum sulfate and 40g matter
It measures the aqueous acetic acid that percent concentration is 85% to mix, 140 DEG C of reaction 4h, after the reaction was completed, the fatty acid for filtering precipitation are solid
10g organic solvent ether and stratification is added in body, filtrate decompression distillation later, recovery of acetic acid, obtain organic solution and
Catalyst after reaction, is distilled off organic solvent, obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%,
The molar yield 97% of triacetyl glycerine；5g methanol and 0.02g zinc sulfate, 180 DEG C of reactions are added in obtained fatty acid
4h, then vacuum distillation removes methanol, while zinc sulfate is precipitated from liquid phase, and zinc sulfate is recovered by filtration, and obtains liquid phase as biology
Diesel product, by chromatography, fatty acid methyl ester molar yield 95%, content 99.3%.
Embodiment 10
The compound lard (mass ratio 1:3) of 1.0g lard and butter, 0.1g sodium acetate and 10g mass percent is dense
Degree mixes for 95% aqueous acetic acid, and 120 DEG C of reaction 6h filter the fatty-acid solid of precipitation, later after the reaction was completed
50g organic solvent toluene and stratification is added in filtrate decompression distillation, recovery of acetic acid, urging after obtaining organic solution and reacting
Organic solvent is distilled off in agent, obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, three triacetins
The molar yield 95% of ester；6g methanol is added in obtained fatty acid and then 0.05g sodium acetate, 140 DEG C of reaction 8h are depressurized
Distillation for removing methanol, while sodium acetate is precipitated from liquid phase, and sodium acetate is recovered by filtration, obtaining liquid phase is biodiesel oil product, warp
Cross chromatography, fatty acid methyl ester molar yield 98%, content 99.6%.
Embodiment 11
The compound lard (mass ratio 1:2) of 1.0g palm oil and hydrogenated oil and fat, 0.2g zinc acetate and 0.8g glacial acetic acid is mixed
It closes, 120 DEG C of reaction 8h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid is returned
Acetic acid is received, 80g organic solvents, chloroform and stratification is added, the catalyst after obtaining organic solution and reaction has been distilled off
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield of triacetyl glycerine
97%；8g methanol and 0.08g zinc acetate is added in obtained fatty acid, 150 DEG C of reaction 1.5h, then vacuum distillation removes first
Alcohol, while zinc acetate is precipitated from liquid phase, and zinc acetate is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography point
Analysis, fatty acid methyl ester molar yield 96%, content 99.2%.
Embodiment 12
The compound lard (mass ratio 1:1) of 1.0g gutter oil and butter, 0.4g potassium hydroxide and 1g glacial acetic acid is mixed
It closes, 120 DEG C of reaction 4h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid is returned
Acetic acid is received, 100g organic solvent toluene is added and is filtered, the catalyst after obtaining organic solution and reaction is distilled off organic
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield 98% of triacetyl glycerine；
10g methanol and 0.01g potassium acid sulfate is added in obtained fatty acid, 160 DEG C of reaction 40min, then vacuum distillation removes first
Alcohol, while potassium acid sulfate is precipitated from liquid phase, and potassium acid sulfate is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography
Analysis, fatty acid methyl ester molar yield 95%, content 99.0%.
Embodiment 13
The aqueous acetic acid that 1.0g soybean oil, 0.6g potassium acid sulfate and 40g mass percent concentration are 80% is mixed,
160 DEG C of reaction 1h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid, recycling
20g organic solvent toluene and stratification is added in acetic acid, and the catalyst after obtaining organic solution and reaction is distilled off organic
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield 97% of triacetyl glycerine；
2g methanol and 0.02g sodium carbonate is added in obtained fatty acid, 160 DEG C of reaction 8h, then vacuum distillation removes methanol, simultaneously
Sodium carbonate is precipitated from liquid phase, and sodium carbonate is recovered by filtration, and obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid
Methyl esters molar yield 92%, content 99.4%.
Embodiment 14
1.0g rapeseed oil, 0.02g sodium carbonate and 2g glacial acetic acid are mixed, 200 DEG C of reaction 0.8h, after the reaction was completed, is stood
It is layered the fatty acid being precipitated, 10g organic solvent ether and mistake is added in the liquid phase vacuum distillation after removing fatty acid, recovery of acetic acid
Filter, the catalyst after obtaining organic solution and reaction, is distilled off organic solvent, obtains triacetyl glycerine, through analyzing grease
Conversion ratio be 100%, the molar yield 95% of triacetyl glycerine；5g methanol and 0.04g carbon is added in obtained fatty acid
Sour hydrogen sodium, 150 DEG C of reaction 10h, then vacuum distillation removes methanol, while sodium bicarbonate is precipitated from liquid phase, and carbon is recovered by filtration
Sour hydrogen sodium, obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid methyl ester molar yield 94%, content
99.3%.
Embodiment 15
The aqueous acetic acid that 1.0g peanut oil, 0.04g sodium hydroxide and 20g mass percent concentration are 90% is mixed,
220 DEG C of reaction 0.6h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid are returned
Acetic acid is received, 5g organic solvent toluene and stratification is added, the catalyst after obtaining organic solution and reaction has been distilled off
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield of triacetyl glycerine
95%；6g methanol and 0.06g sodium hydroxide is added in obtained fatty acid, 180 DEG C of reaction 4h, then vacuum distillation removes first
Alcohol, while catalyst solid is precipitated from liquid phase, and catalyst is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography
Analysis, fatty acid methyl ester molar yield 95%, content 99.6%.
Embodiment 16
1.0g lard and the compound lard (mass ratio 1:3) of soybean, 0.06g zinc chloride and 8g glacial acetic acid are mixed,
180 DEG C of reaction 1h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid, recycling
Acetic acid is added 2g organic solvents, chloroform and filters, and organic solvent is distilled off in the catalyst after obtaining organic solution and reaction,
Triacetyl glycerine is obtained, the conversion ratio for being analyzed grease is 100%, the molar yield 99% of triacetyl glycerine；It is obtaining
Fatty acid 4g methanol and 0.08g phosphotungstic acid, 140 DEG C of reaction 5h, then vacuum distillation removing methanol, while phosphotungstic acid is added
It is precipitated from liquid phase, phosphotungstic acid is recovered by filtration, obtaining liquid phase is biodiesel oil product, and by chromatography, fatty acid methyl ester rubs
That yield 98%, content 99.6%.
Embodiment 17
The aqueous acetic acid that 1.0g gutter oil, 0.08g phosphotungstic acid and 50g mass percent concentration are 85% is mixed,
160 DEG C of reaction 2h, after the reaction was completed, the fatty acid that stratification is precipitated, the liquid phase vacuum distillation after removing fatty acid, recycling
0.5g organic solvent ether and stratification is added in acetic acid, and the catalyst after obtaining organic solution and reaction has been distilled off
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed grease is 100%, the molar yield of triacetyl glycerine
98%；6g methanol and 0.05g zinc sulfate is added in obtained fatty acid, 150 DEG C of reaction 2h, then vacuum distillation removes methanol,
Zinc sulfate is precipitated from liquid phase simultaneously, and zinc sulfate is recovered by filtration, and obtaining liquid phase is biodiesel oil product, by chromatography, rouge
Fatty acid methyl esters molar yield 96%, content 99.4%.
Embodiment 18
By the compound lard (mass ratio 1:1) of 1.0g gutter oil and soybean oil, 0.3g acidic resins D001 and 25g ice
Acetic acid mixing, 120 DEG C of reaction 6h, 80 DEG C of filterings, obtain acidic resins, filtrate is cooled to 35 DEG C, stratification after the reaction was completed
The fatty acid of precipitation, reaction solution vacuum distillation later, recovery of acetic acid, and triacetyl glycerine is obtained, through turning for analysis grease
Rate is 100%, the molar yield 97% of triacetyl glycerine；5g methanol and 0.01g silica alumina ratio is added in obtained fatty acid
For the ZMS-5 molecular sieve of 50:1, then molecular sieve is recovered by filtration in 150 DEG C of reaction 4h, vacuum distillation removes methanol, obtains liquid phase
For biodiesel oil product, by chromatography, fatty acid methyl ester molar yield 92%, content 98.8%.
Embodiment 19
1.0g glyceryl tristearate, the ZMS-5 molecular sieve that 0.5g silica alumina ratio is 50:1 and 15g mass percent is dense
Degree mixes for 95% aqueous acetic acid, 180 DEG C of reaction 1h, after the reaction was completed 50 DEG C of filterings, obtains molecular sieve, and filtrate is cooling
To 30 DEG C, the fatty-acid solid of precipitation is filtered, filtrate decompression distillation later, recovery of acetic acid, and triacetyl glycerine is obtained,
The conversion ratio for being analyzed glyceryl tristearate is 100%, the molar yield 96% of triacetyl glycerine；In obtained fat
It is the ZMS-5 molecular sieve of 50:1 that 2g methanol and 0.08g silica alumina ratio, which is added, in acid, then molecular sieve is recovered by filtration in 150 DEG C of reaction 2h,
Then vacuum distillation removes methanol, and obtaining liquid phase is biodiesel oil product, by chromatography, fatty acid methyl ester molar yield
96%, content 99.2%.
Embodiment 20
1.0g glyceryl tristearate, 0.2g basic resin D311 and 12g glacial acetic acid are mixed, 140 DEG C of reaction 4h, instead
45 DEG C of filterings, obtain basic resin, filtrate is cooled to 40 DEG C, filters the fatty-acid solid of precipitation, filtrate later after the completion of answering
Vacuum distillation, recovery of acetic acid, and triacetyl glycerine is obtained, the conversion ratio for being analyzed grease is 100%, triacetyl glycerine
Molar yield 95%；2g methanol and 0.08g phosphomolybdic acid is added in obtained fatty acid, 140 DEG C of reaction 4h, then decompression is steamed
Methanol is removed in distillation, while phosphomolybdic acid is precipitated from liquid phase, and phosphomolybdic acid is recovered by filtration, and obtaining liquid phase is biodiesel oil product, passes through
Chromatography, fatty acid methyl ester molar yield 98%, content 99.5%.
Embodiment 21
The compound lard (mass ratio 1:1) of 1.0g gutter oil and hydrogenated oil and fat, 0.2g phosphomolybdic acid and 10g glacial acetic acid is mixed
It closes, 160 DEG C of reaction 2h, after the reaction was completed 50 DEG C of filterings, obtains the phosphomolybdic acid insoluble in acetic acid, filtrate is cooled to 0 DEG C, stands
It is layered the fatty acid being precipitated, filtrate decompression distillation later, recovery of acetic acid, and triacetyl glycerine is obtained, through analysis grease
Conversion ratio is 100%, the molar yield 98% of triacetyl glycerine；2g methanol and 0.06g phosphorus tungsten is added in obtained fatty acid
Acid, 160 DEG C of reaction 2h, then vacuum distillation removes methanol, while phosphotungstic acid is precipitated from liquid phase, and phosphotungstic acid is recovered by filtration, and obtains
It is biodiesel oil product to liquid phase, by chromatography, fatty acid methyl ester molar yield 94%, content 99.2%.
Embodiment 22
The aqueous acetic acid for being 95% by 1.0g glyceryl tristearate, 0.5g silico-tungstic acid and 5g mass percent concentration
Mixing, 180 DEG C of reaction 2h filter the fatty acid of precipitation after the reaction was completed, the liquid phase vacuum distillation after removing fatty acid, recycling
0.8g organic solvent ether and stratification is added in acetic acid, and the catalyst after obtaining organic solution and reaction has been distilled off
Solvent obtains triacetyl glycerine, and the conversion ratio for being analyzed glyceryl tristearate is 100%, and triacetyl glycerine rubs
That yield 99%；2g methanol and 0.08g phosphotungstic acid is added in obtained fatty acid, 180 DEG C of reaction 2h, then vacuum distillation removes
Methanol is removed, while phosphotungstic acid is precipitated from liquid phase, phosphotungstic acid is recovered by filtration, obtaining liquid phase is biodiesel oil product, by chromatography
Analysis, fatty acid methyl ester molar yield 98%, content 99.6%.
Claims (14)
1. a kind of method for producing biodiesel and triacetyl glycerine, it is characterised in that include the following steps:
(1) grease, acetic acid and catalyst are sufficiently mixed, are made into catalystic converter system；
(2) it is reacted 0.2-10 hours at 120-250 DEG C, separates reaction product after reaction, obtain long chain fatty acids and three
Acetoglyceride；
(3) esterification occurs for isolated long chain fatty acids and methanol, obtains long chain fatty acids methyl esters i.e. biodiesel.
2. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (1)
The grease is the ester type compound that fatty acid and glycerol are bonded, and is animal fat, vegetable fat, in waste grease
It is one or more of.
3. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (1)
The acetic acid is the aqueous solution of glacial acetic acid or acetic acid, and wherein the mass percent concentration of acetic acid is greater than in the aqueous solution of acetic acid
80%。
4. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (1)
The catalyst is inorganic acid alkali catalyst or organic acids and base catalyst.
5. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that organic acid
Base catalyst catalyst is benzene sulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid or tri-tert ammonium hydroxide.
6. benefit require 1 described in a kind of method for producing biodiesel and triacetyl glycerine, it is characterised in that organic acids and base is urged
Agent is phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, sodium acetate, zinc acetate, potassium acid sulfate, sodium carbonate, sodium bicarbonate, hydrogen
Sodium oxide molybdena, acidic molecular sieve, acidic resins, basic resin or heteropoly acid.
7. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (1)
The mass ratio of the acetic acid and grease is 0.2-100:1.
8. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (1)
The mass ratio of the catalyst and grease is 0.01-1:1.
9. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step (2)
The long chain fatty acids are the fatty acid that carbon atom number is 16-22.
10. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step
(2) the separation reaction product described in refers to:
(1), for step (1) catalyst be liquid condition when, using following technique:
(a), reaction product is through filtering or stratification, or is centrifugally separating to obtain long chain fatty acids and mixed solution；
(b), mixed solution is heated and collects acetic acid, obtained reaction mixture, be by organic solvent and animal and plant fat mass ratio
Organic solvent is added in reaction mixture and filters after evenly mixing, obtains organic solution and catalyst by 0.01-100:1, evaporates
The organic solvent in organic solution is removed, triacetyl glycerine is obtained；
(2), when for step (1) catalyst, to be catalyst be solid, using following technique:
(a) reaction product filters after being heated to 40 DEG C -80 DEG C, obtains solid catalyst and mixed solution A；
(b) mixed solution A obtains long chain fatty acids and mixed solution B in 0-35 DEG C of filtering or stratification；
(c) mixed solution B is distilled and collects acetic acid, and obtain triacetyl glycerine.
11. a kind of method for producing biodiesel and triacetyl glycerine as claimed in claim 10, it is characterised in that step
(1) organic solvent is ether, chloroform, toluene or benzene in；A kind of production biodiesel as described in claim 1 and three vinegar
The method of acid glyceride, it is characterised in that step.
12. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that (3) institute
It states long chain fatty acids and the acid base catalysator of esterification occurs for methanol for phosphoric acid, sulfuric acid, hydrochloric acid, zinc chloride, aluminum sulfate, chlorination
Aluminium, zinc sulfate, sodium acetate, zinc acetate, potassium acid sulfate, sodium carbonate, sodium bicarbonate, sodium hydroxide, acidic molecular sieve or heteropoly acid.
13. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step
(3) it is the first at 140-200 DEG C, reaction time 10min-10h that the condition of esterification, which occurs, for the long chain fatty acids and methanol
Alcohol and the mass ratio of long chain fatty acids are 0.1-2:1, and the mass ratio of catalyst and long chain fatty acids is 0.005-0.1:1.
14. a kind of method for producing biodiesel and triacetyl glycerine as described in claim 1, it is characterised in that step
(3) biodiesel described in is obtained by following separating technology:
For homogeneous catalysis system, be distilled to recover methanol, remaining thing liquid filtering or centrifugation obtain long chain fatty acids methyl esters and
Catalyst；For the catalyst system that solid catalyst participates in, solid catalyst is recovered by filtration first, is then distilled to recover methanol simultaneously
Obtain biodiesel.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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