Summary of the invention
The invention provides a kind of homogeneous phase, prepare method of bio-diesel oil continuously, operational condition is simple, can realize serialization production, and shortens the reaction times greatly, reduces temperature of reaction, improves equipment capacity, reduces production costs.
The present invention adopts following technical scheme to realize:
With natural fats and oils or frying waste oil, methyl alcohol, as the alkali metal hydroxide of catalyzer and can make mixed solution form homogeneous organic solvent mixed together, sending into temperature is in 30~50 ℃ of preheaters, preheating 1~30 minute, make it to dissolve each other fully, form homogeneous system, wherein organic solvent is an ethers, one or more mixtures in the ketone, it perhaps is the mixture of at least a ethers and/or ketone and at least a saturated alkane, this ethers, ketone is to acid, stable and the boiling point of alkali is below 150 ℃, the saturated alkane carbonatoms is between 6~9, boiling point is below 150 ℃, above-mentioned methyl alcohol and grease are 0.24~2: 1 by volume, organic solvent volume/grease weight=0.1L~4L/kg, catalyzer alkali metal hydroxide consumption accounts for 0.3%~2% of grease weight; It is 40~90 ℃ of pipeline reactors that mixed solution is sent into temperature by preheater, carries out continuous esterification, after 1~30 minute hybrid reaction, get final product biofuel and glycerine; Fractionation by distillation goes out methyl alcohol and organic solvent under normal pressure or decompression, again by the product separation jar, separates obtaining biofuel.
Natural fats and oils of the present invention, be vegetables oil and animal oil, comprise one or more mixtures in rapeseed oil, soybean oil, Oleum Gossypii semen, kostelezkya virginica oil, Jatropha curcas oil, tung oil, plam oil, Oleum Cocois, Semen Maydis oil, Oleum Helianthi, peanut oil, lard, butter, sheep oil, the fish oil, frying waste oil is the culinary art waste oil of above-mentioned natural fats and oils, and greasy acid number is less than 10.Natural fats and oils or frying waste oil raw material water content are lower than 1%, are preferably lower than 0.5%.
Used ethers or ketone are acetone, butanone, tetrahydrofuran (THF), isopropyl ether, 1, the 4-dioxane; Saturated alkane is normal hexane, isohexane, heptane, octane, hexanaphthene, nonane, ethers, ketone are stablized acid, alkali, and promptly under experiment condition, used ethers or ketone do not react, the transformation efficiency of its reaction is also very little even perhaps react, and can ignore.Normal pressure or decompression down the methyl alcohol that obtains of fractionation by distillation and organic solvent as raw material, again with grease with as the alkali metal hydroxide formation reaction raw materials of catalyzer.Normal pressure or decompression are vacuum tightness 0~0.5MPa.Alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
The biodiesel manufacture principle:
The used organic solvent of the present invention can make natural fats and oils or frying waste oil and methyl alcohol and alkali metal hydroxide mixed solution formation homogeneous system; Alkali metal hydroxide is the catalyzer of esterification or transesterification reaction.
Prior art is compared, and the present invention has following advantage:
(1) adding can make mixed solution form the homogeneous organic solvent in the reaction process of the present invention, strengthened the mutual solubility of natural fats and oils or frying waste oil and methyl alcohol, make methyl alcohol and natural fats and oils or frying waste oil form homogeneous system, thereby accelerated reaction speed, shorten the reaction times greatly, reduced temperature of reaction, reduced equipment requirements, make to be reflected at and be easy in the industrial production realize having the favorable industrial using value.
(2) organic solvent that uses in the reaction process of the present invention and the remaining methyl alcohol of reaction are through simple separation recycling capable of circulation.
(3) the invention solves traditional still, tank reactor in production operation intermittently or semicontinuous, automatization, serialization degree are not high, the energy consumption height, " run, leak, drip " phenomenon is serious, waste resource, problems such as contaminate environment.Realize the serialization of production technique, energy consumption is low, and running is efficient.
Specific embodiment
Embodiment 1
With natural fats and oils or frying waste oil, methyl alcohol, as the alkali metal hydroxide of catalyzer and can make mixed solution form homogeneous organic solvent mixed together, sending into temperature is in 30~90 ℃ of preheaters, preheating 1~30 minute, make it to dissolve each other fully, form homogeneous system, wherein organic solvent is an ethers, one or more mixtures in the ketone, it perhaps is the mixture of at least a ethers and/or ketone and at least a saturated alkane, this ethers, ketone is to acid, stable and the boiling point of alkali is below 150 ℃, the saturated alkane carbonatoms is between 6~9, boiling point is below 150 ℃, above-mentioned methyl alcohol and grease are 0.24~2: 1 by volume, organic solvent volume/grease weight=0.1L~4L/kg, catalyzer alkali metal hydroxide consumption accounts for 0.3%~2% of grease weight; It is 40~90 ℃ of pipeline reactors that mixed solution is sent into temperature by preheater, carries out continuous esterification, after 1~30 minute hybrid reaction, get final product biofuel and glycerine; Fractionation by distillation goes out methyl alcohol and organic solvent under normal pressure or decompression, again by the product separation jar, separates obtaining biofuel.Organic solvent can adopt the mixture of ethers, ethers in the present embodiment, as isopropyl ether, 1, the mixture of 4-dioxane, the perhaps mixture of tetrahydrofuran (THF), isopropyl ether, perhaps tetrahydrofuran (THF), 1, the mixture of 4-dioxane, perhaps tetrahydrofuran (THF), isopropyl ether, 1,4-dioxane mixture, its ratio be arbitrarily than; Ketone and ketone mixture, as the mixture of acetone, butanone, its ratio be arbitrarily than; Ethers, ketone mixture, as the mixture of butanone, isopropyl ether, the perhaps mixture of butanone, tetrahydrofuran (THF), the perhaps mixture of acetone, isopropyl ether, perhaps butanone, 1, the mixture of 4-dioxane, its ratio be arbitrarily than; The mixture of ethers and saturated alkane, mixture as tetrahydrofuran (THF), octane, the perhaps mixture of tetrahydrofuran (THF), heptane, perhaps butanone, tetrahydrofuran (THF), isopropyl ether, 1,4-dioxane, 60~90 ℃ the mixture of sherwood oil, perhaps isopropyl ether, 1, the mixture of 4-dioxane, No. 120 petroleum naphthas; Ketone and saturated alkane, as the mixture of acetone, heptane, octane, hexanaphthene, perhaps butanone, nonane, 60~90 ℃ the mixture of sherwood oil, or the mixture of acetone, butanone, heptane, octane; The perhaps mixture of ethers, ketone, saturated alkane, as tetrahydrofuran (THF), acetone, butanone, 1, the mixture of 4-dioxane, isohexane, heptane, octane, hexanaphthene, acetone, isopropyl ether, 1, the mixture of 4-dioxane, octane, hexanaphthene.
Natural fats and oils of the present invention, be vegetables oil and animal oil, comprise one or more mixtures in rapeseed oil, soybean oil, Oleum Gossypii semen, kostelezkya virginica oil, Jatropha curcas oil, tung oil, plam oil, Oleum Cocois, Semen Maydis oil, Oleum Helianthi, peanut oil, lard, butter, sheep oil, the fish oil, frying waste oil is the culinary art waste oil of above-mentioned natural fats and oils, and greasy acid number is less than 10.Natural fats and oils or frying waste oil raw material water content are lower than 1%, are preferably lower than 0.5%.
Used ethers or ketone are acetone, butanone, tetrahydrofuran (THF), isopropyl ether, 1, the 4-dioxane; Saturated alkane is normal hexane, isohexane, heptane, octane, hexanaphthene, nonane.Normal pressure or decompression down the methyl alcohol that obtains of fractionation by distillation and organic solvent as raw material, again with grease with as the alkali metal hydroxide formation reaction raw materials of catalyzer.Alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
Embodiment 2
At first the duct type preheater is preheated to 45 ℃, the pipeline reactor process furnace is heated to 65 ℃.Be that 0.1% soybean oil, methyl alcohol, tetrahydrofuran (THF) (1: 1.2: 0.7 by volume) and the sodium hydroxide that accounts for soybean oil weight 0.7% pump into the duct type preheater again with water content, flow velocity is 840ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 2 minutes, had formed thermograde between preheater and reactor, after 5 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is gone out tetrahydrofuran (THF) and residue methyl alcohol in that vacuum tightness 0~0.5MPa distillation is separable, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 97%.
Embodiment 3
At first the duct type preheater is preheated to 35 ℃, the pipeline reactor process furnace is heated to 62 ℃.With acid value of oil and fat be 8 again, water content is 0.8% salad frying waste oil, methyl alcohol, isopropyl ether (1: 1.7: 1.5 by volume) and accounts for salad to fry the potassium hydroxide of waste oil weight 1.8% and pump into the duct type preheater, flow velocity is 620ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 3 minutes, had formed thermograde between preheater and reactor, after 7 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out isopropyl ether and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 91%.
Embodiment 4
At first the duct type preheater is preheated to 40 ℃, the pipeline reactor process furnace is heated to 58 ℃.With acid value of oil and fat be 0.5 again, water content is 0.4% rapeseed oil: methyl alcohol: acetone: sherwood oil (1: 1.5: 0.5 by volume: 1) and the sodium hydroxide that accounts for grease weight 1% pump into the duct type preheater, flow velocity is 500ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 5 minutes, had formed thermograde between preheater and reactor,, entered distillation tower and separated after 6 minutes through the thorough mixing reaction.Mixed solution is distilled separable go out acetone, sherwood oil and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 93%.
Embodiment 5
At first the duct type preheater is preheated to 50 ℃, the pipeline reactor process furnace is heated to 70 ℃.Again soybean oil, methyl alcohol, tetrahydrofuran (THF) (1: 0.5: 0.4 by volume) and the sodium hydroxide that accounts for grease weight 0.5% are pumped into the duct type preheater, flow velocity is 780ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 1 minute, had formed thermograde between preheater and reactor, after 30 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out tetrahydrofuran (THF) and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 96.4%.
Embodiment 6
At first the duct type preheater is preheated to 35 ℃, the pipeline reactor process furnace is heated to 62 ℃.With acid value of oil and fat be 1.5 again, water content is 0.8% fish oil: methyl alcohol: isopropyl ether (1: 1.5: 1.2 by volume) and the potassium hydroxide that accounts for grease weight 1.2% pump into tubular reactor, and flow velocity is 650ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 3 minutes, had formed thermograde between preheater and reactor, after 20 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out isopropyl ether and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 92%.
Embodiment 7
At first the duct type preheater is preheated to 35 ℃, the pipeline reactor process furnace is heated to 62 ℃.With acid value of oil and fat be 3.5 again, water content is 0.4% sheep oil: methyl alcohol: isopropyl ether: isohexane (1: 1.5: 0.5 by volume: 1) and the potassium hydroxide that accounts for grease weight 1.5% pump into tubular reactor, flow velocity is 580ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 3 minutes, had formed thermograde between preheater and reactor, after 7 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out isopropyl ether, isohexane and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, and biodiesel production rate is more than 91%.
Embodiment 8
At first the duct type preheater is preheated to 40 ℃, the pipeline reactor process furnace is heated to 65 ℃.With acid value of oil and fat be 2 again, water content is 0.5% Semen Maydis oil, methyl alcohol, tetrahydrofuran (THF), normal hexane (1: 1: 0.5 by volume: 0.5) and the sodium hydroxide that accounts for grease weight 1% pump into the duct type preheater, flow velocity is 860ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 10 minutes, had formed thermograde between preheater and reactor, after 15 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out tetrahydrofuran (THF), normal hexane and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 94%.
Embodiment 9
At first the duct type preheater is preheated to 50 ℃, the pipeline reactor process furnace is heated to 85 ℃.With acid value of oil and fat be 1 again, water content is 0.2% Semen Maydis oil, methyl alcohol, 1,4-dioxane (1: 1: 0.7 by volume) and the sodium hydroxide that accounts for grease weight 0.9% pump into the duct type preheater, flow velocity is 770ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 10 minutes, had formed thermograde between preheater and reactor, after 15 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution distilled separablely go out 1,4-dioxane and residue methyl alcohol turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 95%.
Embodiment 10
At first the duct type preheater is preheated to 30 ℃, the pipeline reactor process furnace is heated to 60 ℃.Again with rapeseed oil, methyl alcohol, acetone, hexane (1: 1: 0.41 by volume: 0.59) and the sodium hydroxide that accounts for grease weight 1% pump into the duct type preheater, flow velocity is 600ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 8 minutes, had formed thermograde between preheater and reactor, after 15 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out acetone, hexane and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 96%.
Embodiment 11
At first the duct type preheater is preheated to 50 ℃, the pipeline reactor process furnace is heated to 70 ℃.Again with soybean oil, methyl alcohol, isopropyl ether, hexane (1: 1: 0.47 by volume: 0.53) and the sodium hydroxide that accounts for grease weight 1% pump into the duct type preheater, flow velocity is 800ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 5 minutes, had formed thermograde between preheater and reactor, after 10 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out isopropyl ether, hexane and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 95%.
Embodiment 12
At first the duct type preheater is preheated to 30 ℃, the pipeline reactor process furnace is heated to 65 ℃.Again with Oleum Gossypii semen, methyl alcohol, acetone, isopropyl ether (1: 1: 0.61 by volume: 0.39) and the sodium hydroxide that accounts for grease weight 1% pump into the duct type preheater, flow velocity is 740ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 10 minutes, had formed thermograde between preheater and reactor, after 15 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is distilled separable go out acetone, isopropyl ether and residue methyl alcohol, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 97%.
Embodiment 13
At first the duct type preheater is preheated to 40 ℃, the pipeline reactor process furnace is heated to 70 ℃.Again with soybean oil, methyl alcohol, isopropyl ether, soybean extracting solvent no.6 (1: 1.8: 2.2 by volume: 0.7) and the sodium hydroxide that accounts for soybean oil weight 0.7% pump into the duct type preheater, flow velocity is 840ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 30 minutes, had formed thermograde between preheater and reactor, after 5 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is gone out isopropyl ether, soybean extracting solvent no.6 and residue methyl alcohol in that vacuum tightness 0~0.5MPa distillation is separable, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 98%.
Embodiment 14
At first the duct type preheater is preheated to 50 ℃, the pipeline reactor process furnace is heated to 90 ℃.With water content be again 0.1% soybean oil, methyl alcohol, acetone, No. 120 petroleum naphthas (1: 1.2: 3 by volume: 0.7) and the sodium hydroxide that accounts for soybean oil weight 0.7% pump into the duct type preheater, flow velocity is 840ml/hr.Mixed solution preheating in preheater entered in the pipeline reactor after 1 minute, had formed thermograde between preheater and reactor, after 30 minutes, entered distillation tower through the thorough mixing reaction.Mixed solution is gone out acetone, No. 120 petroleum naphthas and residue methyl alcohol in that vacuum tightness 0~0.5MPa distillation is separable, turn back to recycle in the fresh feed pump after the condensation.Still liquid enters the product separation jar and leaves standstill, and separablely goes out biofuel and raw glycerine product, biodiesel production rate 96%.