CN103013676B - Method for reducing biodiesel crude product acid value, and biodiesel preparation method - Google Patents
Method for reducing biodiesel crude product acid value, and biodiesel preparation method Download PDFInfo
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- CN103013676B CN103013676B CN201110280398.5A CN201110280398A CN103013676B CN 103013676 B CN103013676 B CN 103013676B CN 201110280398 A CN201110280398 A CN 201110280398A CN 103013676 B CN103013676 B CN 103013676B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The present invention discloses a method for reducing a biodiesel crude product acid value, and a biodiesel preparation method, wherein the biodiesel crude product acid value is 3-20 mg KOH/g. The method comprises that: in the presence of a catalyst, a biodiesel crude product and a monohydric alcohol are subjected to a continuous contact reaction, wherein conditions of the contact reaction comprise that: a reaction temperature is 70-220 DEG C, a reaction pressure is 0.2-3 MPa, and an amount of the catalyst is 0.001-0.4 wt% of the biodiesel crude product. With the method, under mild conditions, the acid value of the high acid value biodiesel crude product can be substantially reduced by adopting a minimal amount of the catalyst, wherein preferably the acid value can be less than 0.8 mg KOH/g.
Description
Technical field
The present invention relates to a kind of method of biodiesel coarse product acid number and a kind of preparation method of biofuel of reducing.
Background technology
Biofuel can be carried out transesterification reaction by raw oil material and monohydroxy-alcohol and be made; in reacting coarse product, there is fatty acid ester; also have monoacylglycerol ester, two acyl glyceride, glycerine, and unreacted alcohol and raw oil material (main component is triglyceride level).In prior art, the preparation method of biofuel can be divided into base catalysis method, acid base catalysis method, enzyme catalysis method and supercritical methanol technology etc.
JP9-235573 discloses the discarded edible oil of a kind of use and methyl alcohol is prepared the method for diesel-fuel under the existence of sodium hydroxide, in natural fats and oils, conventionally contain free fatty acids, in the situation that free fatty acids is more, use base metal catalysts, can produce fatty acid soaps, base metal catalysts will be excessive and be made the difficulty of fatty acid ester layer and the separated change of glycerin layer like this.
CN102041177A discloses a kind of method of preparing biofuel, the method comprises that take pretreated animal grease, Vegetable oil lipoprotein is stock oil, in reactor by 4: 1-8: 1 molar ratio of methanol to oil adds methyl alcohol, the vitriol oil that under agitation adds the 3-5 % by weight of stock oil weight, at 75 ℃, react 2 hours, make in system acid number below 3mgKOH/g and complete pre-esterification; Then add in water and washing, dehydration impurity elimination, be dried, reenter reactor and be warming up to 75 ℃, under agitation add 3% NaOH methanol solution, making acid number in system to 1mgKOH/g, complete transesterify, obtaining coarse biodiesel after separating lower floor's glycerine methanol solution; Finally by crossing multiple-grade molecular distillation, obtain biofuel.
DE3444893 discloses a kind of method, adopt acid catalyst, at normal pressure, 50-120 ℃, free fatty acids and alcohol are carried out to esterification, oil plant is carried out to pre-esterification treatment, then under base metal catalysts, carry out transesterification reaction, but the acid catalyst of leaving over will neutralize by alkali, the amount of base metal catalysts can increase.
Adopt above-mentioned acid base catalysis method, make that work flow is elongated, energy consumption significantly rises, facility investment increases, and in addition, basic catalyst need be removed from product, has a large amount of waste water to produce, in addition, sweet oil recovery difficulty.
US5713965A discloses a kind ofly usings lipase as the method for biodiesel, and the method is included under the existence of lipase, with hexane, as solvent, grease and alcohol reaction is prepared to fatty acid methyl ester, i.e. diesel-fuel.
CN1472280A discloses a kind of method of utilizing glyceride stock biodiesel synthesis, and the method comprises usings short-chain aliphatic ester as acyl acceptor, utilizes biological enzyme bio-oil to carry out transesterification reaction production biofuel.
The deficiency that adopts above-mentioned enzymatic method to exist is: long reaction time, efficiency are lower, and enzyme is more expensive, and in high purity methanol easy inactivation.
CN1287572A discloses a kind of method of being manufactured fatty acid alkyl ester by fats, the method is that grease class is reacted with alcohol, in transesterification reaction, add the tri-glyceride being contained in grease class to manufacture the alkyl ester of lipid acid, it is characterized in that, at described alcohol, become in the atmosphere gas of supercritical state and make it reaction without a kind of in base metal catalysts or acid catalyst.Described temperature of reaction is 250-300 ℃, and reaction pressure is 3-15Mpa, and fatty acid methyl ester production rate is 54-60%.The production rate of the fatty acid methyl ester that employing the method prepares is lower, and there is no open how how the monoacylglycerol ester in reacting coarse product, two acyl glyceride, triglyceride level processing.For adopting continuous middle high-pressure legal system for biofuel, if do not use catalyzer, there is the lower problem of lipid acid monobasic alcohol ester yield.In addition, aforesaid method is to processing high acid value and also not adding explanation containing the reaction effect of the unrefined oil of high unsaponifiables.
By above-mentioned prior art, can find, because the acid number difference of raw oil material is very large, some raw oil material acid numbers can reach 160mgKOH/g, even higher, while using preparing biodiesel by using high acid number feed lipid, general last employing adds the method that alkali neutralizes and carries out deacidification reaction, otherwise, the acid number of biofuel is difficult to remarkable reduction, is more difficult to the standard of reach≤0.8mgKOH/g.
Summary of the invention
The object of the present invention is to provide that a kind of catalyst levels is few, reaction conditions is gentle and can significantly reduce method and a kind of method of preparing biofuel of high acid value biodiesel coarse product acid number.
To achieve these goals, the invention provides a kind of method that reduces biodiesel coarse product acid number, the acid number of described biodiesel coarse product is 3-20mgKOH/g, wherein, the method is included under the existence of catalyzer, and described biodiesel coarse product is reacted with monohydroxy-alcohol Continuous Contact, and described catalytic condition comprises: temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, the 0.001-0.4 % by weight that the consumption of described catalyzer is biodiesel coarse product.
In addition, the present invention also provides a kind of preparation method of biofuel, wherein, the biodiesel coarse product that it is 3-20mgKOH/g that the method comprises acid number carries out deacidification, and the biofuel product after deacidification is distilled, the described method that biodiesel coarse product is carried out to deacidification is method provided by the invention.
Adopt method of the present invention under relatively mild condition, and under the condition that adopts few catalyzer, can significantly reduce the acid number of the biodiesel coarse product with higher acid value.In addition, method of the present invention is specially adapted to adopting the deacidification value reaction of the biodiesel coarse product that foreign matter content raw oil material high, high acid value prepares, when adopting method of the present invention to prepare biofuel, without the raw oil material of preparation biofuel is carried out to pre-treatment, and the acid number of raw oil material is not required.In addition, the method of preparing biofuel of the present invention can make the acid number of biodiesel coarse product effectively be reduced before distillation procedure, preferably can reach the requirement of BD100 standard, and without again carry out deacidification after distillation, thereby greatly simplified operation, improve production efficiency, and reduced energy consumption.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the method of described reduction biodiesel coarse product acid number is included under the existence of catalyzer, by acid number, be 3-20mgKOH/g, the biodiesel coarse product that is preferably 3-15mgKOH/g reacts with monohydroxy-alcohol Continuous Contact, described catalytic condition comprises: temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, the 0.001-0.4 % by weight that the consumption of described catalyzer is biodiesel coarse product.
The present inventor is surprised to find that, under relatively mild reaction conditions, free fatty acids in the catalyzer biodiesel coarse product that effectively catalysis acid number is 3-20mgKOH/g of employing minute quantity and the esterification of monohydroxy-alcohol, significantly to reduce the acid number of described biodiesel coarse product, preferably can make the acid number of biofuel crude product reach below 0.8mgKOH/g.Infer that reason may be: described catalyzer can tie up under lower temperature, pressure and can be dissolved in and react in system with reactant, the performance of described catalyzer is fully played, therefore, can only adopt micro-catalyzer can effectively reduce the acid number of biodiesel coarse product.In addition, under described reaction conditions, the water of generation can effectively remove from oil phase, and thermodynamic(al)equilibrium is moved to product direction, makes reaction more thorough.
According to aforementioned techniques scheme of the present invention, can realize object of the present invention, according to the present invention, described catalytic condition comprises that temperature of reaction is 70-220 ℃, reaction pressure is 0.2-3MPa, the consumption of described catalyzer is the 0.001-0.4 % by weight of biodiesel coarse product, more abundant for what goal of the invention of the present invention was realized, under preferable case, described temperature of reaction is 100-190 ℃, 100-160 ℃ more preferably, described reaction pressure is 0.3-1Mpa, 0.4-0.7Mpa more preferably, the consumption of described catalyzer is the 0.01-0.2 % by weight of biodiesel coarse product, 0.02-0.1 % by weight more preferably.
According to the present invention, described temperature of reaction raises, reaction conversion ratio is higher, because from kinetics angle, temperature raises to be conducive to react and carries out, but reaction product is black, have burnt matter to produce, therefore, temperature of reaction is preferably and is less than or equal to 200 ℃, considering cost and effect, described temperature of reaction most preferably is 100-160 ℃.Improve pressure unfavorable to dewatering, make deacidification molecular balance be difficult to move to product direction, so it is lower that pressure should keep, therefore, described pressure is preferably more than or equals 0.2MPa, considering cost and effect, and described reaction pressure most preferably is 0.4-0.7Mpa.
The present invention is not particularly limited monohydroxy-alcohol and the mol ratio in the described biodiesel coarse product of lipid acid monobasic alcohol ester, generally, monohydroxy-alcohol is excessive, under preferable case, improve monohydroxy-alcohol and can further be beneficial to the mol ratio of described biodiesel coarse product in lipid acid monobasic alcohol ester the carrying out reacting, under preferable case, described monohydroxy-alcohol is 0.1-9 with take the mol ratio of described biodiesel coarse product of lipid acid monobasic alcohol ester: 1, further under preferable case, described monohydroxy-alcohol is 0.4-2 with take the mol ratio of described biodiesel coarse product of lipid acid monobasic alcohol ester: 1, most preferably be 0.6-2: 1.
According to the present invention, the various catalyzer for deacidification that described catalyzer can be known to the skilled person, for example, the most conventional can be for being selected from one or more in sulfuric acid, phosphoric acid, heteropolyacid and ionic liquid.Wherein, described heteropolyacid can be selected from one or more in phospho-wolframic acid, phospho-molybdic acid and the tungstosilicic acid of phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid and load.Described ionic liquid is preferably containing sulfonic ionic liquid.Described ionic liquid can be commercially available, and also can prepare according to the method for well known to a person skilled in the art (for example, described containing sulfonic ionic liquid can prepare according to the disclosed method of CN101759646A).In addition,, when adopting ionic liquid as catalyzer, can also add FeCl simultaneously
3, SnCl
4, ZnCl
4and Zn (NO
3)
2in one or more materials further to strengthen the catalytic activity of described ionic liquid.More preferably in situation, considering cost and effect, the present inventor finds to adopt one or more an acidic catalysts in sulfuric acid, phosphoric acid and heteropolyacid under condition of the present invention, to carry out deacidification can to make the acid number of biofuel be reduced to below 0.8mgKOH/g.
According to the present invention, described monohydroxy-alcohol refers to that carbonatoms is at the aliphatic monobasic alcohol of 1-6, for example, can be saturated alcohol (straight chain or containing the saturated alcohol of side chain) and/or unsaturated alcohol (straight chain or containing the unsaturated alcohol of side chain).Specifically can be selected from one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, vinyl carbinol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol and isomer thereof, more preferably methyl alcohol and/or ethanol.
According to the present invention, under the existence of catalyzer, described biodiesel coarse product is that Continuous Contact is reacted with monohydroxy-alcohol, and the reaction of described Continuous Contact can be carried out in the various reactors that can realize its Continuous Contact, for example, described reaction can be carried out in tubular reactor.Specifically, method provided by the invention adopts tubular reactor, biodiesel coarse product and monohydroxy-alcohol are sent into (send into respectively or its mixture is sent into) described tubular reactor from the bottom feed mouth of described bed tubular reactor, and described trace catalyst can enter reactor with raw material.Before raw material is offered to reactor, available preheater, by material preheating, also can directly enter reactor, if directly raw material is sent into reactor, so, reactor had both played the effect of preheater, also played the effect of reactor.Under preferable case, during the liquid of described biodiesel coarse product, volume space velocity is 0.1-5h
-1, further, under preferable case, during the liquid of described biodiesel coarse product, volume space velocity is 0.6-3h
-1, most preferably be 0.6-2h
-1.
According to the present invention, described acid number refers to, in and the quality (mg) of the required KOH of acidic component in 1 gram of organism.The size of acid number has reflected the number of sample Free Acid (mainly referring to lipid acid) content.
According to the present invention, the biodiesel coarse product that it is 3-20mgKOH/g that the preparation method of described biofuel comprises acid number carries out deacidification, and the biofuel product after deacidification is distilled, the described method that biodiesel coarse product is carried out to deacidification is aforesaid method of the present invention.
According to the present invention, prepare biodiesel coarse product, particularly acid number is higher, as can adopting, the method for the acid number biodiesel coarse product that is 3-20mgKOH/g well known to a person skilled in the art that any means carries out, because the acid number of the biodiesel coarse product obtaining is higher, do not meet national standard, therefore need to further carry out deacidification reaction, therefore, to preparing biodiesel coarse product raw oil material used, be not particularly limited, conventionally can utilize the scrap feed material grease that acid number is higher, on the one hand it is reused, can make at an easy rate the acid number of the biodiesel coarse product that acid number is higher be reduced to by method of the present invention on the other hand and meet national standard.
For example, in the present invention, described raw oil material can be various raw oil materials, as, acid number is more than or equal to 5mg KOH/g, be generally the glyceride stock of 10-200mg KOH/g, for example, described glyceride stock can be selected from one or more in sewer oil, acidification oil, catering trade abendoned oil and discarded animal oil.
As mentioned above, method of the present invention is specially adapted to adopting the deacidification value reaction of the biodiesel coarse product that foreign matter content raw oil material high, high acid value prepares, when adopting method of the present invention to prepare biofuel, without the raw oil material of preparation biofuel is carried out to pre-treatment, and the acid number of raw oil material is not required.
Conventionally; in employing, under high-temperature and high-pressure conditions, make raw oil material and monohydroxy-alcohol carry out transesterification and can carry out catalysis without catalyzer; but; the acid number of the biodiesel coarse product obtaining is higher; also can residual monoacylglycerol ester in crude product, two acyl glyceride, triglyceride level etc., therefore, adopt method of the present invention not only can reduce the acid number of thick product; can also further promote the further reaction of described residue, thereby improve the productive rate of biofuel.The preparation method of described biodiesel coarse product is included under 170-350 ℃, 3-10MPa condition, preferably under 190-230 ℃, 3-6Mpa condition by raw oil material and monohydroxy-alcohol contact reacts, described monohydroxy-alcohol is 3-60 with take the mol ratio of raw oil material of tri-glyceride: 1, be preferably 3-12: 1.
According to the present invention, the method of described underpressure distillation can adopt the method for well known to a person skilled in the art to carry out, the object of described underpressure distillation is the heavy impurity of removing wherein, further to obtain the biofuel product of purifying, actual conditions comprises, the temperature of described underpressure distillation can be 100-300 ℃, and pressure is preferably and is less than 0.1MPa, is more preferably less than 0.04Mpa.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will describe the present invention by embodiment.
In following embodiment, the measuring method of acid number is GB/T5530-2005.
The preparation method of biodiesel coarse product described in embodiment 1-6 and 9 example: under 253 ℃, 6MPa condition, be 130mgKOH/g by acid number, unsaponifiable matter content is stock oil and the methyl alcohol contact reacts of 3.9 % by weight; Methyl alcohol is 6: 1 with take the mol ratio of stock oil of tri-glyceride, and during the liquid of stock oil, volume space velocity is 1.2h
-1obtain the biodiesel coarse product that acid number is 8.5mgKOH/g, and in vacuum tightness, be 0.013MPa by described biodiesel coarse product, tower reactor temperature is to carry out underpressure distillation under the condition of 279 ℃, and the mass yield of biofuel is 85.1% (mass yield of biofuel=(by the quality of the quality/stock oil of the biofuel obtaining after biodiesel coarse product distillation) * 100%).
Embodiment 1
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid are sent in tubular reactor, and wherein, during the liquid of biodiesel coarse product, volume space velocity is 0.6h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.7: 1, take biodiesel coarse product charging as benchmark, sulphuric acid is 0.02 % by weight of biodiesel coarse product volume, in reactor, temperature is 160 ℃, pressure is 0.7Mpa, and the acid number of the biofuel product obtaining after reaction is 0.80mgKOH/g.
Embodiment 2
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid and phosphoric acid are sent in tubular reactor, and wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.7: 1, take biodiesel coarse product charging as benchmark, the add-on of sulfuric acid and phosphoric acid is 0.05 % by weight (weight ratio of sulfuric acid and phosphoric acid 3: 2) of biodiesel coarse product volume, in reactor, temperature is 140 ℃, pressure is 0.4Mpa, and the acid number of the biofuel product obtaining after reaction is 0.55mgKOH/g.Product after the deacidification obtaining is distilled under the distillation condition with identical in biodiesel coarse product preparation example, and the mass yield of the biofuel obtaining is 90.2%.
Embodiment 3
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid and phosphoric acid are sent in tubular reactor, and wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 0.6: 1, take biodiesel coarse product charging as benchmark, the add-on of sulfuric acid and phosphoric acid is 0.2 % by weight (weight ratio of sulfuric acid and phosphoric acid 3: 1) of biodiesel coarse product volume, in reactor, temperature is 100 ℃, pressure is 0.4Mpa, and the acid number of the biofuel product obtaining after reaction is 0.61mgKOH/g.
Embodiment 4
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid and phosphoric acid are sent in tubular reactor, and wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 0.6: 1, take biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.08 % by weight (weight ratio of sulfuric acid and phosphoric acid 9: 1) of biodiesel coarse product volume, in reactor, temperature is 112 ℃, pressure is 0.5Mpa, and the acid number of the biofuel product obtaining after reaction is 0.78mgKOH/g.
Embodiment 5
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid are sent in tubular reactor, and wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.7: 1, take biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.02 % by weight of biodiesel coarse product volume, in reactor, temperature is 187 ℃, pressure is 2.5Mpa, and the acid number of the biofuel product obtaining after reaction is 0.77mgKOH/g.
Embodiment 6
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, sulfuric acid are sent in tubular reactor, and wherein, the hourly space velocity of biodiesel coarse product is 1.2h
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.7: 1, take biodiesel coarse product charging as benchmark, the add-on of sulfuric acid is 0.02 % by weight of biodiesel coarse product volume, in reactor, temperature is 187 ℃, pressure is 1.0Mpa, and the acid number of the biofuel product obtaining after reaction is 0.75mgKOH/g.
Embodiment 7
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
By biodiesel coarse product, (acid number is 12.3mgKOH/g, under the distillation condition with identical in biodiesel coarse product preparation example, distill, the mass yield of biofuel is 83%), methyl alcohol, phospho-wolframic acid is provided in tubular reactor, wherein, volume space velocity is 1.2h during the liquid of biodiesel coarse product
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.9: 1, take biodiesel coarse product charging as benchmark, the add-on of phospho-wolframic acid is 0.1 % by weight of biodiesel coarse product volume, in reactor, temperature is 160 ℃, pressure is 0.4Mpa, the acid number of the biofuel product obtaining after reaction is 1.70mgKOH/g, product after the deacidification obtaining is distilled under the distillation condition with identical in biodiesel coarse product preparation example, and the mass yield of the biofuel obtaining is 90.1%.
Embodiment 8
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
By acid number, be that 4.2mgKOH/g biodiesel coarse product, methyl alcohol, phospho-wolframic acid are provided in tubular reactor, wherein, volume space velocity 1.2h during the liquid of biodiesel coarse product
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 1.2: 1, take biodiesel coarse product charging as benchmark, phospho-wolframic acid add-on is 0.2 % by weight of biodiesel coarse product, in reactor, temperature is 160 ℃, pressure is 0.5Mpa, and the acid number of the biofuel product obtaining after reaction is 0.74mgKOH/g.
Embodiment 9
The present embodiment is for illustrating the method for reduction biodiesel coarse product acid number provided by the invention.
The biodiesel coarse product that is 8.5mgKOH/g by acid number, methyl alcohol, 1-butyl-pyridinium Witco 1298 Soft Acid ionic liquid (preparing according to CN101759646A embodiment 6) and tin chloride (tin chloride is 7 % by weight of described ionic liquid weight) are sent in tubular reactor, wherein, volume space velocity is 1h during the liquid of biodiesel coarse product
-1, methyl alcohol and the mol ratio of described biodiesel coarse product of fatty acid methyl ester of take be 7.6: 1, take biodiesel coarse product charging as benchmark, ionic liquid add-on is 0.4 % by weight of biodiesel coarse product volume, in reactor, temperature is 170 ℃, pressure is 0.7Mpa, and the acid number of the biofuel product obtaining after reaction is 2.49mgKOH/g.
Comparative example 1
This comparative example is for illustrating the acid reduction method of the biodiesel coarse product of prior art.
According to the method for the disclosed embodiment 1 of CN102041177, oil plant is preheating in reactor after 60 ℃, according to oil plant, add 500Kg, methyl alcohol adds 83Kg, under agitation add the vitriol oil, vitriol oil add-on is 4 % by weight of oil plant weight, makes temperature of reaction kettle remain on 75 ℃, react 2 hours, in system, acid number is 3mgKOH/g.
From the above results, can find out, adopt the method for the present invention can be under relatively mild condition, and under the condition that adopts few catalyzer and the acid number that can significantly reduce the biodiesel coarse product with higher acid value in higher liquid hourly space velocity (shorter reaction time).
In addition, the method of preparing biofuel of the present invention, select suitable catalyzer and processing condition, can before distillation procedure, effectively reduce the acid number of biodiesel coarse product, more preferably can reach the requirement of BD100 standard, and without again carry out loaded down with trivial details deacidification after distillation, and only need by simple underpressure distillation, after removing heavy impurity, can obtain qualified biofuel product, and can improve the yield of biofuel, thereby greatly simplified operation, improved production efficiency, and reduced energy consumption.
Claims (9)
1. a method that reduces biodiesel coarse product acid number, the acid number of described biodiesel coarse product is 3-20mgKOH/g, it is characterized in that, the method is included under the existence of catalyzer, described biodiesel coarse product is reacted with monohydroxy-alcohol Continuous Contact, described catalytic condition comprises: temperature of reaction is 70-220 ℃, and reaction pressure is 0.2-3MPa, the 0.001-0.4 % by weight that the consumption of described catalyzer is biodiesel coarse product; Described catalyzer is selected from one or more in sulfuric acid, phosphoric acid, phospho-wolframic acid, phospho-molybdic acid, tungstosilicic acid and ionic liquid; Described ionic liquid is for containing sulfonic ionic liquid.
2. method according to claim 1, wherein, the 0.01-0.2 % by weight that the consumption of described catalyzer is biodiesel coarse product.
3. method according to claim 1, wherein, described reaction is carried out in tubular reactor.
4. according to the method described in claim 1 or 3, wherein, described catalytic condition also comprises: volume space velocity 0.1-5h during the liquid of described biodiesel coarse product
-1, monohydroxy-alcohol is 0.1-9:1 with take the mol ratio of described biodiesel coarse product of lipid acid monobasic alcohol ester.
5. method according to claim 4, wherein, during the liquid of biodiesel coarse product, volume space velocity is 0.6-3h
-1, monohydroxy-alcohol is 0.4-2:1 with take the mol ratio of described biodiesel coarse product of lipid acid monobasic alcohol ester.
6. method according to claim 1, wherein, temperature of reaction is 100-160 ℃, reaction pressure is 0.3-0.7MPa.
7. method according to claim 4, wherein, described monohydroxy-alcohol is that carbonatoms is the aliphatic monobasic alcohol of 1-6.
8. the preparation method of a biofuel, it is characterized in that, the biodiesel coarse product that it is 3-20mgKOH/g that the method comprises acid number carries out deacidification, and the biofuel product after deacidification is carried out to underpressure distillation, the described method that biodiesel coarse product is carried out to deacidification is the method described in any one in claim 1-7.
9. method according to claim 8, wherein, the preparation method of described biodiesel coarse product is included under 170-350 ℃, 3-10MPa condition, by raw oil material and monohydroxy-alcohol contact reacts; Monohydroxy-alcohol is 3-60:1 with take the mol ratio of raw oil material of tri-glyceride; The acid number of described raw oil material is 10-200mgKOH/g.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110280398.5A CN103013676B (en) | 2011-09-20 | 2011-09-20 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
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| CN201110280398.5A CN103013676B (en) | 2011-09-20 | 2011-09-20 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
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| Publication Number | Publication Date |
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| CN103013676A CN103013676A (en) | 2013-04-03 |
| CN103013676B true CN103013676B (en) | 2014-12-03 |
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| CN105199857B (en) * | 2014-06-25 | 2019-04-16 | 中国石油化工股份有限公司 | A method of improving biodiesel yield |
| CN104194948B (en) * | 2014-09-02 | 2017-01-11 | 辽宁石油化工大学 | Method for catalyzing phosphotungstic acid ionic liquid to prepare biodiesel |
| KR20160140138A (en) | 2015-05-29 | 2016-12-07 | 한국에너지기술연구원 | A method for removing organic acid of crude oil using gas hydrate formation inhibitors and catalysts |
| KR101696773B1 (en) * | 2015-12-01 | 2017-01-16 | 한국에너지기술연구원 | A method for removal of organic acids in crude oil by using catalyst and glycerol or their derivatives |
| CN110819445B (en) * | 2018-08-09 | 2023-05-02 | 丰益(上海)生物技术研发中心有限公司 | Method for removing polycyclic aromatic hydrocarbon from grease |
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