CN101089127A - Biodiesel oil producing process - Google Patents
Biodiesel oil producing process Download PDFInfo
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- CN101089127A CN101089127A CNA200610046933XA CN200610046933A CN101089127A CN 101089127 A CN101089127 A CN 101089127A CN A200610046933X A CNA200610046933X A CN A200610046933XA CN 200610046933 A CN200610046933 A CN 200610046933A CN 101089127 A CN101089127 A CN 101089127A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The present invention relates to process of producing biodiesel oil with fatty triglyceride, especially with animal and vegetable oil and grease. Biodiesel oil is produced inside a high efficiency bumping flow reactor, in the presence of inorganic alkali or organic alkali catalyst, under mild condition, and in high conversion rate, with the organic alkali catalyst being used circularly. Compared with available technology, the process of the present invention has the advantages of simple flow path, mild condition, high conversion rate, less side products, capacity of utilizing various kinds of animal and vegetable oil and grease, etc.
Description
Technical field
The present invention relates to a kind of production method of biofuel, particularly from fatty acid triglyceride, especially driven, vegetable tallow and oil, production method of bio-diesel oil.
Background technology
Fatty acid triglyceride, particularly animal and plant fat and oil carry out the monoester that transesterification reaction obtains with the lower molecular weight monohydroxy-alcohol, have similar character to the diesel oil that obtains from petroleum fractions, can be used as fuel and use, generally the fuel that will obtain in this way is called biofuel.
The biofuel of producing by greasy transesterification reaction has the following advantages: 1) good environmental protection characteristic is arranged.The biofuel sulphur content is low, does not also contain the aromatic hydrocarbon that environment is polluted.2) engine cold-starting performance is preferably arranged, condensation point reaches-20 ℃ when additive-free.3) lubricity is preferably arranged, can reduce the wear rate of oil injection pump, engine cylinder-body and connecting rod, prolong its work-ing life.4) good safety performance is arranged, its flash-point height does not belong to hazardous substance.5) good fuel performance is arranged, its cetane value height, combustionproperty is better than ordinary diesel oil.6) has recyclability.Biofuel is as a kind of renewable energy source, and its resource can be inexhausted.
CN1408701A discloses a kind of method and apparatus for preparing fatty acid ester.Under the condition of supercritical state and catalyzer existence, use the reactor of this invention, prepare fatty acid ester.Wherein reactor is returned in the reaction mixture recirculation that contains unreacted reactant and/or intermediate product.The preferred temperature of this method is 240 ℃～400 ℃, and preferred temperature is 245 ℃～350 ℃, and preferred reaction pressure is 0.5MPa～25MPa, and preferred reaction pressure is 2MPa～22MPa, preferred especially 8MPa～20 MPa.This method has increased the reaction interface area, has improved transformation efficiency.CN1408701A also discloses a kind of method of fatty acid ester and fuel of fatty acid esters of preparing.This fatty acid ester is in the presence of catalyst-free, grease and alcohol both one of be under the condition of supercritical state, grease and pure prepared in reaction.This method preferable reaction temperature is no more than 400 ℃, and preferred reaction pressure is 0.4MPa～25.0MPa.Because above two kinds of methods are all carried out under High Temperature High Pressure, can cause the cracking of animal and plant grease, have the high problem of cost of equipment simultaneously.
CN1230945A discloses a kind of from fatty acid triglyceride, especially animal or plant fat and oil, in the presence of homogeneous phase or different-phase catalyst with the method for a kind of lower molecular weight monohydroxy-alcohol by transesterification production fatty acid ester.The fatty acid ester that generates according to this method is extracted from reaction mixture by a kind of extraction agent, and the fatty acid ester purity that obtains like this is higher.The most handy a kind of to have reduced temperature 20 ℃ the time about 0.7 as extraction agent, preferably is equal to or greater than 0.7 low-pressure gas.Preferred extraction agent is carbonic acid gas, propane, butane, dme, ethyl acetate or their mixture.This method make technological process become complicated, and the grease transformation efficiency is still lower in order to improve the yield of product.
Because alcohol is poor with animal and plant grease mutual solubility, reaction system is two-phase, and transesterification reaction is only carried out at the interface, and speed of reaction is low, and in order to improve transformation efficiency, CN1496398A discloses a kind of method that obtains fatty acid ester by alcoholysis from the triacylglycerol ester.In order to accelerate ester-exchange reaction, add a certain amount of at least a alkanol fatty acid ester in initial reaction phase, especially monobasic chain triacontanol ester, preferred methyl esters, ethyl ester and/or ethyl ester, in fat that pending transesterify is arranged and/or oil, so that the reaction mixture that generates thus is made of single-phase.Thereby make this process just keep high reaction rate from beginning.And solved the problem of lipid acid to the reaction conversion ratio influence.Because the starting stage of transesterify can be avoided or shorten to this method, shortened the reaction times, but the selectivity and the transformation efficiency of transesterification reaction there is not too big contribution; Reaction needed is carried out cyclical operation, has increased energy consumption; The selected catalyzer price of reaction process height; Ester-exchange reaction itself generates water, and water is poisonous to reacting selected catalyzer, so catalyst life is short; The catalytic activity salt that is insoluble to reaction mixture will be deposited on the carrier, and catalyzer is made and/or the sepn process complexity.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of novel method of production biofuel.The inventive method has adopted impact flow reactor efficiently, is catalyzer with mineral alkali or organic bases, under the demulcent condition, can obtain very high transformation efficiency.
The production process of biofuel of the present invention comprises following content: with animal and vegetable oil or fat that contains fatty acid triglycercide and the monohydroxy-alcohol with 1～8 carbon atom is raw material, adopt impact flow reactor, catalyzer comprises mineral alkali or organic bases, production biofuel under the demulcent reaction conditions.
Mineral alkali can be one or more of sodium hydroxide, potassium hydroxide, yellow soda ash, and add-on is 0.1%～50% of raw material fat or a weight of oil, and is preferred 0.5%～10%, most preferably 0.5%～5%.Organic bases is the organic amine material that contains 1～10 carbon atom, and add-on is 0.1%～100% of raw material fat or a weight of oil.Preferred 1%～50%, most preferably 5%～10%.It also can be the mixture of two kinds of catalyzer arbitrary proportions.
Transesterification reaction is 40 ℃～200 ℃ of temperature ranges, and preferred 50 ℃～150 ℃, what override was selected is to carry out between 60 ℃～130 ℃.Reaction is to carry out to the pressure of the vapour pressure of lower molecular weight monohydroxy-alcohol at normal pressure.
Any fatty acid glyceryl ester can be made raw material of the present invention, and especially preferred is to have 10～22 carbon atoms with in animal and plant fat and/or the oil, particularly those fatty acid radicals, and preferably 12～18 carbon atoms makes raw material.As the example of vegetable raw material can enumerate soybean oil, rapeseed oil, sunflower seed oil, peanut oil, Oleum Gossypii semen, plam oil, Semen Lini oil, Viscotrol C, beet oil and olive wet goods one or more.The example of animal raw materials such as butter, lard one or both.
The present invention uses lower molecular weight monohydroxy-alcohol and fatty acid glyceryl ester with 1～8 carbon atom to carry out transesterification reaction.The alcohol that preferably has 1～6 carbon atom is especially preferably with methyl alcohol or ethanol.
Be applicable to that organic bases of the present invention comprises: the mixture of one or more of methylamine, dimethylamine, Trimethylamine 99, third rare amine, the rare amine of dipropyl, 3 third rare amine, Isopropylamine, Diisopropylamine, ethamine, diethylamine, triethylamine, 2-DEHA, propylamine, n-Butyl Amine 99, t-butylamine, sec-butylamine, monoethanolamine.What preferentially select is a kind of or mixture of ethamine, diethylamine, Diisopropylamine.
Continous way operation or batch operation are adopted in reaction, and continous way operation hourly space velocity is generally 0.2～10h-1, and can set up the material circulation between impact flow reactor outlet and inlet, and the recycle stock amount is 1%～500% of a feed weight.The batch operation the reaction time is generally 0.1～5h.
When adopting operate continuously, under required temperature of reaction, successive feeds reaction mass in the impact flow reactor according to certain ratio, reaction product is discharged continuously, the product of discharging can be gone out unreacted alcohols material and catalyst separating through distillation procedure, recycles then.Through the reaction product after the distillation, standing separation, the upper strata ester promptly can be used as the biofuel product mutually and uses, and lower floor is that the glycerine of purity more than 82% can be used as the byproduct sale.Sometimes the reaction product of discharging continuously is without above-mentioned distillation procedure, and direct standing separation can obtain biofuel product and purity and be the glycerine more than 82%.
When adopting periodical operation, reaction raw materials fatty acid glyceryl ester, lower molecular weight monohydroxy-alcohol and catalyzer are put into impact flow reactor in the lump, be warmed up to required temperature of reaction then, react.Reaction is emitted reaction product after finishing, and carries out distillation procedure, unreacted alcohols material can be separated, and recirculation is used.Standing separation then, the upper strata that obtains promptly is the biofuel product.Lower floor is that to contain purity be glycerine phase more than 82%.The reaction product of emitting also can be without above-mentioned distillation procedure, and direct standing separation can obtain biofuel product and purity and be the glycerine more than 82%.(among the present invention not the percentage composition of clear and definite benchmark be weight percentage)
According to the present invention, transesterification reaction is to carry out under the pressure between the vapour pressure of selected alcohol at normal pressure.Generally arrive 5.0MPa, preferred 0.10MPa～2.0MPa at normal pressure.Suitable pressure can increase the reaction interface area, improves greasy transformation efficiency.
According to implementation method of the present invention, the mol ratio that transesterification reaction is chosen lower molecular weight monohydroxy-alcohol and animal and plant fat and oil is 3～50, and is preferred 5～30, and what override was selected is 5～15.But find that by test when the add-on of monohydroxy-alcohol was slightly larger than theoretical amount, the selectivity of reaction and transformation efficiency all had raising.
Through discovering in a large number, raw material fat or the mutual solubility between oil and the lower alcohol used in the production of biodiesel process are relatively poor, and reaction only takes place at the two-phase interface place, causes speed of response lower, and transformation efficiency can't improve.The inventive method has increased the mutual solubility of fatty acid triglyceride and lower molecular weight monohydroxy-alcohol by adopting impact flow reactor, has improved mass-transfer efficiency, has accelerated speed of response, has improved greasy transformation efficiency, has reduced the reaction severity.In reaction process, adopt organic alkali catalyst to recycle simultaneously, solved the pollution problem of catalyzer.Therefore, reduced the treating process of product and by product, simplified technical process, low production cost and facility investment.It should be noted that especially, the ester that the present invention obtains mutually in, purpose product (as methyl esters) content unexpectedly improves, generally can reach more than 95%, just the purpose product selectivity is high especially, need the amount of round-robin monoglyceride and triglyceride to significantly reduce, the result is that the reactor of identical scale can be handled more raw materials, and efficient improves greatly.In addition, the boiling point and the methyl alcohol of the organic alkali catalyst that the present invention adopts are close, can separate simultaneously with unreacted methanol, recycle, and have avoided the pollution to product of the separation of catalyzer and catalyzer.
Description of drawings
Fig. 1 is that the present invention adopts the impact flow reactor structural representation.
Fig. 2,3,4,5 is reaction system continuous operation process schematic flow sheet of the present invention.
Embodiment
As shown in Figure 1, impact flow reactor of the present invention comprises: locate and be submerged in the material two guide shells 3,5 and coaxial respectively and be installed in two feed-pipes 1,6 in two guide shells symmetrically to being installed in nearly two ends, container 4 middle parts respectively with becoming.The process stream of packing in the container 1 is the useful volume district of reaction, in order to improve flow efficiency, the cylindrical shell making that container 4 usefulness are circular.Under the promotion of the material of material in two feed-pipes in the guide shell respectively from two ends through guide shell 3,5 high speed flow to container 4 centers, and clash in opposite directions in the center, around impact surface, form impingement region.In this district from relative movement violent between the stream of different directions group make between stream group with liquid phase between effectively contact and mix, carry out transesterification reaction.Behind the bump, fluid returns two ends through the ring casing between guide shell 3,5 and container 4 inwalls, and the mass transport that is fed again then in the pipe 1,7 flows to container 4 centers and bump, circulation so repeatedly once more by guide shell 3,5.Meanwhile transesterification reaction also can take place in material on impact surface, and this perfect mixing effect of circulation in opposite directions makes oil and alcohol reach the purpose that mixes, thereby improved rate of mass transfer and transformation efficiency.The recycle stock handling equipment (as pump) of impact flow reactor can adopt one or several.
As Fig. 2,3,4, shown in 5, to participate in the material of reaction according to stoichiometric ratio, with pump or other equipment for liquid transportation material is input among premix tank D or the tundish C respectively, carry out pre-mixing, then by pump or other equipment for liquid transportation, be input to the opening for feed 1 of impact flow reactor, 7, feed stream under pressure high speed through guide shell 3,5 flow to container 4 centers, and clash in opposite directions in the center, around impact surface, form impingement region, material behind the process bump is from two side outlets 2,6 flow to tundish C, be input to the opening for feed 1 of impact flow reactor again by pump, 7, clash into once more, come controlling reactor pressure by pressure-regulator A, thus uniform mixing generation transesterification reaction.The reaction mass of discharging from pressure-regulator A directly carries out distillation procedure, unreacted alcohols material can be separated, and recycles then.Through the reaction product after the distillation, standing separation, the upper strata ester promptly can be used as the biofuel product mutually and uses, and lower floor is that the glycerine of purity more than 80% can be used as the byproduct sale.Sometimes the reaction product of discharging continuously is without above-mentioned distillation procedure, and direct standing separation can obtain purity and be biofuel product more than 95% and purity and be the glycerine more than 80%.
Further specify method of the present invention and effect below by embodiment and comparative example.
Embodiment 1
Is that 10 ratio is mixed with methyl alcohol and Oleum Gossypii semen according to the mol ratio of methyl alcohol and Oleum Gossypii semen, adds the diethylamine of 10% (accounting for Oleum Gossypii semen weight) then, and equaling the percussion flow reaction volume with the feeding rate of Oleum Gossypii semen (is that the feed volume air speed is 1h
-1, also be to be 1h in the reaction times), Oleum Gossypii semen and methyl alcohol are squeezed into impact flow reactor by pump, transesterification reaction takes place by bump.The recycle stock amount is 95% of an inlet amount.Control reaction temperature is 130 ℃, reaction pressure is 0.8MPa, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 90.5%.The glycerol content of lower floor's glycerine in mutually is 78%.Impact flow reactor is the impact flow reactor of Fig. 1.
According to the method for embodiment 1, just feeding rate is 1/2nd of an impact flow reactor, and the recycle stock amount still is 95% of an inlet amount.Pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 97%, and the fatty acid ester content of middle methyl esters mutually is 93.8%.The glycerol content of lower floor's glycerine in mutually is 80%.
According to the method for embodiment 1, feeding rate is the ratio of impact flow reactor volumetrical 1/4th, and recycle stock speed is 95% of inlet amount.Pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 75%.
According to the method for embodiment 1, feeding rate is the ratio of impact flow reactor volumetrical 1/5th, and recycle stock speed is 200% of inlet amount.Pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 85%.The glycerol content of lower floor's glycerine in mutually is 70%.
Method according to embodiment 1, change Oleum Gossypii semen into salad oil, the diethylamine that adds 20% (accounting for salad oil weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 95%.The glycerol content of lower floor's glycerine in mutually is 75%.
Method according to embodiment 1, the diethylamine that adds 30% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 92%.The glycerol content of lower floor's glycerine in mutually is 70%.
Method according to embodiment 1, the diethylamine that adds 50% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 85%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 8
Method according to embodiment 1, the diethylamine that adds 80% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 80%.The glycerol content of lower floor's glycerine in mutually is 70%.
Embodiment 9
According to the method for embodiment 1, add the diethylamine of 5% (accounting for Oleum Gossypii semen weight) then, feeding rate is 1/2nd of an impact flow reactor, the recycle stock amount still is 95% of an inlet amount.Pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 95%.The glycerol content of lower floor's glycerine in mutually is 81%.
Embodiment 10
Method according to embodiment 1, the Diisopropylamine that adds 10% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 85%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 11
Method according to embodiment 1, the Diisopropylamine that adds 30% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 70%.
Embodiment 12
Method according to embodiment 1, the Diisopropylamine that adds 50% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 80%.The glycerol content of lower floor's glycerine in mutually is 68%.
Embodiment 13
Method according to embodiment 1, the Diisopropylamine that adds 90% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 75%.The glycerol content of lower floor's glycerine in mutually is 70%.
Embodiment 14
Method according to embodiment 1, the Diisopropylamine that adds 5% (accounting for Oleum Gossypii semen weight) then, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 13
Method according to embodiment 1, just the mol ratio of methyl alcohol and Oleum Gossypii semen is 20, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 95%.The glycerol content of lower floor's glycerine in mutually is 79%.
Embodiment 16
Method according to embodiment 1, just the mol ratio of methyl alcohol and Oleum Gossypii semen is 50, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 72%.
Embodiment 17
Method according to embodiment 1, just changing Oleum Gossypii semen into rape seed oil passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 95%.The glycerol content of lower floor's glycerine in mutually is 79%.
Embodiment 18
Method according to embodiment 1, just changing Oleum Gossypii semen into soya-bean oil passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 19
Method according to embodiment 1, just change diethylamine into propylamine, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 90%, and the fatty acid ester content of middle methyl esters mutually is 85%.The glycerol content of lower floor's glycerine in mutually is 70%.
Embodiment 20
Method according to embodiment 1, just changing Oleum Gossypii semen into sunflower seed oil passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 93%.The glycerol content of lower floor's glycerine in mutually is 74.5%.
Embodiment 21
Method according to embodiment 1, just changing Oleum Gossypii semen into Viscotrol C passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 97%, and the fatty acid ester content of middle methyl esters mutually is 94%.The glycerol content of lower floor's glycerine in mutually is 76%.
Embodiment 22
Method according to embodiment 1, just changing Oleum Gossypii semen into lard passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 92%.The glycerol content of lower floor's glycerine in mutually is 74%.
Embodiment 23
With potassium hydroxide (account for respectively Oleum Gossypii semen weight 1%, 10%) and methanol mixed, the mol ratio that adds methyl alcohol and Oleum Gossypii semen then is 10 Oleum Gossypii semen, behind the thorough mixing, squeezes into impact flow reactor by pump, by bump transesterification reaction takes place, the recycle stock amount is 100% of an inlet amount.Control reaction temperature is 130 ℃, reaction pressure is 0.8MPa, reaction times is 1 hour, reaction is emitted reaction product after finishing, and passes through standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, record the fatty acid triglycercide transformation efficiency and be 100%, the fatty acid ester content of middle methyl esters mutually is respectively 96%, 97%.The glycerol content of lower floor's glycerine in mutually is respectively 80%, 82%.
Embodiment 24
Method according to embodiment 1, just impact flow reactor adopts disclosed vertical circulation impact flow reactor among the CN 2659539Y, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 98%, and the fatty acid ester content of middle methyl esters mutually is 94%.The glycerol content of lower floor's glycerine in mutually is 81%.
Embodiment 25
Method according to embodiment 1, just the mol ratio of methyl alcohol and Oleum Gossypii semen is 20, impact flow reactor is adopted disclosed sinking circulation impact flow reactor among the CN2455353Y, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 92%.The glycerol content of lower floor's glycerine in mutually is 79%.
Embodiment 26
Method according to embodiment 1, it is 100 ℃ just with temperature of reaction, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 94%, and the fatty acid ester content of middle methyl esters mutually is 90%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 27
Method according to embodiment 1, it is 60 ℃ just with temperature of reaction, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 85%, and the fatty acid ester content of middle methyl esters mutually is 78.5%.The glycerol content of lower floor's glycerine in mutually is 75%.
Embodiment 28
Method according to embodiment 1, just change methyl alcohol into ethanol, pass through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle ethyl ester mutually is 95%.The glycerol content of lower floor's glycerine in mutually is 80%.
Embodiment 29
Method according to embodiment 1, just change methyl alcohol into ethanol, ethanol and greasy mol ratio are 15, temperature of reaction is 120 ℃, and reaction pressure is 0.5MPa, passes through standing separation from the effusive reaction product of impact flow reactor discharge port, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 99%, and the fatty acid ester content of middle ethyl ester mutually is 94.5%.The glycerol content of lower floor's glycerine in mutually is 80.5%.
Embodiment 30
Method according to embodiment 1, just change oleum gossypii seminis into rape seed oil, the feeding rate of rape seed oil is 1/4th of a static mixer volume, temperature of reaction is 150 ℃, and reaction pressure is 1.0MPa, passes through standing separation from the effusive reaction product of impact flow reactor, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 92.5%.The glycerol content of lower floor's glycerine in mutually is 74.5%.
Embodiment 31
Method according to embodiment 1, temperature of reaction is 200 ℃, reaction pressure is 1.5MPa, pass through standing separation from the effusive reaction product of impact flow reactor, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is 89%.The glycerol content of lower floor's glycerine in mutually is 71%.
Comparative example 1
Soybean salad oil 100 gram, methyl alcohol 50 grams, diethylamine 20 grams are joined in 500 milliliters of withstand voltage glass flask, stir, be heated to 130 ℃ with the stirring velocity of 700rpm, this moment gauge pressure 0.65MPa.Continue down to stir at 130 ℃, reacted 3 hours.React and finish the back by standing separation, obtain fatty acid ester phase (upper strata), utilize the GC-14B gas chromatograph analysis of leading Tianjin company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 92%.From comparative example 1 and embodiment 5 as can be seen, under the close situation of catalyst levels, the inventive method can reach better reaction effect (increase of purpose product selectivity) in the short reaction times, improved production efficiency greatly.
Comparative example 2
Press comparative example 1 method, just change soybean salad oil into Oleum Gossypii semen, catalyzer diethylamine add-on is 50 grams.Product fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 80%.From comparative example 2 and embodiment 7 as can be seen, under the close situation of catalyst levels, the inventive method can reach better reaction effect (increase of purpose product selectivity) in the short reaction times, improved production efficiency greatly.
Comparative example 3
Press comparative example 1 method, just do not add the catalyzer diethylamine, raw material is an Oleum Gossypii semen, and product fatty acid triglycercide transformation efficiency is 90%, and the fatty acid ester content of middle methyl esters mutually is 78%.Comparative example 3 is compared with embodiment 31, and under the situation of not using catalyzer, the inventive method can reach better reaction effect in the shorter reaction times.
Claims (10)
1, a kind of production method of biofuel, comprise following content: with animal and vegetable oil or fat that contains fatty acid triglycercide and the monohydroxy-alcohol with 1～8 carbon atom is raw material, adopt impact flow reactor, catalyzer comprises mineral alkali or organic bases, production biofuel under the demulcent reaction conditions; Wherein mineral alkali is one or more of sodium hydroxide, potassium hydroxide, yellow soda ash, add-on is 0.1%～50% of raw material fat or a weight of oil, organic bases is the organic amine material that contains 1～10 carbon atom, and add-on is 0.1%～100% of raw material fat or a weight of oil.
2, in accordance with the method for claim 1, it is characterized in that described mineral alkali add-on is 0.5%～10% of raw material fat or a weight of oil, the organic bases add-on is 1%～50% of raw material fat or a weight of oil.
3, in accordance with the method for claim 1, it is characterized in that described mineral alkali add-on is 0.5%～5% of raw material fat or a weight of oil, the organic bases add-on is 5%～10% of raw material fat or a weight of oil.
4, in accordance with the method for claim 1, it is characterized in that 40 ℃～200 ℃ of described transesterification reaction temperature scopes.
5, in accordance with the method for claim 1, it is characterized in that described transesterification reaction temperature scope is 50 ℃～150 ℃.
6, in accordance with the method for claim 1, it is characterized in that described transesterification reaction pressure is that normal pressure is to 5.0MPa.
7, in accordance with the method for claim 1, it is characterized in that described organic bases comprises: methylamine, dimethylamine, Trimethylamine 99, third rare amine, the rare amine of dipropyl, 3 third rare amine, Isopropylamine, Diisopropylamine, ethamine, diethylamine, triethylamine, 2-DEHA, propylamine, n-Butyl Amine 99, t-butylamine, sec-butylamine or monoethanolamine.
8, in accordance with the method for claim 1, it is characterized in that described transesterification reaction adopts continous way operation or batch operation, continous way operation hourly space velocity is generally 0.2～10h
-1The batch operation the reaction time is generally 0.1～5h.
9, in accordance with the method for claim 1, it is characterized in that setting up the material circulation between impact flow reactor outlet and inlet, the recycle stock amount is 1%～500% of a feed weight.
10, in accordance with the method for claim 1, it is characterized in that described transesterification reaction monohydroxy-alcohol and animal and plant fat and oily mol ratio are 3～50.
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| CN101531914B (en) * | 2009-04-20 | 2012-09-26 | 韩城市旺源再生燃料有限责任公司 | Method for producing biodiesel by taking pepper seed oil as a raw material and cyclohexane catalysis |
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