CN105199857B - A method of improving biodiesel yield - Google Patents
A method of improving biodiesel yield Download PDFInfo
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- CN105199857B CN105199857B CN201410290721.0A CN201410290721A CN105199857B CN 105199857 B CN105199857 B CN 105199857B CN 201410290721 A CN201410290721 A CN 201410290721A CN 105199857 B CN105199857 B CN 105199857B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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Abstract
The invention discloses a kind of method for improving biodiesel yield, this method includes making grease, monohydric alcohol and acid material haptoreaction, and the catalytic condition includes: that temperature is 100-300 DEG C, pressure 0.2-10MPa.Method of the invention can be improved the yield of biodiesel, moreover, because using acid material as catalyst, and cooperates certain temperature and pressure, handles the grease of high acid value and high impurity content, and yield that still can be high prepares biodiesel.Meanwhile in method provided by the invention, do not need to pre-process the grease (such as pre-esterification processing), thus therefore the process for simplifying preparation biodiesel substantially increases production efficiency.
Description
Technical field
The present invention relates to a kind of methods for improving biodiesel yield.
Background technique
Biodiesel can carry out ester exchange reaction by grease and monohydric alcohol and be made, and have aliphatic ester in reaction product (i.e.
Biodiesel), there are also monoglyceride, two sweet esters, glycerol and unreacted pure and mild greases (i.e. triglycerides).In the prior art
The preparation method of biodiesel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
In method disclosed in DE3444893, with acid catalyst, free fatty acid and alcohol, are carried out ester by normal pressure by 50-120 DEG C
Change, pre-esterification processing is carried out to oil plant, ester exchange reaction is then carried out under base metal catalysts, but the acid catalyst left is wanted
It will increase by the amount of alkali neutralization, base metal catalysts.Using pre-esterification, keep processing flow elongated, equipment investment, energy consumption substantially on
It rises, in addition, basic catalyst need to be removed from product, there are a large amount of waste water to generate, and more difficult recycling glycerol.
CN1031070C uses pre-esterification-base catalysis method, uses the concentrated sulfuric acid, phosphoric acid or p-methyl benzenesulfonic acid, toluenesulfonic acid first
And naphthalene sulfonic acids is catalyst, by oil plant and alcohol under the conditions of 80-160 DEG C, in the tank reactor with stirring, carries out pre-esterification
Reaction.After the reaction was completed, pure and mild excess base is added, first neutralizes acidic catalyst and residual free fatty acid, remaining alkali is as ester
Exchange reaction catalyst.
Acid catalysis pre-esterification-base catalysis technique is compared with base catalysis the problem is that acid catalyst usage amount is big, generally
For the 1-3 weight % of oil plant, even more, a large amount of spent acid seriously pollute environment.Sulfuric acid is as esterification catalyst, in order to reduce height
The acid value of acid value raw material.Pre-esterifying process keeps processing flow elongated, equipment investment, and energy consumption increases.
JP9-235573, which is disclosed, a kind of prepares diesel engine in the presence of sodium hydroxide with discarded edible oil and methanol
Fuel, but in natural oil, free fatty acid is usually contained, in the case where free fatty acid is more, is catalyzed using alkali metal
Agent, can generate fatty acid soaps, and such base metal catalysts want excess and fatty acid ester layer is made to separate the difficulty of change with glycerin layer.
Base-catalyzed transesterification technique has a large amount of waste water to generate the problem is that needing a basic catalyst to remove from product after reaction,
It is difficult to recycle glycerol.
In method disclosed in US5713965A, in the presence of lipase, hexane makees solvent, and grease and alcohol reaction prepare rouge
Fatty acid methyl esters, i.e. diesel fuel.
In method disclosed in CN1472280A, using aliphatic ester as acyl acceptor, in the presence of biological enzyme, catalysis life
Object carries out transesterification reaction and produces biodiesel.Be using deficiency existing for enzyme catalyst: the reaction time is long, efficiency is lower, and enzyme is urged
Agent higher cost, and the easy in inactivation in high purity methanol.
JP9905431 discloses a kind of method for preparing aliphatic ester by grease and monohydric alcohol reaction, and this method includes will
Methanol reacts to obtain aliphatic ester with grease, and under the conditions of 270-280 DEG C, 11-12MPa, fatty acid methyl ester production rate is 55-
60%, it can be seen that using continuous middle and high platen press, there are still the lower problems of aliphatic ester yield.
Summary of the invention
It is raw to provide a kind of new preparation for drawbacks described above in preparation method of the present invention in order to overcome existing biodiesel
The method of object diesel oil, this method process flow is simple and can be improved the yield of biodiesel.
To achieve the goals above, the present invention provides a kind of method for improving biodiesel yield, this method includes making
Grease, monohydric alcohol and acid material haptoreaction, the catalytic condition include: that temperature is 100-300 DEG C, and pressure is
0.2-10MPa。
Method of the invention can be improved the yield of biodiesel, moreover, because use acid material as catalyst, and
Cooperate certain temperature and pressure, the grease of high acid value and high impurity content is handled, yield that still can be high prepares life
Object diesel oil.Meanwhile in method provided by the invention, do not need to pre-process the grease (such as pre-esterification processing), from
And therefore the process for simplifying preparation biodiesel substantially increases production efficiency.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The method provided by the invention for improving biodiesel yield includes keeping grease, monohydric alcohol and acid material contact anti-
It answers, the catalytic condition includes: that temperature is 100-300 DEG C, pressure 0.2-10MPa.
In the present invention, the grease can be various conventional greases, main component be fatty acid triglycercide and/or
In addition fatty acid may be used also for example, the grease can be at least one of vegetable fat, animal fat and microbial oil
To be frying oil and/or rotten waste oil.The vegetable fat for example may include soybean oil, rapeseed oil, peanut oil, sunflower
Seed oil, palm oil, coconut oil and containing from the fruit of various other crops and wild plant, stem, leaf, limb and root
There is the substance of fat-based (including the tall oil generated in paper-making process).Animal fat for example may include lard, butter, sheep
Oil, fish oil etc..
In the present invention, the monohydric alcohol can be monohydric alcohol of the carbon atom number between 1-6, can be saturated alcohols, can also
To be unsaturated alcohol.Under preferable case, the monohydric alcohol be methanol, ethyl alcohol, propyl alcohol, allyl alcohol, butanol and amylalcohol at least
One kind, further preferably methanol and/or ethyl alcohol.The propyl alcohol can be normal propyl alcohol and/or isopropanol, and the butanol can be
The isomers of n-butanol and/or n-butanol, the amylalcohol can be n-amyl alcohol and/or the isomers of n-amyl alcohol.
In the present invention, as long as the grease and monohydric alcohol contact in aforementioned temperature and pressure limit with acid material
The yield of biodiesel is improved, the acidity material refers to provide hydrogen ion and/or provides the material of L acid, is preferably able to mention
For hydrionic material.Under preferable case, the acidity material includes inorganic acid and/or mineral acid oil plant.For 100 weight
The dosage of part grease, the acidity material can be more than 0.001 parts by weight (such as 0.001-50 parts by weight).
When acid material is inorganic acid, to the amount of the acid material of addition, there is no particular limitation.Under preferable case, relatively
In the grease of 100 parts by weight, the dosage of the inorganic acid is 0.001-1 parts by weight, more preferably 0.004-0.5 parts by weight, into
One step is preferably 0.01-0.3 parts by weight, most preferably 0.02-0.3 parts by weight.
In the present invention, the acidity in acid material can come from B acid and/or L acid, but preferably B acid, the inorganic acid are
Various inorganic acids commonly used in the art, under preferable case, the inorganic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
In the present invention, when acid material is mineral acid oil plant, to the amount of the acid material of addition, there is no particular limitation.
Under preferable case, relative to the grease of 100 parts by weight, dosage >=5 parts by weight of the mineral acid oil plant, preferably 5-50 weight
Measure part, more preferably 10-30 parts by weight.
Hydrogen ion in the mineral acid oil plant can by inorganic matter contained in oil plant and/or organic matter ionization and/or
Hydrolysis obtains, it is preferable that hydrionic content is 0.001-10mg/100g (that is, 100g inorganic acid in the mineral acid oil plant
Property oil plant in hydrionic amount be 0.001-10mg), more preferably 0.01-6mg/100g, further preferably 0.1-4mg/
100g, most preferably 0.1-2mg/100g.According to the preferred embodiment of the present invention, need to only contain in the mineral acid oil plant micro-
The hydrogen ion of amount, this can be such that etching problem is significantly solved.
In the present invention, " hydrogen ion content " is measured by conventional method, for example, after can be by mixing oil plant with water
It is measured using the method for sodium hydroxide titration, details are not described herein.
The mineral acid oil plant refer to impure acid oil plant (i.e. fatty acid triglycercide and/or fatty acid with it is miscellaneous
The mixture of matter), it can also include other impurity that wherein impurity, which may include acidic materials (such as organic and or inorganic acids),
Such as phosphorus-containing compound, sulfur-containing compound, nitrogenous compound, metalliferous substance, inorganic acid salt, acylate (such as fatty acid
The metal fatty acid salts such as sodium, fatty acid potassium) and one of vitamin etc. or a variety of.Fatty acid and above-mentioned impurity can be further
The activity of mineral acid oil plant is improved, often using with acid and fatty acid and/or the higher grease of impurity content or acid
The biodiesel yield of property oil plant is higher.The lower oil of activity is added in the higher acid oil plant of fatty acid and/or impurity content
In rouge (for example, foregoing vegetable fat, animal fat or microbial oil), biodiesel can be improved more significantly
Yield.Therefore, the saponifiable matter in the mineral acid oil plant content preferably≤97 weight % (such as 85-95 weight %).It needs
It is noted that " saponifiable content " refers to both fatty acid and fatty acid triglycercides in oil plant content in the present invention
Summation.
The acid value of the mineral acid oil plant can be 1-200mg KOH/g, preferably 30-200mg KOH/g, more preferably
For 70-150mg KOH/g.
In the present invention, the grease is typically different than the mineral acid oil plant, in other words, the hydrogen in at least described grease
Ion concentration is different from the hydrogen ion content in mineral acid oil plant.Preferably, the hydrogen ion content in the grease is lower than nothing
Hydrogen ion content in machine acidity oil plant.
The weight ratio of monohydric alcohol and grease can change in very large range in the method for the present invention, the weight ratio mistake of methanol and oil
Height can be such that Methanol Recovery amount is significantly increased, and plant energy consumption and operating cost increase, and decline the utilization rate of equipment.So grease
Weight ratio with monohydric alcohol can be 1:0.05-1, preferably 1:0.1-0.7, more preferably 1:0.2-0.7.
The haptoreaction can be in the preparation well known by persons skilled in the art for being able to carry out biodiesel and satisfaction
It is carried out in the reactor of aforementioned temperature and pressure limit, the reactor can be tubular reactor, or still reaction
Device (such as autoclave).
When using tank reactor, the reactor preferably has agitating device, in this way, being more advantageous to the biological bavin of raising
The yield of oil.When carrying out the haptoreaction of grease, monohydric alcohol and acid material, the grease, monohydric alcohol and acid material can
To be supplied separately to reactor, is provided after can also mixing and arrive reactor.
When using tubular reactor, grease and monohydric alcohol can be provided independently to reactor, or they are pre-mixed
After be supplied to reactor.Preferably, control liquid hourly space velocity (LHSV) is 0.1-2h-1, preferably 0.1-1.6h-1, be supplied to reactor it
Before, material can be preheated with preheater, reactor can also be directly entered.If, can be by grease and unitary using preheater
Alcohol preheats together after preheating or mix respectively.In tubular reactor, grease and monohydric alcohol preferably from tubular reactor lower part into
Enter in tubular reactor, and reacting coarse product is flowed out from tubular reactor upper end.
In catalytic condition, temperature is higher, and reaction conversion ratio is higher, but temperature be higher than 300 DEG C when, reaction product
It is black, there is burnt matter to generate, meanwhile, also result in glycerol decomposition;Temperature is lower, and can reduce the yield of biodiesel, because
This, in foregoing temperature range, for tank reactor, temperature is preferably 120-200 DEG C, and for tubular reactor, temperature is excellent
It is selected as 200-300 DEG C, more preferably 240-300 DEG C.
Equally, it is advantageous to reaction to improve pressure, but pressure is too high, the investment of device and operating cost is made to improve more, institute
With in foregoing pressure ranges, for tank reactor (such as stirred tank), pressure is preferably 0.4-1.6MPa, makes apparatus system
Pressure is in low pressure, this can significantly reduce the expense of fixed investment;For tubular reactor, pressure is preferably 1-8MPa, more excellent
It is selected as 3-6MPa.Grease carries out esterification and ester exchange reaction simultaneously during haptoreaction, extends the haptoreaction time pair
Reaction yield improves favorably, so, the catalytic time is generally 0.7-10 hours, preferably 1-6 hours, more preferably 1-
4 hours.
In a preferred embodiment, the mixing provided by the invention that the method also includes obtaining after haptoreaction
Fatty acid unitary alcohol ester is isolated in object, and (mixed ester phase contains aliphatic ester, monoglyceride, two sweet esters and unreacted glycerol three
Ester etc.), the isolated method can be implemented using conventional separation method, such as can be real using the method for vacuum distillation
It is existing.
In further preferred embodiment, provided by the invention the method also includes obtaining after haptoreaction
Mixture in isolate and isolate monohydric alcohol before fatty acid unitary alcohol ester.The method for separating monohydric alcohol can be using routine
Method (as distilled) is realized.The monohydric alcohol isolated can be recycled.
In preferred embodiment, method provided by the invention further includes in the mixture obtained after haptoreaction
In isolate after monohydric alcohol and before isolating fatty acid unitary alcohol ester, isolate glycerol.The method for separating glycerol can be with
It is realized, such as can be realized by the method for sedimentation separation using conventional method.The glycerol isolated can be recycled benefit
With.
The method provided according to the present invention, to the acid value of the grease, there is no particular limitation, such as can be 0.1-
200mg KOH/g.Method of the invention can also be prepared when carrying out haptoreaction using the grease of high acid value with higher yields
Biodiesel, therefore, the acid value of the grease can be 60-200mg KOH/g, more preferably 90-200mg KOH/g." acid
Value " refers under test conditions, the milligram number of potassium hydroxide needed for free fatty acid in 1g grease is neutralized, according to GB/T5530-
Indicator method in 1998 standards is measured.
The present invention is described in detail by the following examples.Raw material used in embodiment, unless stated otherwise,
For commercial product.And in the examples below, the yield of biodiesel is calculate by the following formula:
The yield of biodiesel=(quality/grease quality of the biodiesel finally obtained) × 100%.
Embodiment 1
The soybean oil for being 0.3mg KOH/g by 100g acid value, 17g methanol and 0.02g sulfuric acid are added in autoclave together,
Under conditions of 140 DEG C of temperature, pressure 0.7MPa and 200 revs/min of mixing speed, reacts 3.5 hours, obtain reacting coarse product.
Reacting coarse product is distilled, removes methanol under conditions of 150 DEG C of < in bottom, and carry out recycling and repeat to make to methanol
With, after surplus material is isolated glycerol phase, obtained mixed ester is mutually evaporated under reduced pressure, steaming material is biodiesel,
The yield of biodiesel is 93.5%.
Embodiment 2
Biodiesel is prepared according to the method for embodiment 1, unlike, sulphuric acid 0.8g, the receipts of biodiesel
Rate is 88%.
Embodiment 3
Rapeseed oil, 17g methanol and 0.2g sulfuric acid that 100g acid value is 67mg KOH/g are added in autoclave together,
Under conditions of 140 DEG C of temperature, pressure 0.7MPa and 200 revs/min of mixing speed, reacts 3.5 hours, obtain reacting coarse product.It will
Reacting coarse product is distilled, and removes methanol under conditions of 150 DEG C of < in bottom, and methanol is recycled and reused,
After surplus material is isolated glycerol phase, obtained mixed ester is mutually evaporated under reduced pressure, steaming material is biodiesel, biology
The yield of diesel oil is 96%.
Embodiment 4
The waste grease for being 97mg KOH/g by 100g acid value, 20g methanol and 0.3g sulfuric acid are added in autoclave together,
Under conditions of 140 DEG C of temperature, pressure 0.8MPa and 200 revs/min of mixing speed, reacts 3.5 hours, obtain reacting coarse product.
Reacting coarse product is distilled, removes methanol under conditions of 150 DEG C of < in bottom, and carry out recycling and repeat to make to methanol
With, after surplus material is isolated glycerol phase, obtained mixed ester is mutually evaporated under reduced pressure, steaming material is biodiesel,
The yield of biodiesel is 94.1%.
Embodiment 5
Using the waste grease that acid value is 20mg KOH/g as raw material, the mineral acid oil that weight is grease weight 12% is added
Material (hydrogen ion content is 0.12mg/100g, and acid value is 79mg KOH/g, and saponifiable content is 94.7 weight %), in alcohol oil
Mass ratio 0.17, liquid hourly space velocity (LHSV) 1h-1Under conditions of, it mixes oil plant and methanol is continuously entered from tubular reactor lower part
In tubular reactor, controlling temperature in reactor is 240 DEG C, and pressure 4MPa, reacting coarse product is distilled out unreacted first
Alcohol is recycled, is reused, settle and separate glycerol phase, is evaporated under reduced pressure mixed ester phase, and steaming material is biodiesel, biology
The yield of diesel oil is 64%.
Comparative example 1
Biodiesel is prepared according to the method for embodiment 5, unlike, mineral acid oil plant is not added, biodiesel
Yield is 51.1%.
Embodiment 6
Using the waste grease that acid value is 46mg KOH/g as raw material (saponifiable content is 95.2 weight %), weight is added
For the mineral acid oil plant of grease weight 30%, (hydrogen ion content is 1mg/100g, and acid value is 38.7mg KOH/g, saponifiable matter
Content is 93.2 weight %), in alcohol oil quality than 0.17, liquid hourly space velocity (LHSV) 1h-1Under conditions of, it mixes oil plant and methanol is successive
Ground enters in tubular reactor from tubular reactor lower part, and controlling temperature in reactor is 260 DEG C, pressure 6MPa, reaction
Crude product is distilled out unreacted methanol, is recycled, is reused, settle and separate glycerol phase, is evaporated under reduced pressure mixed ester phase,
Steaming material is biodiesel, and the yield of biodiesel is 92.8%.
Comparative example 2
Biodiesel is prepared according to the method for embodiment 6, unlike, mineral acid oil plant is not added, biodiesel
Yield is 57%.
Comparative example 3
Using waste grease that acid value is 73mg KOH/g as raw material (hydrogen ion content for 0.006mg/100g, saponifiable matter
Content is 95 weight %), in alcohol oil quality than 0.17, liquid hourly space velocity (LHSV) 1h-1Under conditions of, oil plant and methanol are continuously from pipe
Formula reactor lower part enters in tubular reactor, and controlling temperature in reactor is 260 DEG C, pressure 6MPa, reacting coarse product
Unreacted methanol is distilled out, recycled, reused, settle and separate glycerol phase is evaporated under reduced pressure mixed ester phase, steams material
As biodiesel, the yield of biodiesel are 64%.
As can be seen from the above embodiments, method of the invention can significantly improve the yield of biodiesel.Compare implementation
The result of example 1 and embodiment 2 can be seen that when the dosage of acid material is in preferred scope of the invention, biodiesel
Yield is higher.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of method for improving biodiesel yield, which is characterized in that this method includes making grease, monohydric alcohol and acid material
Haptoreaction, the catalytic condition include: that temperature is 100-300 DEG C, pressure 0.2-10MPa;The acidity material
For mineral acid oil plant;Hydrionic content is 0.1-4mg/100g, the mineral acid oil plant in the mineral acid oil plant
Acid value be 30-200mg KOH/g;Wherein, the grease relative to 100 parts by weight, the dosage of the mineral acid oil plant are 5-
50 parts by weight.
2. according to the method described in claim 1, wherein, hydrionic content is 0.1-2mg/ in the mineral acid oil plant
100g;The acid value of the mineral acid oil plant is 70-150mg KOH/g.
3. according to the method described in claim 1, wherein, the weight ratio of the grease and monohydric alcohol is 1:0.05-1.
4. the contact is anti-according to the method described in claim 1, wherein, the haptoreaction carries out in tank reactor
The condition answered includes: that temperature is 120-200 DEG C, pressure 0.4-1.6MPa.
5. the contact is anti-according to the method described in claim 1, wherein, the haptoreaction carries out in tubular reactor
The condition answered includes: that temperature is 200-300 DEG C, pressure 1-8MPa.
6. the contact is anti-according to the method described in claim 1, wherein, the haptoreaction carries out in tubular reactor
The condition answered includes: that temperature is 240-300 DEG C, pressure 3-6MPa.
7. according to the method described in claim 1, wherein, the acid value of the grease is 0.1-200mg KOH/g.
8. according to the method described in claim 1, wherein, the acid value of the grease is 60-200mg KOH/g.
9. according to the method described in claim 1, wherein, the acid value of the grease is 90-200mg KOH/g.
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