CN105087083B - A method of preparing biodiesel - Google Patents
A method of preparing biodiesel Download PDFInfo
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- CN105087083B CN105087083B CN201410191345.XA CN201410191345A CN105087083B CN 105087083 B CN105087083 B CN 105087083B CN 201410191345 A CN201410191345 A CN 201410191345A CN 105087083 B CN105087083 B CN 105087083B
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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
A method of biodiesel is prepared, including：Using metal sulfide as catalyst, by grease and C1~C6Monohydric alcohol mixes in the reactor, reacts under 100~200 DEG C of reaction temperature, 0.3~3Mpa of pressure, biodiesel is detached from the material after reaction.Sulfide solid catalyst is combined by the present invention with low pressure, the reactive mode of low temperature, and the biodiesel of high yield is can be obtained by single step reaction.
Description
Invention field
The present invention relates to the methods for preparing biodiesel by grease and monohydric alcohol reaction.
Background technology
Biodiesel (i.e. aliphatic acid monoalkyl ester) can carry out ester exchange reaction by grease and monohydric alcohol and be made, reaction production
There are aliphatic acid monoalkyl ester, also monoglyceride, two sweet esters, glycerine and unreacted alcohol and grease (i.e. triglycerides) in object.
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.
CN1473907A use vegetable oil refining leftover bits and pieces and edible oil recovery for raw material, catalyst by sulfuric acid, hydrochloric acid,
P-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids etc. are inorganic and organic acid compounds, acidified removal of impurities, continuous dehydration, ester
The processes such as change, layering, vacuum distillation are produced, and the pressure of continuous vacuum dehydration is 0.08~0.09Mpa, temperature 60~95
DEG C, it is dehydrated to water content 0.2% hereinafter, esterif iotacation step catalyst charge 1~3%, 60~80 DEG C of esterification temperature, reaction time
6 hours.Product, which first neutralizes, after reaction removes catalyst, and then, layering removes water, and product obtains biology through vacuum distillation after removing water
Diesel oil.
Acid catalysis the problem is that reaction speed is slow, has a large amount of spent acid and generates, pollute environment compared with base catalysis.
JP9-235573 is disclosed a kind of preparing diesel engine with discarded edible oil and methanol in the presence of sodium hydroxide
Fuel, but in natural oil, free fatty is usually contained, in the case where free fatty is more, it is catalyzed using alkali metal
Agent, will produce fatty acid soaps, and such base metal catalysts want excess and aliphatic acid ester layer is made to be become difficult with glycerine layer separation.
DE3444893 discloses a kind of method, with acid catalyst, normal pressure, 50~120 DEG C, by free fatty and alcohol into
Row esterification carries out pre-esterification processing, the acid catalysis that ester exchange reaction is then carried out under base metal catalysts, but is left to oil plant
Agent will can be increased by alkali neutralization, the amount of base metal catalysts.Using pre-esterification, keep processing flow elongated, equipment investment, energy consumption is big
Width rises, in addition, basic catalyst need to be removed from product, has a large amount of waste water to generate, and recycling glycerine is difficult.
US5713965A discloses a kind of method, and in the presence of lipase, hexane makees solvent, prepared by grease and alcohol reaction
Fatty acid methyl ester, i.e. diesel fuel.
CN1472280A discloses a kind of method, using aliphatic ester as acyl acceptor, in the presence of biological enzyme, and biology
It is catalyzed transesterification reaction and produces biodiesel.It is using deficiency existing for enzyme catalyst：Reaction time is long, less efficient, and enzyme is more expensive,
And the easy in inactivation in high purity methanol.
A kind of method that CN1111591C discloses grease and monohydric alcohol reaction prepares aliphatic ester, this method includes by first
Alcohol obtains aliphatic ester with grease reaction, and at 270~280 DEG C, under the conditions of 11~12Mpa, fatty acid methyl ester production rate is 55
~60%, fatty acid methyl ester production rate is relatively low.
By the above-mentioned prior art it can be found that using continuous middle and high platen press, if not using catalyst, there are fat
The relatively low problem of acid esters yield.
Invention content
The present invention provides a kind of method preparing biodiesel, and this method can be located under lower temperature and pressure condition
Manage high acid value, high impurity oil plant.
It is provided by the invention prepare biodiesel method include：Using metal sulfide as catalyst, by grease and C1~C6
Monohydric alcohol mixes in the reactor, reacts under 100~200 DEG C of reaction temperature, 0.1~3Mpa of pressure, after reaction
Fractionation of fatty acid esters in material.
The main component of the grease is fatty acid triglycercide, including various animal and plant fats, additionally includes and
Oil plant from the substances such as microorganism, algae.Vegetable fat for example soybean oil, rapeseed oil, peanut oil, sunflower seed oil, palm oil,
Coconut oil and come from the fruits of various other crops and wild plant, stem, leaf, limb and root the object containing fat-based
Matter (including the tall oil generated in paper-making process).Animal fat such as lard, butter, sheep oil, fish oil etc..The grease can be with
It is non-polished fat, polished fat, acidification grease and waste grease etc..
The monohydric alcohol refers to unitary fatty alcohol of the carbon atom number between 1~6, can be saturated alcohols or unsaturation
Alcohol.Such as methanol, ethyl alcohol, propyl alcohol, isopropanol, allyl alcohol, n-butanol and its isomers, amylalcohol and its isomers.It can be used single
Only alcohol or their mixture.It is preferred that methanol or ethyl alcohol.
The catalyst be the sulfide selected from VI B, the B of VII B, VIII, I and II B races metal, preferably zinc, copper, iron, nickel, molybdenum,
One or more of the sulfide of tungsten, manganese, the addition of catalyst are the 0.05%~10% of grease weight, preferably 0.1%
~5%, more preferable 0.1%~2%.
The reactor can be autoclave or fixed bed reactors.If it is tank reactor, can by grease, alcohol and
Catalyst is added in reactor, is reacted after being sufficiently mixed, obtains reacting coarse product, be filtered to remove solid catalyst, from liquid
Monohydric alcohol is steamed in phase reaction crude product, mixed ester phase (is contained into aliphatic ester, monoglyceride, two sweet esters, unreacted glycerine three
Ester) it is detached with glycerine, mixed ester phase and glycerine are obtained into high purity fatty acid ester and glycerine by distillation respectively.If it is fixation
Bed reactor, preferably tubular reactor, oil and methanol are preferably entered from tubular reactor lower part in tubular reactor, and reaction is thick
Product is flowed out from tubular reactor upper end, and unreacted methanol, standing separation glycerine phase, rectification under vacuum are steamed from reacting coarse product
Ester phase, obtains biodiesel.
Temperature of reactor be 100~200 DEG C, preferably 120~170 DEG C, 0.1~3Mpa of pressure, preferably 0.5~2Mpa, more
It is preferred that the weight ratio of 0.5~1.2Mpa, grease and monohydric alcohol is 1：0.05~2.It is preferred that 1：0.1~1.5.It is reacted using stirred tank
Device, 0.1~10 hour haptoreaction time, preferably 0.5~5 hour, more preferable 1~4 hour.Use fixed bed liquid hourly space velocity (LHSV)
0.1~10h-1, preferably 0.1~5h-1, more preferable 0.1~2h-1。
Temperature increases, and reaction conversion ratio is higher, because for aerodynamic point, temperature raising is conducive to reaction and carries out,
But when temperature is higher than 300 DEG C, reaction product is black, has burnt matter to generate, meanwhile, also result in glycerine decomposition, therefore, reaction
Device temperature answers 300 DEG C of ＜, best 100~200 DEG C.
Pressure is higher to reacting more advantageous, but pressure is too high, so that plant investment and operating cost is improved more, so, pressure
0.1~3Mpa of power, preferably 0.5~2Mpa, more preferable 0.5~1.2Mpa.
The ratio of monohydric alcohol and grease can change in very large range in the method for the present invention, the excessively high meeting of ratio of methanol and oil
Methanol Recovery amount is set to be significantly increased, plant energy consumption and operating cost increase, and the utilization rate of equipment is made to decline.So grease and one
The weight ratio of first alcohol is 1：0.05~2.It is preferred that 1：0.1~1, more preferable 1：0.1~0.4.
The applicable feedstock oil of the method for the present invention is very extensive, and acid value can change within a large range, such as acid value 0.1~
200mgKOH/g is particularly suitable for high acid value, high impurity oil plant, such as unsaponifiable matter content is up to the grease of 4~10g/100g.
It can be without pretreatment using the method for the present invention raw oil material.
Sulfide solid catalyst is combined by the present invention with low pressure, the reactive mode of low temperature, passes through single step reaction
The biodiesel of high yield is obtained, oil plant not only carries out esterification during single step reaction, but also has carried out ester exchange reaction.
Specific implementation mode
It is further illustrated the present invention below by example, but the present invention is not limited thereto.
Embodiment 1
The acidification oil of acid value 117mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The CuS of grease weight 0.6% is as catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 2.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 91.1%, acid value 8.5mgKOH/g.
Embodiment 2
The soybean oil of acid value 40mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The CuS of grease weight 0.6% is as catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 3.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 95%, acid value 14.9mgKOH/g.
Embodiment 3
The acidification oil of acid value 117mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The FeS of grease weight 0.6% is as catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 2.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 87.2%, acid value 9.2mgKOH/g.
Embodiment 4
The soybean oil of acid value 40mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The FeS of grease weight 0.6% is as catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 3.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 97%, acid value 3.8mgKOH/g.
Embodiment 5
The acidification oil of acid value 117mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.20:1, it is added
The ZnS of grease weight 0.6% is as catalyst, under conditions of 160 DEG C, pressure 1.1Mpa of temperature, 400 revs/min of mixing speed,
Reaction 2.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 82.2%, acid value 13.0mgKOH/g.
Embodiment 6
The soybean oil of acid value 40mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.30:1, it is added
The MoS of grease weight 2%2As catalyst, under conditions of 160 DEG C, pressure 1.1Mpa of temperature, 600 revs/min of mixing speed,
Reaction 3.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 57.7%, acid value 3.7mgKOH/g.
Embodiment 7
The acidification oil of acid value 40mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The WS of grease weight 0.6%2As catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 3.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield 97% of oil, acid value 3.2mgKOH/g.
Embodiment 8
The acidification oil of acid value 40mgKOH/g, methanol are added in autoclave together, alcohol oil quality is than 0.16:1, it is added
The MnS of grease weight 0.6% is as catalyst, under conditions of 140 DEG C, pressure 0.7Mpa of temperature, 200 revs/min of mixing speed,
Reaction 3.5 hours, obtains reacting coarse product and is distilled, 150 DEG C of removing excessive methanols of ＜ in bottom, and is returned to methanol
It receives, reuse, after surplus material is isolated glycerine phase, obtained mixed ester is mutually evaporated under reduced pressure, biological bavin is obtained
The yield of oil is 96%, acid value 2.2mgKOH/g.
Embodiment 9
S5.7 grams of granularity 26-40 mesh catalyst Fe 8 millimeters of internal diameter of loading is taken, made of the stainless steel that 391 millimeters of length
In tubular reactor, using the waste grease of acid value 91mg KOH/g as raw material, in alcohol oil quality than 0.2, liquid hourly space velocity (LHSV) 0.38h-1
Under conditions of, oil and methanol are continuously entered from tubular reactor lower part in tubular reactor, 140 DEG C of reaction temperature,
Pressure 0.7Mpa, reaction product are flowed out from tubular reactor upper end, and for reacting coarse product through steaming unreacted methanol, standing separation is sweet
Oil phase, rectification under vacuum ester phase obtain biodiesel yield 85.2%, acid value 8.5mgKOH/g.
Embodiment 10
S5.8 grams of granularity 26-40 mesh catalyst Fe 8 millimeters of internal diameter of loading is taken, made of the stainless steel that 391 millimeters of length
In tubular reactor, using the acidification oil of acid value 117mg KOH/g as raw material, in alcohol oil quality than 0.2, liquid hourly space velocity (LHSV) 0.37h-1's
Under the conditions of, oil and methanol are continuously entered from tubular reactor lower part in tubular reactor, 140 DEG C of reaction temperature, pressure
Power 0.7Mpa, reaction product are flowed out from tubular reactor upper end, and reacting coarse product is through steaming unreacted methanol, standing separation glycerine
Phase, rectification under vacuum ester phase obtain biodiesel yield 87.9mol%.Acid value 8.9mgKOH/g.
Claims (8)
1. a kind of method preparing biodiesel, including：Using metal sulfide as catalyst, by grease and C1~C6Monohydric alcohol exists
It mixes in reactor, reacts under 100~200 DEG C of reaction temperature, 0.1~3MPa of pressure, divide from the material after reaction
From biodiesel, the catalyst is selected from one or more of the sulfide of copper, iron, tungsten, manganese.
2. according to the method for claim 1, wherein the grease main component is fatty acid triglycercide.
3. according to the method for claim 1, wherein the monohydric alcohol is methanol and/or ethyl alcohol.
4. according to the method for claim 1, wherein the addition of catalyst is the 0.05%~10% of grease weight.
5. according to the method for claim 1, wherein the reactor is autoclave or fixed bed reactors.
6. according to the method for claim 1, wherein the reactor is tubular reactor, and grease and methanol are anti-from tubular type
Device lower part is answered to enter, reacting coarse product is flowed out from tubular reactor upper end, and unreacted methanol is steamed from reacting coarse product, quiet
Separation glycerine phase is set, rectification under vacuum ester phase obtains biodiesel.
7. according to the method for claim 1, wherein temperature of reactor is 120~170 DEG C, 0.5~2MPa of pressure.
8. according to the method for claim 1, wherein the weight ratio of grease and monohydric alcohol is 1：0.05~2, when haptoreaction
Between 0.1~10 hour.
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| CN103242914A (en) * | 2013-05-30 | 2013-08-14 | 广州市特种承压设备检测研究院 | Method for rapidly producing biodiesel from kitchen garbage and produced biodiesel |
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| CN103242914A (en) * | 2013-05-30 | 2013-08-14 | 广州市特种承压设备检测研究院 | Method for rapidly producing biodiesel from kitchen garbage and produced biodiesel |
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