CN105087083A - Method for preparing biodiesel - Google Patents
Method for preparing biodiesel Download PDFInfo
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- CN105087083A CN105087083A CN201410191345.XA CN201410191345A CN105087083A CN 105087083 A CN105087083 A CN 105087083A CN 201410191345 A CN201410191345 A CN 201410191345A CN 105087083 A CN105087083 A CN 105087083A
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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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- 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 for preparing biodiesel comprises the steps of: with metal sulfide as a catalyst, mixing grease with C1-C6 monohydric alcohol in a reactor, performing a reaction at a reaction temperature of 100-200 DEG C with a pressure being 0.3-3 Mpa, and separating the biodiesel from a material obtained after the reaction. According to the method, the sulfide solid catalyst is combined with a low-pressure and low-temperature reaction mode, so that the biodiesel can be produced in a high yield through the one-step reaction.
Description
Invention field
The present invention relates to and react by grease and monohydroxy-alcohol the method preparing biofuel.
Background technology
Biofuel (i.e. lipid acid mono alkyl ester) is carried out transesterification reaction by grease and monohydroxy-alcohol and is obtained, lipid acid mono alkyl ester is had in reaction product, also have mono-glycerides, two sweet esters, glycerine, and unreacted alcohol and grease (i.e. triglyceride level).In prior art, the preparation method of biofuel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
CN1473907A adopts the tankage of vegetable oil refining and edible refiltered oil to be raw material, catalyzer forms by sulfuric acid, hydrochloric acid, tosic acid, Witco 1298 Soft Acid, naphthene sulfonic acid etc. are inorganic and organic acid is composite, produce through operations such as acidifying removal of impurities, continuously dehydrating, esterification, layering, underpressure distillation, the pressure of continous vacuum dehydration is 0.08 ~ 0.09Mpa, temperature 60 ~ 95 DEG C, dehydration is to water-content less than 0.2%, esterif iotacation step catalyst charge 1 ~ 3%, esterification temperature 60 ~ 80 DEG C, 6 hours reaction times.Reaction after product first neutralizes removing catalyzer, and then, layering is except anhydrating, and the after product that anhydrates obtains biofuel through underpressure distillation.
Acid catalysis Problems existing compared with base catalysis is that speed of response is slow, has a large amount of spent acid and produces, contaminate environment.
JP9-235573 discloses edible oil that a kind of use discards and methyl alcohol prepares diesel-fuel under the existence of sodium hydroxide, but in natural fats and oils, usually containing free fatty acids, when free fatty acids is more, use base metal catalysts, can produce fatty acid soaps, such base metal catalysts is wanted excessive and lipid acid ester layer is separated with glycerin layer to become difficulty.
DE3444893 discloses a kind of method, with acid catalyst, normal pressure, 50 ~ 120 DEG C, free fatty acids and alcohol are carried out esterification, pre-esterification process is carried out to oil plant, then under base metal catalysts, carry out transesterification reaction, but the acid catalyst left over will be neutralized by alkali, the amount of base metal catalysts can increase.Adopt pre-esterification, make work flow elongated, facility investment, energy consumption significantly rises, and in addition, basic catalyst need be removed from product, has a large amount of waste water to produce, and reclaims glycerine difficulty.
US5713965A discloses a kind of method, and under the existence of lipase, hexane makes solvent, and grease and alcohol reaction prepare fatty acid methyl ester, i.e. diesel-fuel.
CN1472280A discloses a kind of method, using fatty acid ester as acyl acceptor, under the existence of biological enzyme, and biocatalysis transesterification reaction production biofuel.Adopt enzyme catalyst exist deficiency be: long reaction time, efficiency are lower, and enzyme is more expensive, and in high purity methanol easy in inactivation.
CN1111591C discloses a kind of grease and monohydroxy-alcohol reacts the method preparing fatty acid ester, the method comprise by methyl alcohol with grease reaction obtain fatty acid ester, at 270 ~ 280 DEG C, under 11 ~ 12Mpa condition, fatty acid methyl ester production rate is 55 ~ 60%, and fatty acid methyl ester production rate is lower.
Can be found by above-mentioned prior art, adopt the middle and high platen press of continuous print, if do not use catalyzer, there is the problem that fatty acid ester yield is lower.
Summary of the invention
The invention provides a kind of method preparing biofuel, the method can under lesser temps and pressure condition, process high acid value, high impurity oil plant.
The method preparing biofuel provided by the invention comprises: take metallic sulfide as catalyzer, by grease and C
1~ C
6monohydroxy-alcohol mixes in the reactor, temperature of reaction 100 ~ 200 DEG C, reacts under pressure 0.1 ~ 3Mpa, separating out fat acid esters from reacted material.
The main component of described grease is fatty acid triglycercide, comprises various animal-plant oil, also comprises from the oil plant in the material such as microorganism, algae in addition.Vegetable oil lipoprotein is as soybean oil, rapeseed oil, peanut oil, wunflower seed oil, plam oil, Oleum Cocois and the material (comprising the tall oil produced in paper-making process) containing fatty group coming from the fruit of other various farm crop and wild plant, stem, leaf, limb and root.Animal grease is as lard, butter, sheep oil, fish oil etc.Described grease can Shi Wei polished fat, polished fat, acidifying grease and waste grease etc.
Described monohydroxy-alcohol refers to the unitary fatty alcohol of carbonatoms between 1 ~ 6, can be saturated alcohol or unsaturated alcohol.As methyl alcohol, ethanol, propyl alcohol, Virahol, vinyl carbinol, propyl carbinol and isomer thereof, amylalcohol and isomer thereof etc.Independent alcohol or their mixture can be used.Particular methanol or ethanol.
Described catalyzer be selected from VI B, VII B, VIII, the sulfide of I B and II B race metal, one or more in the sulfide of preferred zinc, copper, iron, nickel, molybdenum, tungsten, manganese, the add-on of catalyzer is 0.05% ~ 10% of grease weight, preferably 0.1% ~ 5%, more preferably 0.1% ~ 2%.
Described reactor can be autoclave or fixed-bed reactor.If tank reactor, can grease, alcohol and catalyzer be added in reactor, react after abundant mixing, obtain reacting coarse product, solids removed by filtration catalyzer, from liquid phase reaction crude product, steam monohydroxy-alcohol, mixed ester phase (containing fatty acid ester, mono-glycerides, two sweet esters, unreacted triglyceride level) is separated with glycerine, mixed ester phase and glycerine are obtained high purity fatty acid ester and glycerine respectively by distillation.If fixed-bed reactor, preferred tubular reactor, oil and methyl alcohol preferably enter into tubular reactor from tubular reactor bottom, reacting coarse product flows out from tubular reactor upper end, unreacted methanol is steamed from reacting coarse product, standing separation glycerine phase, rectification under vacuum ester phase, obtains biofuel.
Temperature of reactor is 100 ~ 200 DEG C, preferably 120 ~ 170 DEG C, pressure 0.1 ~ 3Mpa, preferably 0.5 ~ 2Mpa, more preferably 0.5 ~ 1.2Mpa, and the weight ratio of grease and monohydroxy-alcohol is 1:0.05 ~ 2.Preferred 1:0.1 ~ 1.5.Adopt stirred-tank reactor, 0.1 ~ 10 hour contact reacts time, preferably 0.5 ~ 5 hour, more preferably 1 ~ 4 hour.Use fixed bed liquid hourly space velocity 0.1 ~ 10h
-1, preferably 0.1 ~ 5h
-1, more preferably 0.1 ~ 2h
-1.
Temperature raises, reaction conversion ratio is higher, because say from aerodynamic point, temperature rising is conducive to reaction and carries out, but when temperature is higher than 300 DEG C, reaction product is black, has burnt matter to produce, simultaneously, also glycerine can be caused to decompose, therefore, temperature of reactor answers < 300 DEG C, best 100 ~ 200 DEG C.
Pressure is higher more favourable to reaction, but pressure is too high, makes plant investment and process cost improve more, so, pressure 0.1 ~ 3Mpa, preferably 0.5 ~ 2Mpa, more preferably 0.5 ~ 1.2Mpa.
In the inventive method, the ratio of monohydroxy-alcohol and grease can in very large range change, and methyl alcohol makes Methanol Recovery amount significantly increase with the too high meeting of ratio of oil, and plant energy consumption and process cost increase, and the utilization ratio of equipment is declined.So the weight ratio of grease and monohydroxy-alcohol is 1:0.05 ~ 2.Preferred 1:0.1 ~ 1, more preferably 1:0.1 ~ 0.4.
Widely, acid number can change the stock oil that the inventive method is suitable within a large range, such as acid number 0.1 ~ 200mgKOH/g, and be particularly useful for high acid value, high impurity oil plant, such as unsaponifiable matter content is up to the grease of 4 ~ 10g/100g.The inventive method raw oil material is adopted not carry out pre-treatment.
The reactive mode of sulfide solid catalyzer with low pressure, low temperature combines by the present invention, can be obtained the biofuel of high yield by single step reaction, and in single step reaction process, oil plant both carried out esterification, has carried out transesterification reaction again.
Embodiment
Further illustrate the present invention below by example, but the present invention is not limited to this.
Embodiment 1
By the acidification oil of acid number 117mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.16:1, add the CuS of grease weight 0.6% as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 2.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 91.1%, acid number 8.5mgKOH/g.
Embodiment 2
By the soybean oil of acid number 40mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.16:1, add the CuS of grease weight 0.6% as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 3.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 95%, acid number 14.9mgKOH/g.
Embodiment 3
By the acidification oil of acid number 117mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.16:1, add the FeS of grease weight 0.6% as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 2.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 87.2%, acid number 9.2mgKOH/g.
Embodiment 4
By the soybean oil of acid number 40mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.16:1, add the FeS of grease weight 0.6% as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 3.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 97%, acid number 3.8mgKOH/g.
Embodiment 5
By the acidification oil of acid number 117mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.20:1, add the ZnS of grease weight 0.6% as catalyzer, temperature 160 DEG C, pressure 1.1Mpa, under the condition that stirring velocity is 400 revs/min, react 2.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 82.2%, acid number 13.0mgKOH/g.
Embodiment 6
The soybean oil of acid number 40mgKOH/g, methyl alcohol are joined together in autoclave, alcohol oil quality, than 0.30:1, adds the MoS of grease weight 2%
2as catalyzer, temperature 160 DEG C, pressure 1.1Mpa, under the condition that stirring velocity is 600 revs/min, react 3.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and reclaims methyl alcohol, reuses, leftover materials are isolated glycerine mutually after, carry out underpressure distillation mutually to the mixed ester obtained, the yield obtaining biofuel is 57.7%, acid number 3.7mgKOH/g.
Embodiment 7
The acidification oil of acid number 40mgKOH/g, methyl alcohol are joined together in autoclave, alcohol oil quality, than 0.16:1, adds the WS of grease weight 0.6%
2as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 3.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and reclaims methyl alcohol, reuses, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, obtains the yield 97% of biofuel, acid number 3.2mgKOH/g.
Embodiment 8
By the acidification oil of acid number 40mgKOH/g, methyl alcohol joins in autoclave together, alcohol oil quality compares 0.16:1, add the MnS of grease weight 0.6% as catalyzer, temperature 140 DEG C, pressure 0.7Mpa, under the condition that stirring velocity is 200 revs/min, react 3.5 hours, obtain reacting coarse product to distill, at the bottom of still, < 150 DEG C removes excessive methanol, and methyl alcohol is reclaimed, reuse, leftover materials are isolated glycerine mutually after, mutually underpressure distillation is carried out to the mixed ester obtained, the yield obtaining biofuel is 96%, acid number 2.2mgKOH/g.
Embodiment 9
Get granularity 26-40 order catalyst Fe S5.7 gram and load internal diameter 8 millimeters, in the tubular reactor that the stainless steel that length is 391 millimeters is made, with the waste grease of acid number 91mgKOH/g for raw material, in alcohol oil quality than 0.2, liquid hourly space velocity 0.38h
-1condition under, oil and methyl alcohol continuously enter into tubular reactor from tubular reactor bottom, temperature of reaction 140 DEG C, pressure 0.7Mpa, reaction product flows out from tubular reactor upper end, and reacting coarse product is through steaming unreacted methanol, standing separation glycerine phase, rectification under vacuum ester phase, obtains biofuel yield 85.2%, acid number 8.5mgKOH/g.
Embodiment 10
Get granularity 26-40 order catalyst Fe S5.8 gram and load internal diameter 8 millimeters, in the tubular reactor that the stainless steel that length is 391 millimeters is made, with the acidification oil of acid number 117mgKOH/g for raw material, in alcohol oil quality than 0.2, liquid hourly space velocity 0.37h
-1condition under, oil and methyl alcohol continuously enter into tubular reactor from tubular reactor bottom, temperature of reaction 140 DEG C, pressure 0.7Mpa, reaction product from tubular reactor upper end flow out, reacting coarse product through steaming unreacted methanol, standing separation glycerine phase, rectification under vacuum ester phase, obtains biofuel yield 87.9mol%.Acid number 8.9mgKOH/g.
Claims (10)
1. prepare a method for biofuel, comprising: take metallic sulfide as catalyzer, by grease and C
1~ C
6monohydroxy-alcohol mixes in the reactor, temperature of reaction 100 ~ 200 DEG C, reacts under pressure 0.1 ~ 3Mpa, separating bio diesel oil from reacted material.
2. in accordance with the method for claim 1, wherein, described grease main component is fatty acid triglycercide.
3. in accordance with the method for claim 1, wherein, described monohydroxy-alcohol is methyl alcohol and/or ethanol.
4. in accordance with the method for claim 1, wherein, described catalyzer be selected from VI B, VII B, VIII, the sulfide of I B and II B race metal.
5. in accordance with the method for claim 1, wherein, described catalyzer is selected from one or more in the sulfide of zinc, copper, iron, nickel, molybdenum, tungsten, manganese.
6. in accordance with the method for claim 1, wherein, the add-on of catalyzer is 0.05% ~ 10% of grease weight.
7. in accordance with the method for claim 1, wherein, described reactor is autoclave or fixed-bed reactor.
8. in accordance with the method for claim 1, wherein, described reactor is tubular reactor, oil and methyl alcohol enter from tubular reactor bottom, reacting coarse product flows out from tubular reactor upper end, steams unreacted methyl alcohol, standing separation glycerine phase from reacting coarse product, rectification under vacuum ester phase, obtains biofuel.
9. in accordance with the method for claim 1, wherein, temperature of reactor is 120 ~ 170 DEG C, pressure 0.5 ~ 2Mpa.
10. in accordance with the method for claim 1, wherein, the weight ratio of grease and monohydroxy-alcohol is 1:0.05 ~ 2,0.1 ~ 10 hour contact reacts time.
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