CN102391914A - Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material - Google Patents
Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material Download PDFInfo
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- CN102391914A CN102391914A CN2011102946264A CN201110294626A CN102391914A CN 102391914 A CN102391914 A CN 102391914A CN 2011102946264 A CN2011102946264 A CN 2011102946264A CN 201110294626 A CN201110294626 A CN 201110294626A CN 102391914 A CN102391914 A CN 102391914A
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- sba
- earth oxide
- rare
- mesoporous
- rare earth
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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 method for preparing biodiesel by the catalysis of a rare-earth oxide mesoporous material. In the method, the biodiesel is prepared by reacting vegetable oil serving as a raw material with methanol or ethanol and adding a certain amount of catalyst under the action of esterification and ester exchange. The method comprises the following steps of: adding the vegetable oil and the methanol or the ethanol into a high-pressure reaction kettle, wherein a mass ratio of the vegetable oil to the methanol or the ethanol is (0.2-2):1; adding the rare-earth oxide mesoporous material in an amount which is 1 to 20 percent of the mass of the vegetable oil, and stirring mechanically at the temperature of between 60 and 240 DEG C to perform ester exchange reaction for 1 to 5 hours; after reaction is finished, performing suction filtration while the mixture is hot, and separating a rare-earth oxide mesoporous catalyst from the mixture; distilling a liquid phase to recover the methanol or the ethanol; and transferring the liquid phase to a separating funnel, and standing, so that the upper layer is coarse biodiesel, and the lower layer is glycerol serving as a byproduct. The production process is simple, the catalytic activity is high, the catalyst can be recycled, the aftertreatment is convenient, and industrial waste water is avoided.
Description
Technical field
The present invention relates to green, field of renewable energy technology, specifically, is to belong to a kind of novel method for preparing biodiesel, refers in particular to the method that adopts rare earth oxide mesoporous material catalysis for preparing biodiesel oil.
Background technology
Biofuel is meant that with vegetables oil or animal oil be raw material, the organic aliphatic acid methyl esters or the ethyl ester class A fuel A that obtain through transesterification and methyl alcohol or ethanol synthesis.It is a kind of renewable, biodegradable and eco-friendly biofuel.Its performance and traditional petrifaction diesel are approaching, have to pollute little characteristics, and be a kind of good substitute of traditional petrifaction diesel.The operational path of biodiesel manufacture is general in the industrial production at present adopts two to go on foot the homogeneous catalysis methods.The first step is to utilize H
2SO
4Deng homogeneous acid catalyst, the raw oil that contains high free fatty acid is carried out pre-treatment, make wherein free fatty acids and methyl alcohol carry out esterification, reduce its acid number; Second step was to utilize homogeneous phase alkaline catalystss such as sodium hydroxide, Pottasium Hydroxide, and pretreated raw oil is carried out transesterification reaction, and it is heavy by 1% that catalyst levels accounts for oil, and temperature of reaction is generally the boiling temperature of methyl alcohol, transformation efficiency high (more than 95%).But exist pretreatment catalyst to separate the relatively problem of difficulty in the homogeneous phase method, simultaneously, can produce a large amount of trade effluents in the last handling process, be prone to cause weak points such as environmental pollution.
Summary of the invention
The objective of the invention is to overcome traditional industry produce in two step homogeneous phase legal systems be equipped with the shortcoming of biofuel, provide the mesoporous catalytic material single stage method of a kind of employing rare earth oxide to prepare method of bio-diesel oil.The mesoporous catalytic material of rare earth oxide is used for this transesterification reaction, and to have production technique simple, and it is neutral that product and sub product all are, and the washing that need not neutralize can not produce characteristics such as trade effluent and catalyzer can reuse.
The present invention realizes through following concrete technical scheme:
The present invention is a kind of method of rare earth oxide mesoporous material catalysis for preparing biodiesel oil, utilizes vegetables oil for raw material and methyl alcohol or ethanol synthesis, adds a certain amount of catalyzer, obtains biofuel through over-churning and transesterification; Its concrete steps are described below:
(1), in reaction autoclave, add vegetables oil and methyl alcohol or ethanol, wherein vegetables oil and methyl alcohol or alcoholic acid mass ratio are 0.2～2: between 1;
(2), add the mesoporous catalytic material of rare earth oxide, consumption is a vegetables oil quality 1～20%, carries out transesterification reaction 1～5 hour 60～240 ℃ of following mechanical stirring;
(3), suction filtration while hot after the reaction, isolate the rare earth oxide mesoporous catalyst;
(4), liquid phase reclaims methyl alcohol or ethanol through distillation;
(5), shift liquid phase to separating funnel, leave standstill, the upper strata is a coarse biodiesel, lower floor is a sub product glycerine.
As a kind of improvement, the acid number of vegetables oil of the present invention is 0-30mg KOH/g.
As a kind of improvement, rare earth oxide mesoporous catalyst according to the invention is to be the loading type rare earth oxide catalyst of carrier with SBA-15: like La
2O
3/ SBA-15, CeO
2/ SBA-15, Pr
6O
11/ SBA-15, Nd
2O
3/ SBA-15, Sm
2O
3/ SBA-15, Eu
3O
3/ SBA-15, Gd
2O
3/ SBA-15, Y
2O
3A kind of or wherein mixing of oxide compound more than two kinds and two kinds among/the SBA-15.
As a kind of improvement, of the present invention is that the preparation method of the loading type rare earth oxide of carrier is to be carrier with SBA-15 with SBA-15, the nitrate soln La (NO of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium
3)
3, Ce (NO
3)
3, Pr (NO
3)
3, Nd (NO
3)
3, Sm (NO
3)
3, Eu (NO
3)
3, Gd (NO
3)
3, Y (NO
3)
3Be raw material, adopting the charge capacity of single stage method preparation is the mesoporous rare-earth MOX La of 5-35% (W/W)
2O
3/ SBA-15, CeO
2/ SBA-15, Pr
6O
11/ SBA-15, Nd
2O
3/ SBA-15, Sm
2O
3/ SBA-15, Eu
2O
3/ SBA-15, Gd
2O
3/ SBA-15, Y
2O
3/ SBA-15.
As a kind of improvement; Single stage method of the present invention prepares the method for the mesoporous catalytic material of rare earth oxide; Be in the aqueous nitric acid that 75 milliliters of 2mol/L are housed, to add 2 gram block compound P123; Add proper amount of rare-earth metal nitrate solid after 0.5 hour 40 ℃ of following heated and stirred, continue to stir 1 hour, treat that rare-earth metal nitrate dissolves the back fully and adds 4.25 gram tetraethoxys; Uniform temp continues down to stir 24 hours, then mixed solution is transferred in 100 milliliters of crystallizing kettles, in 100-160 ℃ of following crystallization 12-72 hour; After crystallization finished, mixed solution was poured into to revolve in 250 milliliters of round-bottomed flasks to steam and is dewatered, and the gained solid is the mesoporous rare-earth oxide catalyzer.
As a kind of improvement, mesoporous rare-earth oxide catalyzer of the present invention is to add before the autoclave in retort furnace 400-1000 ℃ of following roasting 4 hours.
Beneficial effect of the present invention is following:
Adopt the catalyzer of the mesoporous catalytic material of this rare earth oxide as single stage method esterification, transesterification reaction, the products obtained therefrom transformation efficiency with NaOH, KOH, NaOCH
3For two-step approach of catalyzer etc. similar.Biofuel after refining is the same with homogeneous phase alkaline purification products obtained therefrom, all meets 0
#The performance index of diesel oil.Great advantage is a convenient post-treatment, and the washing that need not neutralize does not have trade effluent to produce.
Embodiment
Through specific embodiment technical scheme of the present invention is described further below:
Embodiment 1
In 100 milliliters of autoclaves, be 2: 1 ratio in pure oil quality ratio, add 20 gram refined soybean oils, 40 gram methyl alcohol add 4 gram 30%La again
2O
3/ SBA-15 catalyzer, temperature of reaction are controlled at 60 ℃, and mechanical stirring speed is 600rpm, 5 hours reaction times; Suction filtration while hot after reaction finishes is isolated catalyzer, and methyl alcohol, the standing stay-over demixion of will filtrating are then reclaimed in distillation.The upper strata product is a biofuel, and lower floor is a glycerine; Through liquid chromatographic detection, the productive rate of gained biofuel is 57.3%.
Embodiment 2
In 100 milliliters of autoclaves, be that 1.5: 1 ratio adds 20 gram quassias oil according to pure oil quality ratio, 30 gram methyl alcohol add 2g 20%Eu again
2O
3/ SBA-15 catalyzer, temperature of reaction are controlled at 120 ℃, and mechanical stirring speed is 600rpm, 3 hours reaction times; Suction filtration while hot after reaction finishes is isolated catalyzer, and methyl alcohol, the standing stay-over demixion of will filtrating are then reclaimed in distillation; The upper strata product is a biofuel, and lower floor is a glycerine.Through liquid chromatographic detection, the productive rate of gained biofuel is 82.3%.
Embodiment 3
In 100 milliliters of autoclaves, be that 0.2: 1 ratio adds 20 gram curcas oils according to pure oil quality ratio, 4 gram methyl alcohol add 2g 10%Sm again
2O
3/ SBA-15 catalyzer, temperature of reaction are controlled at 160 ℃, and magnetic agitation speed is 600rpm, 3 hours reaction times; Suction filtration while hot after reaction finishes is isolated catalyzer, and methyl alcohol, the standing stay-over demixion of will filtrating are then reclaimed in distillation; The upper strata product is a biofuel, and lower floor is a glycerine.Through liquid chromatographic detection, the productive rate of gained biofuel is 75.0%.
Embodiment 4
In 100 milliliters of autoclaves, be that 1: 1 ratio adds 20 gram peanut oil according to pure oil quality ratio, 20 gram methyl alcohol add 1g 10%Sm again
2O
3/ SBA-15 catalyzer, temperature of reaction are controlled at 200 ℃, and magnetic agitation speed is 600rpm, 2 hours reaction times; Suction filtration while hot after reaction finishes is isolated catalyzer, and methyl alcohol, the standing stay-over demixion of will filtrating are then reclaimed in distillation; The upper strata product is a biofuel, and lower floor is a glycerine.Through liquid chromatographic detection, the productive rate of gained biofuel is 98.6%.
Embodiment 5
In 100 milliliters of autoclaves, be that 1: 1 ratio adds the wild soya-bean oil of 20 grams according to pure oil quality ratio, 20 gram methyl alcohol add 0.2g 5%La again
2O
3/ SBA-15 catalyzer, temperature of reaction are controlled at 240 ℃, and magnetic agitation speed is 600rpm, 1 hour reaction times; Suction filtration while hot after reaction finishes is isolated catalyzer, and methyl alcohol, the standing stay-over demixion of will filtrating are then reclaimed in distillation; The upper strata product is a biofuel, and lower floor is a glycerine.Through liquid chromatographic detection, the productive rate of gained biofuel is 94.5%.
Five embodiment summary sheets
Claims (6)
1. the method for a rare earth oxide mesoporous material catalysis for preparing biodiesel oil is characterized in that utilizing vegetables oil for raw material and methyl alcohol or ethanol synthesis, adds a certain amount of catalyzer, obtains biofuel through over-churning and transesterification; Its concrete steps are described below:
(1), in reaction autoclave, add vegetables oil and methyl alcohol or ethanol, wherein vegetables oil and methyl alcohol or alcoholic acid mass ratio are 0.2～2: between 1;
(2), add the mesoporous catalytic material of rare earth oxide, consumption is a vegetables oil quality 1～20%, carries out transesterification reaction 1～5 hour 60～240 ℃ of following mechanical stirring;
(3), suction filtration while hot after the reaction, isolate the rare earth oxide mesoporous catalyst;
(4), liquid phase reclaims methyl alcohol or ethanol through distillation;
(5), shift liquid phase to separating funnel, leave standstill, the upper strata is a coarse biodiesel, lower floor is a sub product glycerine.
2. the mesoporous catalytic material of rare earth oxide according to claim 1 prepares method of bio-diesel oil, and the acid number that it is characterized in that described vegetables oil is 0-30mg KOH/g.
3. the mesoporous catalytic material of rare earth oxide according to claim 1 prepares method of bio-diesel oil, it is characterized in that said rare earth oxide mesoporous catalyst is to be the loading type rare earth oxide catalyst of carrier with SBA-15: like La
2O
3/ SBA-15, CeO
2/ SBA-15, Pr
6O
11/ SBA-15, Nd
2O
3/ SBA-15, Sm
2O
3/ SBA-15, Eu
3O
3/ SBA-15, Gd
2O
3/ SBA-15, Y
2O
3A kind of or wherein mixing of oxide compound more than two kinds and two kinds among/the SBA-15.
4. the mesoporous catalytic material of rare earth oxide according to claim 3 prepares method of bio-diesel oil; It is characterized in that described is that the preparation method of the loading type rare earth oxide of carrier is to be carrier with SBA-15 with SBA-15, the nitrate soln La (NO of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium
3)
3, Ce (NO
3)
3, Pr (NO
3)
3, Nd (NO
3)
3, Sm (NO
3)
3, Eu (NO
3)
3, Gd (NO
3)
3, Y (NO
3)
3Be raw material, adopting the charge capacity of single stage method preparation is the mesoporous rare-earth MOX La of 5-35% (W/W)
2O
3/ SBA-15, CeO
2/ SBA-15, Pr
6O
11/ SBA-15, Nd
2O
3/ SBA-15, Sm
2O
3/ SBA-15, Eu
2O
3/ SBA-15, Gd
2O
3/ SBA-15, Y
2O
3/ SBA-15.
5. the mesoporous catalytic material of rare earth oxide according to claim 4 prepares method of bio-diesel oil; It is characterized in that the method that described single stage method prepares the mesoporous catalytic material of rare earth oxide is in the aqueous nitric acid that 75 milliliters of 2mol/L are housed, to add 2 gram block compound P123; Add proper amount of rare-earth metal nitrate solid after 0.5 hour 40 ℃ of following heated and stirred; Continue to stir 1 hour, treat that rare-earth metal nitrate dissolves the back fully and adds 4.25 gram tetraethoxys; Uniform temp continues down to stir 24 hours, then mixed solution is transferred in 100 milliliters of crystallizing kettles, in 100-160 ℃ of following crystallization 12-72 hour; After crystallization finished, mixed solution was poured into to revolve in 250 milliliters of round-bottomed flasks to steam and is dewatered, and the gained solid is the mesoporous rare-earth oxide catalyzer.
6. the mesoporous catalytic material of rare earth oxide according to claim 5 prepares method of bio-diesel oil, it is characterized in that described mesoporous rare-earth oxide catalyzer is to add before the autoclave in retort furnace 400-1000 ℃ of following roasting 4 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102946264A CN102391914A (en) | 2011-09-30 | 2011-09-30 | Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material |
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|---|---|---|---|
| CN2011102946264A CN102391914A (en) | 2011-09-30 | 2011-09-30 | Method for preparing biodiesel by catalysis of rare-earth oxide mesoporous material |
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|---|---|
| CN102391914A true CN102391914A (en) | 2012-03-28 |
Family
ID=45859300
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924144A (en) * | 2012-11-30 | 2013-02-13 | 浙江师范大学 | Method for preparing mesoporous cerium praseodymium composite oxide |
| CN105419885A (en) * | 2015-11-24 | 2016-03-23 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN110694609A (en) * | 2019-10-25 | 2020-01-17 | 中国林业科学研究院林产化学工业研究所 | Catalytic pyrolysis self-activation in-situ synthesis carbon-based La2O3Catalyst process and products thereof |
| CN116836757A (en) * | 2023-08-14 | 2023-10-03 | 平湖市晨星科技实业有限公司 | Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460641A (en) * | 2003-06-06 | 2003-12-10 | 南京大学 | Mesopore solid alkali, mesopore functional material, its preparation method and application |
| CN101591574A (en) * | 2009-07-02 | 2009-12-02 | 浙江大学 | A kind of method of preparing biodiesel by zirconia solid base catalyst |
-
2011
- 2011-09-30 CN CN2011102946264A patent/CN102391914A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460641A (en) * | 2003-06-06 | 2003-12-10 | 南京大学 | Mesopore solid alkali, mesopore functional material, its preparation method and application |
| CN101591574A (en) * | 2009-07-02 | 2009-12-02 | 浙江大学 | A kind of method of preparing biodiesel by zirconia solid base catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924144A (en) * | 2012-11-30 | 2013-02-13 | 浙江师范大学 | Method for preparing mesoporous cerium praseodymium composite oxide |
| CN105419885A (en) * | 2015-11-24 | 2016-03-23 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN105419885B (en) * | 2015-11-24 | 2017-05-10 | 华东理工大学 | Synthesis method for preparing carboxylic ester with low content of residual acids under catalysis of solid super acid |
| CN110694609A (en) * | 2019-10-25 | 2020-01-17 | 中国林业科学研究院林产化学工业研究所 | Catalytic pyrolysis self-activation in-situ synthesis carbon-based La2O3Catalyst process and products thereof |
| CN110694609B (en) * | 2019-10-25 | 2022-07-19 | 中国林业科学研究院林产化学工业研究所 | Catalytic pyrolysis self-activation in-situ synthesis carbon-based La2O3Catalyst process and products thereof |
| CN116836757A (en) * | 2023-08-14 | 2023-10-03 | 平湖市晨星科技实业有限公司 | Method for producing biodiesel by utilizing rare earth compound and solid super acidic catalyst |
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Application publication date: 20120328 |