CN105642266A - Glycerin-free prepared biodiesel composite solid base catalyst and preparation method - Google Patents
Glycerin-free prepared biodiesel composite solid base catalyst and preparation method Download PDFInfo
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- CN105642266A CN105642266A CN201410640235.7A CN201410640235A CN105642266A CN 105642266 A CN105642266 A CN 105642266A CN 201410640235 A CN201410640235 A CN 201410640235A CN 105642266 A CN105642266 A CN 105642266A
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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
The present invention relates to a glycerin-free prepared biodiesel composite solid base catalyst and a preparation method. The preparation method comprises the following steps: 1) a calcium salt is dissolved in a solvent, the mass of the solvent is 5-20 times the mass of the calcium salt; 2) a carbonate is added into the solution to obtain a mixture, the mass of the carbonate is 5-20 times the mass of the calcium salt; 3) the solvent in the above mixture is evaporated to dryness; and 4) the mixture which is evaporated to dryness is heated at 800-1000 DEG C for 4-10 hours, and cooled to room temperature to prepare the glycerin-free prepared biodiesel composite solid base catalyst. The super base and weak base composite solid base catalyst is prepared by indirectly loading calcium oxide onto the carbonate, when the glycerin-free prepared biodiesel composite solid base catalyst is used in production of biodiesel, the glycerin-free prepared biodiesel composite solid base catalyst is conducive to upgrading of the production process of the biodiesel, and improves the economic benefits of the biodiesel industry.
Description
Technical field
The present invention relates to and a kind of prepare the composite solid alkaline catalysts of biofuel and its preparation method and application without glycerine method, belong to technical field of biodiesel preparation.
Background technology
In recent years; energy scarcity problem is increasingly severe, international oil price rising all the way, impels countries in the world actively to research and develop renewable substitute energy; biofuel is as a kind of extremely promising bioenergy, and its large-scale production receives the concern of academia and industrial community.
But, often producing 9 tons of biofuel just has the thick product of the glycerine of 1 ton to generate, and the output adding tradition glycerine (natural glycerin, ferment glycerin, synthetic glycerine) is inherently bigger, causes the market maintenance of glycerine to be far longer than demand. It is estimated that only glycerine market maintenance in 2010 has just exceeded 1.2 hundred ten thousand tons, therefore how the low price raw glycerine produced in production of biodiesel process is carried out the problem that effective comprehensive utilization has become the sternness of biofuel industry and key.
Biofuel must meet the requirement of relevant criterion as mediation raw material before introducing to the market, wherein the specification of biofuel has been made corresponding regulation by ASTMD6751 and EU criteria council standard EN 14214, limits the amount of free glycerol and the amount of glyceryl ester in biofuel. Free glycerol is the by product in production of biodiesel, and direactive glyceride, two glyceryl ester, Witepsol W-S 55 are the pollutents in biofuel, and the free glycerol of high-content and glyceryl ester can cause the increase of engine deposits.
Two ester-interchange method is biodiesel oil preparing process emerging in recent years, the method adopts natural fats and oils and methyl esterification reagent (such as methylcarbonate) reaction, it is carbonic ether by transformation of glycerol while preparation biofuel, both the problem of glycerine remnants in traditional biological diesel production can have been solved, the carbonic acid glyceride of high added value can be obtained again simultaneously, make multiple step height such as the preparation of biofuel, the separation of by product integrated, not only be conducive to the upgrading of biofuel preparation technology, and improve the economic benefit of biofuel industry.
Although the at present existing report adopting natural fats and oils and dimethyl carbonate synchronously to prepare biofuel and carbonic acid glyceride, but it exists that the reaction times is longer, raw material and product very easily saponification, ultimate yield is not high, saponified is difficult to shortcomings such as being separated.
Summary of the invention
For solving the problems of the technologies described above, it is an object of the invention to provide a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, this catalyzer has higher activity in the reaction preparing biofuel without glycerine method, and can reduce saponification problems, simplifies separable programming.
The present invention also aims to provide the preparation method and application of the above-mentioned composite solid alkaline catalysts preparing biofuel without glycerine method.
For achieving the above object, the present invention provides the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, and it comprises the following steps:
The first step, is dissolved in solvent by calcium salt, and the quality of solvent is 5-20 times of calcium salt quality;
2nd step, adds carbonate in above-mentioned solution, obtains mixture, and the quality of carbonate is 5-20 times of calcium salt quality;
3rd step, steams dry by the solvent in said mixture;
4th step, heats steaming the mixture after doing 4-10 hour at 800-1000 DEG C, is cooled to room temperature, obtains preparing without glycerine method the composite solid alkaline catalysts of biofuel.
In above-mentioned preparation method, it may be preferred that described calcium salt is calcium formiate, lime acetate or nitrocalcite, and its purity is preferably at least chemical pure.
In above-mentioned preparation method, it may be preferred that described solvent is methyl alcohol or ethanol, and its purity is preferably at least chemical pure.
In above-mentioned preparation method, it may be preferred that described carbonate is sodium carbonate, salt of wormwood or cesium carbonate, and its purity is preferably at least chemical pure.
Present invention also offers a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, this catalyzer is obtained by above-mentioned preparation method.
Present invention also offers the application of the above-mentioned composite solid alkaline catalysts preparing biofuel without glycerine method in preparation biofuel.
In above-mentioned application, it may be preferred that it comprises the following steps:
By grease, methyl alcohol, methylcarbonate mixing, add the above-mentioned composite solid alkaline catalysts preparing biofuel without glycerine method and react, wherein: the amount of substance of described grease, methyl alcohol, methylcarbonate is than being 1:5-10:1-3.
In above-mentioned application, it may be preferred that the consumption of described composite solid alkaline catalysts is the 1-15% of the amount of lipid phase.
In above-mentioned application, it may be preferred that described grease, methyl alcohol, methylcarbonate and composite solid alkaline catalysts under reflux conditions react, the reaction times is 1-6 hour, it is more preferable to be 2-6 hour.
Calcium oxide is prepared the composite solid alkaline catalysts of super base and weak base by the present invention by mode load indirectly on carbonate; It is applied to prepare among the grease-methyl alcohol-dimethyl carbonate system of biofuel, grease, methyl alcohol and methylcarbonate, fast reaction speed can be activated on the one hand, it is to increase reaction yield simultaneously; Calcium oxide is carried on the surface of salt of wormwood/sodium carbonate on the other hand, and good dispersity, utilization ratio height, also enhances the stability of calcium oxide. Such catalyst grease-methyl alcohol-dimethyl carbonate, synchronous preparation biofuel and carbonic acid glyceride, the transformation efficiency of grease can reach more than 95%.
Embodiment
In order to the technology feature to the present invention, object and useful effect have understanding clearly, the existing technical scheme to the present invention carries out following detailed explanation, but can not be interpreted as to the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 5 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the calcium formiate of chemical pure, and solvent is the methyl alcohol of chemical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 5 times of calcium salt quality, and carbonate is the salt of wormwood of chemical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 10 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 800 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:5:1, the consumption of composite solid alkaline catalysts is the 5% of the amount of substance of grease, reaction system under reflux conditions reacts 5 hours, obtain biofuel, the transformation efficiency of grease reaches 96%, and glycerine is synchronously converted into carbonic acid glyceride.
Embodiment 2
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 8 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the lime acetate of chemical pure, and solvent is the ethanol of chemical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 10 times of calcium salt quality, and carbonate is the sodium carbonate of chemical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 5 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 850 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:6:1, the consumption of composite solid alkaline catalysts is the 6% of the amount of substance of grease, reaction system under reflux conditions reacts 5 hours, obtain biofuel, the transformation efficiency of grease reaches 97%, and glycerine is synchronously converted into carbonic acid glyceride.
Embodiment 3
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 10 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the nitrocalcite of chemical pure, and solvent is the ethanol of analytical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 10 times of calcium salt quality, and carbonate is the cesium carbonate of chemical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 5 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 900 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:8:2, the consumption of composite solid alkaline catalysts is the 5% of the amount of substance of grease, reaction system under reflux conditions reacts 3 hours, obtain biofuel, the transformation efficiency of grease reaches 96%, and glycerine is synchronously converted into carbonic acid glyceride.
Embodiment 4
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 15 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the calcium formiate of analytical pure, and solvent is the ethanol of chemical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 20 times of calcium salt quality, and carbonate is the cesium carbonate of analytical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 6 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 900 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:9:3, the consumption of composite solid alkaline catalysts is the 10% of the amount of substance of grease, reaction system under reflux conditions reacts 2 hours, obtain biofuel, the transformation efficiency of grease reaches 98%, and glycerine is synchronously converted into carbonic acid glyceride.
Embodiment 5
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 20 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the nitrocalcite of chemical pure, and solvent is the methyl alcohol of chemical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 20 times of calcium salt quality, and carbonate is the salt of wormwood of chemical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 6 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 850 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:10:1, the consumption of composite solid alkaline catalysts is the 15% of the amount of substance of grease, reaction system under reflux conditions reacts 2 hours, obtain biofuel, the transformation efficiency of grease reaches 98%, and glycerine is synchronously converted into carbonic acid glyceride.
Embodiment 6
Present embodiments provide the preparation method of a kind of composite solid alkaline catalysts preparing biofuel without glycerine method, comprise the following steps:
The first step, is dissolved in the solvent of 10 times of quality by calcium salt, stirs and makes it dissolve, and calcium salt is the calcium formiate of analytical pure, and solvent is the ethanol of analytical pure;
2nd step, adds carbonate in above-mentioned solution while stirring, obtains mixture, and the quality of carbonate is 15 times of calcium salt quality, and carbonate is the salt of wormwood of analytical pure;
3rd step, steams dry by the solvent in said mixture;
4th step, is placed in retort furnace by steaming the mixture after doing, heats 5 hours, be cooled to the composite solid alkaline catalysts that namely room temperature obtains preparing without glycerine method biofuel at 900 DEG C.
When this composite solid alkaline catalysts is applied to grease-methyl alcohol-dimethyl carbonate system, in system, the amount of substance of grease-methyl alcohol-methylcarbonate is than being 1:8:1.1, the consumption of composite solid alkaline catalysts is the 15% of the amount of substance of grease, reaction system under reflux conditions reacts 1 hour, obtain biofuel, the transformation efficiency of grease reaches 98%, and glycerine is synchronously converted into carbonic acid glyceride.
Claims (9)
1. prepare a preparation method for the composite solid alkaline catalysts of biofuel without glycerine method, it comprises the following steps:
The first step, is dissolved in solvent by calcium salt, and the quality of solvent is 5-20 times of calcium salt quality;
2nd step, adds carbonate in above-mentioned solution, obtains mixture, and the quality of carbonate is 5-20 times of calcium salt quality;
3rd step, steams dry by the solvent in said mixture;
4th step, heats steaming the mixture after doing 4-10 hour at 800-1000 DEG C, is cooled to room temperature, obtains preparing without glycerine method the composite solid alkaline catalysts of biofuel.
2. preparation method according to claim 1, wherein: described calcium salt is calcium formiate, lime acetate or nitrocalcite, and its purity is preferably at least chemical pure.
3. preparation method according to claim 1 and 2, wherein: described solvent is methyl alcohol or ethanol, and its purity is preferably at least chemical pure.
4. preparation method according to any one of claim 1 to 3, wherein: described carbonate is sodium carbonate, salt of wormwood or cesium carbonate, and its purity is preferably at least chemical pure.
5. prepare a composite solid alkaline catalysts for biofuel without glycerine method, it is prepared by the method according to any one of Claims 1-4.
6. the application of the composite solid alkaline catalysts preparing biofuel without glycerine method according to claim 5 in preparation biofuel.
7. application according to claim 6, it comprises the following steps:
By grease, methyl alcohol, methylcarbonate mixing, add the composite solid alkaline catalysts preparing biofuel without glycerine method according to claim 5 and react, wherein: the amount of substance of described grease, methyl alcohol, methylcarbonate is than being 1:5-10:1-3.
8. application according to claim 6 or 7, wherein: the consumption of described composite solid alkaline catalysts is the 1-15% of the amount of substance of grease.
9. application according to any one of claim 6 to 8, wherein: described grease, methyl alcohol, methylcarbonate and composite solid alkaline catalysts under reflux conditions react, the reaction times is 1-6 hour, it is preferable that 2-6 hour.
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| CN201410640235.7A CN105642266B (en) | 2014-11-13 | 2014-11-13 | The complex solid base catalyst and preparation method of no glycerol method preparation biodiesel |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531916A (en) * | 2009-04-21 | 2009-09-16 | 合肥工业大学 | Solid alkali catalytic method for preparing biological diesel oil |
| CN102061224A (en) * | 2010-10-11 | 2011-05-18 | 西安石油大学 | Method for preparing biodiesel by catalysis of modified calcium oxide |
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
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- 2014-11-13 CN CN201410640235.7A patent/CN105642266B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531916A (en) * | 2009-04-21 | 2009-09-16 | 合肥工业大学 | Solid alkali catalytic method for preparing biological diesel oil |
| CN102061224A (en) * | 2010-10-11 | 2011-05-18 | 西安石油大学 | Method for preparing biodiesel by catalysis of modified calcium oxide |
| CN103436369A (en) * | 2013-09-04 | 2013-12-11 | 西安石油大学 | Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol |
Non-Patent Citations (1)
| Title |
|---|
| 张秋云等: "纳米K2CO3/CaO催化大豆油制备生物柴油", 《化学工程》 * |
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