CN106807447A - The preparation method of production of biodiesel composite catalyst - Google Patents
The preparation method of production of biodiesel composite catalyst Download PDFInfo
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- CN106807447A CN106807447A CN201510840550.9A CN201510840550A CN106807447A CN 106807447 A CN106807447 A CN 106807447A CN 201510840550 A CN201510840550 A CN 201510840550A CN 106807447 A CN106807447 A CN 106807447A
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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
The invention discloses a kind of preparation method of production of biodiesel composite catalyst, by in water soluble phenol resin, ferrocene, PVOH and ethanol addition reactor, pH to neutrality is sufficiently stirred for and adjusted, obtain homogeneous phase solution, it is placed in resistance furnace after vaccum dewatering, heat drying, in N2Under protection, more than 2h is incubated after rising to 600~800 DEG C from normal temperature with the heating rate of 1~5 DEG C/min, obtains phenolic resin base magnetic active carbon；It is then immersed in the aqueous solution of alkaline earth metal hydroxide and alkali metal hydroxide, after agitated dipping 0.5-12h, heating solvent evaporated, 200-400 DEG C fired more than 0.5 hour, it is size-reduced with screening after target product, phenolic resin base magnetic active carbon addition and alkaline earth metal hydroxide and alkali metal hydroxide total mass ratio are 2-5：100, the simple production process is with low cost, after the completion of reaction can convenient enriching and recovering by externally-applied magnetic field.
Description
Technical field
The present invention relates to a kind of preparation method of production of biodiesel composite catalyst.
Background technology
Using biomass materials such as the soybean oil of wide material sources, rapeseed oil, rice bran oil, the former oil expression of transgenosis oil crops, catering trade waste grease and industrial oil foots, with the fatty acid methyl ester that methyl alcohol carries out ester exchange reaction preparation, as the substitute fuel of mineral diesel, have the advantages that power performance it is good, using safety, pollutant emission index is low and resource is renewable.
Relative to acid catalytic systems, base-catalyzed transesterification reaction is high with reaction specific activity and alcohol ester is than requiring relatively low advantage, but in the technique of the liquid base catalyzed transesterification such as NaOH, sodium methoxide, the washing of complex steps isolates and purifies link and still inevitably increases running cost and Environmental costs；And in the production of biodiesel of lipase-catalyzed esterification, existing reaction efficiency is low, catalyst is expensive and methyl alcohol the problems such as poisoning effect, also limit competitiveness of the method on applied generalization to enzyme catalyst.Solid base catalyst can be on the premise of high activity of catalyst be maintained, Simplified flowsheet link, and reducing production cost turns into the object competitively studied
Existing solid base catalyst reduces its particle diameter in order to increase specific surface area, typically, which increases its specific surface area, improves catalysis activity, but particle diameter gets over small catalyst and is just more difficult to separate and reclaim, and is that its commercial Application brings difficulty.
The content of the invention
The invention provides a kind of preparation method of production of biodiesel composite catalyst, the simple production process is with low cost, after the completion of reaction can convenient enriching and recovering by externally-applied magnetic field.
In order to solve the above problems, the technical solution adopted by the present invention is a kind of such, preparation method of production of biodiesel composite catalyst, is comprised the following steps：
1）By water soluble phenol resin, ferrocene, PVOH and ethanol with mass ratio 100:1-10：8-15:100-200 is added in reactor, is sufficiently stirred for and adjusts pH to neutrality, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution vaccum dewatering, heat drying obtain solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, under inert gas shielding, more than 2h is incubated after rising to 600~800 DEG C from normal temperature with the heating rate of 1~5 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）Phenolic resin base magnetic active carbon is immersed in the aqueous solution of alkaline earth metal hydroxide and alkali metal hydroxide, after agitated dipping 0.5-12 h, heating solvent evaporated, 200-400 DEG C after fired more than 0.5 hour, it is size-reduced with screening after target product, wherein, both alkaline earth metal hydroxide and alkali metal hydroxide gross mass and addition step 4）In phenolic resin base magnetic active carbon mass ratio be 2-5:100.
Preferably, alkali metal hydroxide and the mass ratio of alkaline earth metal hydroxide are 5:40:60:95.
Preferably, alkali metal hydroxide is the mixture of one or more arbitrary proportions in LiOH, NaOH, KOH；Alkaline earth metal hydroxide is Mg（OH）2、Ca（OH）2In one or two arbitrary proportions mixture.
Preferably, the solid content of the water soluble phenol resin is 25.0~45.0w%.
Preferably, during homogeneous phase solution vaccum dewatering, the vacuum for using is -0.080~-0.098MPa, and temperature is 20~60 DEG C, and the time is 1~10 h.
Preferably, the reagent used by regulation pH is selected from any one in trimethylamine, triethylamine or hexamethylenetetramine or mixture of more than two kinds.
Beneficial effect：Alkali metal oxide and alkaline earth oxide are carried on phenolic resin base magnetic active carbon surface by the present invention, the hydroxyl produced after the metal oxide surface absorption water of the support type and electronegative Lattice Oxygen, so as under gentle reaction condition, promoting the exchange reaction of fatty acid ester is efficiently carried out, ester exchange amount is big, the conversion ratio of grease is up to more than 90%, in addition, because phenolic resin base magnetic active carbon has magnetic, using externally-applied magnetic field to catalyst enriching and recovering after thus reaction terminates, reuse, reduce the running cost and Environmental costs of production of biodiesel.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and these embodiments are only used for explaining the present invention, are not intended to limit the scope of the present invention..
Embodiment 1
A kind of preparation method of production of biodiesel composite catalyst, specific preparation method is as follows：
1）It is the water soluble phenol resin of 25.0w% by 100g solid contents, during 1g ferrocene, 8g PVOHs and 100g ethanol adds reactor, is sufficiently stirred for and adjusts pH to neutrality with hexamethylenetetramine, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution is -0.080~-0.098MPa in vacuum, and temperature is at 40 DEG C, after the h of vaccum dewatering 1~10, heat drying obtains solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, in N2Under protection, 2~5h is incubated after rising to 600 DEG C from normal temperature with the heating rate of 1 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）By 0.8gNaOH and 1.20g Mg（OH）2It is dissolved in 100ml water, obtains NaOH and Mg（OH）2Mixed solution, weigh 100g phenolic resin base magnetic active carbons and be immersed in mixed solution, after agitated dipping 0.5-12 h, heat solvent evaporated, at 400 DEG C after fired more than 2 hours, it is size-reduced with screening after obtain target product.
Embodiment 2
A kind of preparation method of production of biodiesel composite catalyst, specific preparation method is as follows：
1）It is the water soluble phenol resin of 30.0w% by 100g solid contents, during 6g ferrocene, 12g PVOHs and 120g ethanol adds reactor, is sufficiently stirred for and adjusts pH to neutrality with hexamethylenetetramine, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution is -0.080~-0.098MPa in vacuum, and temperature is at 40 DEG C, after the h of vaccum dewatering 1~10, heat drying obtains solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, in N2Under protection, 2~5h is incubated after rising to 600 DEG C from normal temperature with the heating rate of 2 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）By 0.1gNaOH and 1.9g Ca（OH）2It is dissolved in 100ml water, obtains NaOH and Ca（OH）2Mixed solution, weigh 100g phenolic resin base magnetic active carbons and be immersed in mixed solution, after agitated dipping 0.5-12 h, heat solvent evaporated, at 200 DEG C after fired more than 2 hours, it is size-reduced with screening after obtain target product.
Embodiment 3
A kind of preparation method of production of biodiesel composite catalyst, specific preparation method is as follows：
1）It is the water soluble phenol resin of 45.0w% by 100g solid contents, during 8g ferrocene, 12g PVOHs and 150g ethanol adds reactor, is sufficiently stirred for and adjusts pH to neutrality with hexamethylenetetramine, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution is -0.080~-0.098MPa in vacuum, and temperature is at 60 DEG C, after the h of vaccum dewatering 1~10, heat drying obtains solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, in N2Under protection, 2~5h is incubated after rising to 600 DEG C from normal temperature with the heating rate of 2 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）By 1.2gKOH, 1.4g Mg（OH）2、1.4g Ca（OH）2It is dissolved in 100ml water, obtains NaOH, Mg（OH）2With Ca（OH）2Mixed solution, weigh 100g phenolic resin base magnetic active carbons and be immersed in mixed solution, after agitated dipping 0.5-12 h, heat solvent evaporated, at 300 DEG C after fired more than 2 hours, it is size-reduced with screening after obtain target product.
Embodiment 4
A kind of preparation method of production of biodiesel composite catalyst, specific preparation method is as follows：
1）It is the water soluble phenol resin of 45.0w% by 100g solid contents, during 10g ferrocene, 15g PVOHs and 20g ethanol adds reactor, is sufficiently stirred for and adjusts pH to neutrality with hexamethylenetetramine, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution is -0.080~-0.098MPa in vacuum, and temperature is at 60 DEG C, after the h of vaccum dewatering 1~10, heat drying obtains solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, in N2Under protection, 2~5h is incubated after rising to 600 DEG C from normal temperature with the heating rate of 2 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）By 1.1gNaOH, 1.2gKOH, 1.25g Mg（OH）2With 1.45g Ca（OH）2It is dissolved in 100ml water, obtains NaOH, KOH, Mg（OH）2With Ca（OH）2Mixed solution, weigh 100g phenolic resin base magnetic active carbons and be immersed in mixed solution, after agitated dipping 0.5-12 h, heat solvent evaporated, at 300 DEG C after fired more than 2 hours, it is size-reduced with screening after obtain target product.
Respectively by the catalyst in embodiment 1-4（Catalyst charge is that rapeseed oil 2-4wt% is added in reactor, by rapeseed oil and methyl alcohol with mol ratio be 1:4 are added to reactor, are reacted 1-2 hours at a temperature of mechanical agitation and 40-70 DEG C, after reaction terminates, after reclaiming catalyst through filtering and magnetic, are continuously heating to 100-120 DEG C, and methyl alcohol is steamed；Stratification, lower floor glycerine is reclaimed, then vacuum distillation, is to steam required product fatty acid methyl ester under the conditions of -0.08--0.10MPa, temperature are 180-260 DEG C in pressure, and after testing, the conversion ratio of grease is up to more than 90%.
The above embodiments merely illustrate the technical concept and features of the present invention; its object is to allowing person skilled in the art to will appreciate that present disclosure and implementing according to this; it is not intended to limit the scope of the present invention; any equivalent change or modification in accordance with the spirit of the invention, should all be included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of production of biodiesel composite catalyst, it is characterised in that comprise the following steps：
1）By water soluble phenol resin, ferrocene, PVOH and ethanol with mass ratio 100:1-10：8-15:100-200 is added in reactor, is sufficiently stirred for and adjusts pH to neutrality, obtains homogeneous phase solution；
2）By step 1）Gained homogeneous phase solution vaccum dewatering, heat drying obtain solids phenol-formaldehyde resin mixture；
3）By step 2）Gained solid mixture is placed in resistance furnace, under inert gas shielding, more than 2h is incubated after rising to 600~800 DEG C from normal temperature with the heating rate of 1~5 DEG C/min, obtains phenolic resin base magnetic active carbon；
4）Phenolic resin base magnetic active carbon is immersed in the aqueous solution of alkaline earth metal hydroxide and alkali metal hydroxide, after agitated dipping 0.5-12 h, heating solvent evaporated, 200-400 DEG C after fired more than 0.5 hour, it is size-reduced with screening after target product, wherein, both alkaline earth metal hydroxide and alkali metal hydroxide gross mass and addition step 4）In phenolic resin base magnetic active carbon mass ratio be 2-5：100.
2. the preparation method of a kind of production of biodiesel composite catalyst according to claim 1, it is characterised in that alkali metal hydroxide is 5 with the mass ratio of alkaline earth metal hydroxide:40:60:95.
3. the preparation method of a kind of production of biodiesel composite catalyst according to claim 1 and 2, it is characterised in that alkali metal hydroxide is the mixture of one or more arbitrary proportions in LiOH, NaOH, KOH；Alkaline earth metal hydroxide is Mg（OH）2、Ca（OH）2In one or two arbitrary proportions mixture.
4. the preparation method of a kind of production of biodiesel composite catalyst according to claim 1, it is characterised in that the solid content of the water soluble phenol resin is 25.0~45.0w%.
5. a kind of preparation method of production of biodiesel composite catalyst according to claim 1, it is characterised in that during homogeneous phase solution vaccum dewatering, the vacuum for using is -0.080~-0.098MPa, and temperature is 20~60 DEG C, and the time is 1~10 h.
6. the preparation method of a kind of production of biodiesel composite catalyst according to claim 1, it is characterised in that the reagent used by regulation pH is selected from any one or mixture of more than two kinds in trimethylamine, triethylamine or hexamethylenetetramine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376836A (en) * | 2017-07-20 | 2017-11-24 | 安徽理工大学 | A kind of preparation method of ature of coal magnetic-particle activated carbon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101157037A (en) * | 2007-11-12 | 2008-04-09 | 中兴能源技术（武汉）有限公司 | A method for preparing biology diesel oil and the used magnetic solid base catalyst |
| CN104492436A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院西双版纳热带植物园 | Carbon-based magnetic solid alkali catalyst and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157037A (en) * | 2007-11-12 | 2008-04-09 | 中兴能源技术（武汉）有限公司 | A method for preparing biology diesel oil and the used magnetic solid base catalyst |
| CN104492436A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院西双版纳热带植物园 | Carbon-based magnetic solid alkali catalyst and application thereof |
Non-Patent Citations (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376836A (en) * | 2017-07-20 | 2017-11-24 | 安徽理工大学 | A kind of preparation method of ature of coal magnetic-particle activated carbon |
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Application publication date: 20170609 |