CN103657626A - Preparation method of Al2O3/CaMgO composite solid base catalyst - Google Patents
Preparation method of Al2O3/CaMgO composite solid base catalyst Download PDFInfo
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- CN103657626A CN103657626A CN201210341533.7A CN201210341533A CN103657626A CN 103657626 A CN103657626 A CN 103657626A CN 201210341533 A CN201210341533 A CN 201210341533A CN 103657626 A CN103657626 A CN 103657626A
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- camgo
- catalyst
- solid base
- base catalyst
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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
Abstract
The invention discloses a preparation method of an Al2O3/CaMgO composite solid base catalyst. The preparation method comprises the steps of adding aluminium oxide powder into mixed liquid of Ca(NO3)2.4H2O and Mg(NO3)2.6H2O, mixing according to the proportion, adding alkali to form colloidal precipitate, ageing for 24 hours, precipitating, filtering, separating, cleaning, then drying, putting a mixture in a muffle furnace to calcine for 6 hours at the temperature of 800 DEG C, grinding and sieving to obtain the Al2O3/CaMgO composite solid base catalyst with the particle diameter being 140-200mum. The preparation method disclosed by the invention has the advantages that the CaMgO in the catalyst accounts for 15-30% of the catalyst in mass fraction, the mechanical strength and the stability are good, the separation is easy, and the repeated use for multiple times can be achieved; the catalyst is utilized for catalyzing the ester exchange reaction between waste vegetable oil and alcohol, the reaction condition is mild and the yield of biodiesel is up to 97%. The preparation method is applicable to the solid base catalyst for preparing the biodiesel by adopting the waste vegetable oil as a raw material.
Description
Technical field
The present invention relates to a kind of Al
2o
3the preparation method of/CaMgO complex solid base catalyst, specifically a kind of Al based on alumina support
2o
3the preparation method of/CaMgO complex solid base catalyst, catalyst activity composition CaMgO is dispersed on the alumina support with high-specific surface area.This catalyst can be used for take waste vegetable oil as main material production biodiesel.
Background technology
The waste vegetable oil (main component triglycerides) of take is raw material, by the ester exchange reaction of base catalysis (or acid catalysis) triglycerides and methyl alcohol or ethanol, production biodiesel processes is easy, product is used to have as oil product and is easy to degrade, pollute little feature, and can reclaim the waste vegetable oil that catering industry produces, effectively a large amount of utilize " waste oils " simultaneously.With waste vegetable oil production biodiesel, conventionally use homogeneous phase base catalyst as NaOH, potassium hydroxide etc., although catalytic rate is very fast, alkali is dissolved in reaction system conventionally, is difficult to separated recovery, and produce a large amount of alkali wasteliquids or cause product basicity higher, be difficult to process.Adopt heterogeneous solid base catalyst to address these problems, and catalyst can reuse.The solid base catalyst such as calcium oxide and magnesia (heterogeneous catalysis) is catalyzed transesterification effectively, for the production of biodiesel, but calcium oxide and magnesia etc. is easily sintering and reunion in preparation process, make its specific area very little, catalytic active site is difficult to effectively expose and make full use of, thereby has a strong impact on catalytic activity.And calcium oxide and the equal mechanical strength of magnesia and poor stability, in ester exchange reaction rapid mixing process, partly " dissolving " (fragmentation or partial hydrolysis), in reaction system, forms suspension, makes to have reacted rear catalyst separation difficulty.Therefore, calcium oxide and magnesia (production biodiesel catalyst) specific area is low, be difficult to disperse, and mechanical strength and poor stability become the essential problem solving of its application.
Summary of the invention
Low in order to solve in prior art calcium oxide and magnesia catalyst specific area, and the problem of mechanical strength and poor stability, improve its catalytic activity and stability in biodiesel ester exchange reaction, the invention provides a kind of Al
2o
3the preparation method of/CaMgO complex solid base catalyst.The Al that utilizes the method to prepare
2o
3/ CaMgO complex solid base catalyst has higher specific area (> 150m
2/ g), good catalytic activity and mechanical strength, during use, in biodiesel preparation feedback system, can " not dissolve ", and can improve the productive rate of target product (biodiesel) and selective.Utilize Al
2o
3the ester exchange reaction of/CaMgO complex solid base catalyst catalysis waste vegetable oil and ethanol, reaction condition gentle (70 ℃ of reaction temperatures, normal pressure), catalyst amount low (approximately 10%), finally can obtain biodiesel, and yield is up to 97%.Catalyst is easy to than separated in product by filtration, and repeatedly reusable, still can maintain good catalytic activity.The present invention is applicable to be made to take waste vegetable oil and prepares the solid base catalyst of biodiesel as raw material.
The present invention will address the above problem, and the technical scheme adopting is:
Utilize the compound alkali solid catalyst of CaMgO to replace original calcium oxide and magnesia single catalyst, and utilize the alumine with high specific surface area supported catalyst active component CaMgO with good mechanical strength and stability, thereby significantly improve catalyst decentralization and active site concentration, and reduce sintering and the reunion in preparation process, improve catalyst mechanical strength and stability.Al
2o
3the preparation process of/CaMgO complex solid base catalyst comprises:
(1) wet impregnation: utilize alumine with high specific surface area dipping calcium magnesium precursor solution;
(2) precipitation and ageing: add alkali and form colloidal precipitation, and ageing 24 hours;
(3) isolated by filtration;
(4) dry;
(5) calcination;
(6) pulverize;
(7) screening.
The concrete implementation method of the present invention is as follows:
Take certain amount of alumina powder, add corresponding nitrate solution (Ca (NO
3)
24H
2o, Mg (NO
3)
26H
2o) in, mix according to a certain ratio, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours.Sedimentation and filtration is separated, uses deionized water cyclic washing, and dry at 120 ℃.Dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, and take out after being cooled to room temperature and grind, then through sieving to such an extent that particle diameter is the Al of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
By different this reactions of raw material proportioning, can control Al
2o
3the mass fraction that in/CaMgO catalyst, CaMgO accounts in catalyst is respectively 15%, 20%, 25%, 30%.Utilize the ester exchange reaction of this catalyst waste vegetable oil and ethanol, reaction condition is gentle, and biodiesel yield is up to 97%.And find to work as Al
2o
3in/CaMgO catalyst, during CaMgO mass fraction 15-25%, with CaMgO in catalyst, increase, catalytic activity increases to some extent, but while surpassing 25%, catalyst activity composition is reunited to some extent, and catalytic activity is declined on the contrary to some extent.
The specific embodiment:
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Embodiment 1:
Al
2o
3in/CaMgO complex solid base catalyst, CaMgO mass fraction 15% is implemented.
Take 81.6g alumina powder, add 100mL Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2in O mixed solution, (be 2mol/L), be fully uniformly mixed, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours.Sedimentation and filtration is separated, use deionized water cyclic washing, and dry at 120 ℃.Dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, grinds after taking out cooling room temperature, then through sieving to such an extent that particle diameter is the Al of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
Utilize this Al
2o
3the ester exchange reaction of/CaMgO complex solid base catalyst catalysis waste vegetable oil and ethanol, at 70 ℃ of reaction temperatures, normal pressure, Al
2o
3/ CaMgO catalyst amount 10% (accounting for reactant quality mark 10%), reactant molar ratio (triglycerides in waste vegetable oil: ethanol) 1: 8 o'clock, finally obtain biodiesel yield and reach 88.5%.
Embodiment 2:
Al
2o
3in/CaMgO complex solid base catalyst, CaMgO mass fraction 20% is implemented.
Take 57.6g alumina powder, add 100mL Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2in O mixed solution, (be 2mol/L), be fully uniformly mixed, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours.Sedimentation and filtration is separated, use deionized water cyclic washing, and dry at 120 ℃.Dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, grinds after taking out cooling room temperature, then through sieving to such an extent that particle diameter is the Al of 90-140 micron and two kinds of different-grain diameters of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
Utilize this Al
2o
3the ester exchange reaction of/CaMgO complex solid base catalyst catalysis waste vegetable oil and ethanol, at 70 ℃ of reaction temperatures, normal pressure, Al
2o
3/ CaMgO catalyst amount 10% (accounting for reactant quality mark 10%), reactant molar ratio (triglycerides in waste vegetable oil: ethanol) 1: 8 o'clock, finally obtain biodiesel yield and reach 93.8%.
Embodiment 3:
Al
2o
3in/CaMgO complex solid base catalyst, CaMgO mass fraction 25% is implemented.
Take 43.2g alumina powder, add 100mL Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2in O mixed solution, (be 2mol/L), be fully uniformly mixed, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours.Sedimentation and filtration is separated, use deionized water cyclic washing, and dry at 120 ℃.Dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, grinds after taking out cooling room temperature, then through sieving to such an extent that particle diameter is the Al of 90-140 micron and two kinds of different-grain diameters of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
Utilize this Al
2o
3the ester exchange reaction of/CaMgO complex solid base catalyst catalysis waste vegetable oil and ethanol, at 70 ℃ of reaction temperatures, normal pressure, Al
2o
3/ CaMgO catalyst amount 10% (accounting for reactant quality mark 10%), reactant molar ratio (triglycerides in waste vegetable oil:, finally obtain biodiesel yield up to 97.2% at ethanol) 1: 8 o'clock.
Embodiment 4:
Al
2o
3in/CaMgO complex solid base catalyst, CaMgO mass fraction 30% is implemented.
Take 33.6g alumina powder, add 100mL Ca (NO
3)
24H
2o and Mg (NO
3)
26H
2in O mixed solution, (be 2mol/L), be fully uniformly mixed, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours.Sedimentation and filtration is separated, use deionized water cyclic washing, and dry at 120 ℃.Dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, grinds after taking out cooling room temperature, then through sieving to such an extent that particle diameter is the Al of 90-140 micron and two kinds of different-grain diameters of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
Utilize this Al
2o
3the ester exchange reaction of/CaMgO complex solid base catalyst catalysis waste vegetable oil and ethanol, at 70 ℃ of reaction temperatures, normal pressure, Al
2o
3/ CaMgO catalyst amount 10% (accounting for reactant quality mark 10%), reactant molar ratio (triglycerides in waste vegetable oil: ethanol) 1: 8 o'clock, finally obtain biodiesel yield and reach 94.1%.
Claims (3)
1. an Al
2o
3the preparation method of/CaMgO complex solid base catalyst, is characterized in that alumina powder to add to corresponding nitrate solution (Ca (NO
3)
24H
2o, Mg (NO
3)
26H
2o) in, mix according to a certain ratio, slowly add Na
2cO
3with NaOH solution, regulate 8 to the 9 formation colloidal precipitations of pH of mixed value, mixture was in 60 ℃ of rapid stirring ageings 24 hours, sedimentation and filtration is separated, use deionized water cyclic washing, and dry at 120 ℃, dried sediment is placed in Muffle furnace calcination 6 hours at 800 ℃, taking-up grinds after being cooled to room temperature, then through sieving to such an extent that particle diameter is the Al of 140-200 micron
2o
3/ CaMgO complex solid base catalyst.
2. according to right 1, require described Al
2o
3/ CaMgO complex solid base catalyst, is characterized in that: Al
2o
3in/CaMgO catalyst, CaMgO accounts for the mass fraction 15-30% in catalyst, catalyst particle size 140-200 micron.
3. according to right 1, require described Al
2o
3/ CaMgO complex solid base catalyst, is characterized in that: described catalyst activity composition is CaMgO, and catalyst carrier is alumine with high specific surface area, for take waste vegetable oil as raw material production biodiesel.
Priority Applications (1)
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|---|---|---|---|
| CN201210341533.7A CN103657626A (en) | 2012-09-03 | 2012-09-03 | Preparation method of Al2O3/CaMgO composite solid base catalyst |
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| CN201210341533.7A CN103657626A (en) | 2012-09-03 | 2012-09-03 | Preparation method of Al2O3/CaMgO composite solid base catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289237A (en) * | 2014-09-28 | 2015-01-21 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
| CN109603801A (en) * | 2018-12-19 | 2019-04-12 | 山东大学 | A kind of load type solid body base catalyst and its preparation method and application producing biodiesel |
| CN109663585A (en) * | 2018-11-13 | 2019-04-23 | 湖南理工学院 | A kind of preparation method of solid base catalyst |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
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| JP2008274030A (en) * | 2007-04-26 | 2008-11-13 | Oita Univ | Method for producing biodiesel fuel |
| CN102557889A (en) * | 2012-01-09 | 2012-07-11 | 南昌大学 | Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst |
| CN102603494A (en) * | 2012-02-14 | 2012-07-25 | 南昌大学 | Method for synthesizing polyglycerol with solid base catalyst |
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2012
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Patent Citations (3)
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|---|---|---|---|---|
| JP2008274030A (en) * | 2007-04-26 | 2008-11-13 | Oita Univ | Method for producing biodiesel fuel |
| CN102557889A (en) * | 2012-01-09 | 2012-07-11 | 南昌大学 | Method for synthesizing polyglycerol by using load type sodium hydroxide solid alkali catalyst |
| CN102603494A (en) * | 2012-02-14 | 2012-07-25 | 南昌大学 | Method for synthesizing polyglycerol with solid base catalyst |
Non-Patent Citations (3)
| Title |
|---|
| Y.H.TAUFIQ-YAP ET AL.: "Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel", 《BIOMASSAND BIOENERGY》 * |
| 卞进发等: "《化工基本生产技术》", 30 September 2010, 化学工业出版社 * |
| 江德恩等: "硝酸镁在γ -Al 2O3 上的热分解及MgO/γ -Al2O3的碱性", 《物理化学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289237A (en) * | 2014-09-28 | 2015-01-21 | 佛山市天晟隆油脂化工有限公司 | Preparation method of solid base catalyst |
| CN109663585A (en) * | 2018-11-13 | 2019-04-23 | 湖南理工学院 | A kind of preparation method of solid base catalyst |
| CN109603801A (en) * | 2018-12-19 | 2019-04-12 | 山东大学 | A kind of load type solid body base catalyst and its preparation method and application producing biodiesel |
| CN109603801B (en) * | 2018-12-19 | 2020-07-31 | 山东大学 | Supported solid base catalyst for producing biodiesel as well as preparation method and application thereof |
| CN113509946A (en) * | 2020-04-10 | 2021-10-19 | 中石化南京化工研究院有限公司 | Supported alumina solid base catalyst |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
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Application publication date: 20140326 |
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