CN104923235A - Magnetic calcium-based solid base catalyst for synthesizing glycerol carbonate and preparation method for magnetic calcium-based solid base catalyst - Google Patents
Magnetic calcium-based solid base catalyst for synthesizing glycerol carbonate and preparation method for magnetic calcium-based solid base catalyst Download PDFInfo
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- CN104923235A CN104923235A CN201510242480.7A CN201510242480A CN104923235A CN 104923235 A CN104923235 A CN 104923235A CN 201510242480 A CN201510242480 A CN 201510242480A CN 104923235 A CN104923235 A CN 104923235A
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Abstract
The invention discloses a magnetic calcium-based solid base catalyst for synthesizing glycerol carbonate and a preparation method for the magnetic calcium-based solid base catalyst. A carrier of the magnetic calcium-based solid base catalyst is any one of magnetic cores CoFe2O4, MnFe2O4, ZnFe2O4 and MgFe2O4, and an active component of the magnetic calcium-based solid base catalyst is CaO. The specific preparation method comprises the following steps of: synthesizing magnetic cores by a hydrothermal method; and loading CaO by a coprecipitation method to prepare magnetic calcium-based solid base catalyst CaO/magnetic cores. The invention has the advantage that the prepared catalyst is used for reaction for synthesizing glycerol carbonate by virtue of ester exchange of glycerol and alkyl carbonate, is not only high in reaction activity, good in selectivity, but also has unique magnetic separation characteristic; and the preparation method is a green production process, and has good industrial prospect.
Description
Technical field
The present invention relates to the magnetic calcium based solid alkali Catalysts and its preparation method of carbonate synthesis glyceride, belong to and catalyze and synthesize carbonic acid glyceride technical field.
Background technology
Since energy crisis, development substitutability and the recyclability energy are all being tried to explore in countries in the world, and biodiesel becomes rapidly the focus of global new energy development.In the process of production of biodiesel, a large amount of byproduct containing crude glycerine can be produced, often produce the biodiesel of 10kg according to statistics, about obtain the glycerinated accessory substance of 1kg, because yield of biodiesel is huge, if these crude glycerine waste liquids can not utilize timely and effectively and process, likely become the burden of production of biodiesel enterprise, serious, new pollution sources may be become.Therefore the glycerine how in Appropriate application biological diesel oil byproduct, becomes the focus that many scientific workers pay close attention to.
Carbonic acid glyceride is as green chemical, of many uses, can be applicable to the industries such as polyurethane foam plastics, coating, washing agent, cosmetics.Carbonic acid glyceride is as the important intermediate of organic chemical industry simultaneously, has the advantages such as combustibility is low, toxicity is little, boiling point is high, biodegradable, has good prospects for commercial application.Adopt glycerine and alkyl carbonate ester exchange process carbonate synthesis glyceride, fundamentally can solve the Utilizing question of glycerine, alleviate the environmental problem caused by crude glycerine surplus, become the developing direction with good prospect.
This synthesis technique many employings solid base catalyst at present, ubiquity that particle is large, the inefficient shortcoming of macroreaction, for improving reaction rate, the particle size of catalyst must be reduced, but particle size is too small, can cause again the problem of catalyst and product separation difficulty, such as granule calcium oxide is present in reaction system with suspensoid state usually, be difficult to and product separation after reaction terminates, constrain the process of industrialization catalyzing and synthesizing carbonic acid glyceride.Magnetic solid base catalyst has highly active advantage, has again unique Magneto separate characteristic, fundamentally can solve the problem that catalyst particle difficulty is separated, improve the recovery utilization rate of catalyst, cause the concern of researcher.
Summary of the invention
Magnetic retention calcium base base catalyst that the object of the present invention is to provide a kind of carbonate synthesis glyceride and preparation method thereof.Catalyst prepared in this way has high activity and unique Magneto separate characteristic.
The present invention is realized by following technical proposals, a kind of magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride, described is glycerine and alkyl carbonate ester exchange carbonate synthesis glyceride, the preparation method of the magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride, it is characterized in that comprising following process
(1) preparation of magnetic core: be metal sulfate and the FeCl of 1: 1 ~ 1: 4 by mol ratio
36H
2o is dissolved in 10 ~ 25mL deionized water respectively, stirring 5 ~ 30min makes it mix, and separately by the KOH solution 20 ~ 80mL of 0.5 ~ 5mol/L, under agitation dropwise joins in above-mentioned mixed liquor, stirring 5 ~ 30min makes it mix, then above-mentioned mixed solution is put into reactor, at 140 ~ 200 DEG C, react 6 ~ 12h, cooling, be separated in magnetic field and take out, deionized water washing 3 ~ 6 times, at 200 DEG C, dry 3 ~ 8h, namely obtains graininess magnetic core;
(2) active component Ca salt is dissolved in deionized water, graininess magnetic core obtained above is evenly spread in Ca saline solution, the mol ratio of magnetic core and Ca salt is 1: 1 ~ 1: 10, drip the aqueous solution of precipitating reagent under agitation, the mol ratio of precipitating reagent and Ca salt is 2: 1 ~ 2.5: 1, dropwise and continue stirring 20 ~ 40min, then be warming up to 65 DEG C of ageing 10 ~ 24h, then with saturated Ca (OH)
2solution washing 3 ~ 6 times, 80 DEG C of vacuum drying 8 ~ 20h, gained sample, at 400 ~ 900 DEG C of roasting 1 ~ 5h, naturally cools to room temperature, obtains magnetic calcium based solid alkali catalyst.
The preparation method of the magnetic calcium based solid alkali catalyst of above-mentioned carbonate synthesis glyceride, it is characterized in that, metal sulfate is CoSO
47H
2o, MnSO
4h
2o, ZnSO
47H
2o and MgSO
47H
2any one in O.
The preparation method of the magnetic calcium based solid alkali catalyst of above-mentioned carbonate synthesis glyceride, it is characterized in that, active component Ca salt is Ca (NO
3)
2, CaBr
2, Ca (CH
3cOO)
2with any one in calcium lactate.
The preparation method of the magnetic calcium based solid alkali catalyst of above-mentioned carbonate synthesis glyceride, it is characterized in that, precipitating reagent is KOH, NH
3h
2o, (NH
4)
2cO
3, Na
2cO
3and K
2cO
3in any one.
The invention has the advantages that: 1, the magnetic calcium based solid alkali catalyst activity of the present invention's employing is high, cost of material is low, good stability; 2, such catalysis fixture has unique Magneto separate characteristic, thus is easy to realization and is recycled, and greatly reduces the pollution to environment, is conducive to economizing on resources simultaneously.
Below by specific embodiment, the present invention is further illustrated, but do not limited the present invention.
Detailed description of the invention
[embodiment 1]
The preparation of magnetic core: by the CoSO of 0.01mol
47H
2the FeCl of O and 0.02mol
36H
2o is dissolved in 15mL deionized water respectively, stirs 10min and makes it mix.Separately take the KOH solution 40mL of 2mol/L, under agitation dropwise join in above-mentioned mixed liquor, stirring 20min makes it mix, then above-mentioned mixed solution is put into reactor, at 180 DEG C, react 10h, cooling, be separated in magnetic field and take out, after deionized water washs 4 times at 200 DEG C dry 4h, namely obtain magnetic core CoFe
2o
4particle;
By the Ca (NO of 0.01mol
3)
2be dissolved in 20mL deionized water, by magnetic core CoFe obtained above
2o
4evenly spread to Ca (NO
3)
2in the aqueous solution, Ca (NO
3)
2with CoFe
2o
4mol ratio be 5: 1, drip the KOH aqueous solution of the 1mol/L of 20mL under stirring condition, drip off rear continuation and stir 30min, then be warming up to 65 DEG C of ageing 18h, with saturated Ca (OH)
2solution washing 4 times, 80 DEG C of vacuum drying 12h, sample, at 500 DEG C of roasting 3h, naturally cools to room temperature, obtains magnetic calcium based solid alkali catalyst CaO/CoFe
2o
4.
[embodiment 2-4]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only by the CoSO in preparation method
47H
2o changes MnSO into
4h
2o, ZnSO
47H
2o and MgSO
47H
2o, obtains three kinds of magnetic calcium based solid alkali catalyst.
[embodiment 5-9]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only by the Ca (NO in preparation method
3)
2with CoFe
2o
4mol ratio is change 1: 1,3: 1,6: 1,7: 1 and 10: 1 at 5: 1, obtains five kinds of magnetic calcium based solid alkali catalyst.
[embodiment 10-14]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the sintering temperature in preparation method 500 DEG C into 400 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, obtain five kinds of magnetic calcium based solid alkali catalyst.
[reaction embodiment 15-18]
In 1L reactor, add reactant 10.2g glycerine and 64.3g dimethyl carbonate, add 2.5g magnetic calcium based solid alkali catalyst, be 120 DEG C in reaction temperature, pressure is 2Mpa, and stir speed (S.S.) is react 6h under 800rpm condition.With the selective S of carbonic acid glyceride and yield Y for index, the catalytic performance of the catalyst of gained is as shown in table 1.
The catalytic performance of table 1 magnetic calcium based solid alkali catalyst synthesizing carbonate ester glycerine
[reaction embodiment 19]
The recycling performance of magnetic calcium based solid alkali catalyst.
In 1L reactor, add reactant 10.2g glycerine and 64.3g dimethyl carbonate, add 2.5g magnetic calcium based solid alkali catalyst, be 120 DEG C in reaction temperature, pressure is 2Mpa, and stir speed (S.S.) is react 6h under 800rpm condition.By catalyst filtration after reaction, 90 DEG C of dry 4h, use this catalyst recycle, and with the selective S of carbonic acid glyceride and yield Y for index, the recycling performance of gained catalyst is as shown in table 2.
The recycling performance of table 2 magnetic calcium based solid alkali catalyst
Claims (4)
1. a preparation method for the magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride, is characterized in that comprising following process,
(1) preparation of magnetic core: be metal sulfate and the FeCl of 1: 1 ~ 1: 4 by mol ratio
36H
2o is dissolved in 10 ~ 25mL deionized water respectively, stirring 5 ~ 30min makes it mix, and separately by the KOH solution 20 ~ 80mL of 0.5 ~ 5mol/L, under agitation dropwise joins in above-mentioned mixed liquor, stirring 5 ~ 30min makes it mix, then above-mentioned mixed solution is put into reactor, at 140 ~ 200 DEG C, react 6 ~ 12h, cooling, be separated in magnetic field and take out, deionized water washing 3 ~ 6 times, at 200 DEG C, dry 3 ~ 8h, namely obtains graininess magnetic core;
(2) active component Ca salt is dissolved in deionized water, graininess magnetic core obtained above is evenly spread in Ca saline solution, the mol ratio of magnetic core and Ca salt is 1: 1 ~ 1: 10, drip the aqueous solution of precipitating reagent under agitation, the mol ratio of precipitating reagent and Ca salt is 2: 1 ~ 2.5: 1, dropwise and continue stirring 20 ~ 40min, then be warming up to 65 DEG C of ageing 10 ~ 24h, then with saturated Ca (OH)
2solution washing 3 ~ 6 times, 80 DEG C of vacuum drying 8 ~ 20h, gained sample, at 400 ~ 900 DEG C of roasting 1 ~ 5h, naturally cools to room temperature, obtains magnetic calcium based solid alkali catalyst.
2., by the preparation method of the magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride according to claim 1, it is characterized in that, metal sulfate is CoSO
47H
2o, MnSO
4h
2o, ZnSO
47H
2o and MgSO
47H
2any one in O.
3., by the preparation method of the magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride according to claim 1, it is characterized in that, active component Ca salt is Ca (NO
3)
2, CaBr
2, Ca (CH
3cOO)
2with any one in calcium lactate.
4., by the preparation method of the magnetic calcium based solid alkali catalyst of carbonate synthesis glyceride according to claim 1, it is characterized in that, precipitating reagent is KOH, NH
3h
2o, (NH
4)
2cO
3, Na
2cO
3and K
2cO
3in any one.
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| CN108201887A (en) * | 2018-01-25 | 2018-06-26 | 中国科学院广州能源研究所 | It is a kind of using diatomite as glycerol carbonate catalyst of carrier and preparation method thereof |
| CN108484564A (en) * | 2018-05-02 | 2018-09-04 | 西安石油大学 | A kind of method that complex solid base catalysis quickly prepares carbonic acid glyceride |
| CN108620080A (en) * | 2018-06-01 | 2018-10-09 | 江南大学 | A kind of rare earth doped calcium base magnetic solid base catalyst and preparation method thereof |
| CN111974211A (en) * | 2020-08-05 | 2020-11-24 | 天津大沽化工股份有限公司 | Method for treating epoxypropane-containing process waste gas |
| CN113385163A (en) * | 2021-06-16 | 2021-09-14 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
| CN115646497A (en) * | 2022-10-17 | 2023-01-31 | 天津大学 | Magnetic bi-component calcium-based solid base catalyst for biodiesel as well as preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108201887A (en) * | 2018-01-25 | 2018-06-26 | 中国科学院广州能源研究所 | It is a kind of using diatomite as glycerol carbonate catalyst of carrier and preparation method thereof |
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| CN108620080A (en) * | 2018-06-01 | 2018-10-09 | 江南大学 | A kind of rare earth doped calcium base magnetic solid base catalyst and preparation method thereof |
| CN111974211A (en) * | 2020-08-05 | 2020-11-24 | 天津大沽化工股份有限公司 | Method for treating epoxypropane-containing process waste gas |
| CN113385163A (en) * | 2021-06-16 | 2021-09-14 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
| CN113385163B (en) * | 2021-06-16 | 2022-11-01 | 西南林业大学 | Foam carbon heterogeneous solid base catalyst for grease transesterification and preparation method thereof |
| CN115646497A (en) * | 2022-10-17 | 2023-01-31 | 天津大学 | Magnetic bi-component calcium-based solid base catalyst for biodiesel as well as preparation method and application thereof |
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Application publication date: 20150923 |