CN102430400B - Preparation method for natural calcium base porous solid alkaline catalyst for catalysis in interesterification - Google Patents
Preparation method for natural calcium base porous solid alkaline catalyst for catalysis in interesterification Download PDFInfo
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Abstract
The invention discloses a preparation method for a natural calcium base porous solid alkaline catalyst for catalysis in interesterification. The method is characterized by comprising the following steps of: simply heating and stirring cheap calcium carbonate-enriched natural calcium base materials serving as a raw material and C12-C22 fatty acid as a modifier to form a fatty acid compound; and baking to form a porous catalyst with a larger surface area. The preparation method is simple, low in cost and high in operability. The catalyst prepared by applying the method shows higher catalytic performance compared with the catalyst prepared by the conventional method (direct baking); and the catalytic efficiency can be increased by over 25 percent under the same condition.
Description
Technical field
The present invention relates to the preparation method for hole, the natural calcium Quito solid base catalyst of ester exchange reaction, and the application of catalyst in the ester exchange reaction of preparation biodiesel.
Background technology
Along with the day by day exhaustion of fossil energy and the day by day sternness of pressure of environmental pollution.Biodiesel has been subject to as a kind of emerging biomass energy paying close attention to widely.In numerous reported patents both domestic and external, document, calcium oxide goes out the heterocatalysis behavior with its main manifestations in catalytic reaction and receives much concern.In recent years, take the natural calcium sill that is rich in calcium carbonate as raw material, can be prepared into solid base catalyst for ester exchange reaction through simple roasting, such as calcite, dolomite, birds, beasts and eggs shell, Carapax Eriocheir sinensis and molluscan shell etc.
[1-5]Although these cheap natural calcium sills can obtain take CaO as main product through simple roasting, but in order to obtain satisfied catalytic effect, large catalyst amount (〉=6 wt.%), the long reaction time (〉=3h) and high molar ratio of methanol to oil (〉=10:1) be necessary.In fact, the ester exchange catalytic activity of common CaO is quite low.Liu etc.
[6]Directly with commercially available CaO(specific area: 0.56 m
2/ g) be catalyst action in soybean oil/methanol system, be atmospheric pressure reflux 3h under the condition of 8 wt.% at catalyst amount, conversion ratio only is about 80%.Demirbas
[7]The commercially available CaO that studies show that 1 wt.% acts on ester exchange reaction 3 h under normal pressure, conversion ratio only is 5%.Follow-up research thinks that the low ester exchange catalytic activity of common CaO is low, the low density shortcoming of active sites of the surface area of itself.Kouzu etc.
[8]Discovery roasting gained CaO-He alkali number in helium atmosphere is four times through air atmosphere roasting gained CaO-Air, under the equal conditions, and the former catalytic conversion (productive rate: 93 %) obviously be better than latter's (productive rate≤10 %).
In recent years, in order to improve the catalytic activity of CaO, series of measures is studied, report in succession.Demirbas
[7]The commercially available CaO that studies show that 1 wt.% acts on ester exchange reaction 3 h under normal pressure, conversion ratio only is 5 %.And under supercriticality, reaction only needs 20 min to finish.Liu etc.
[9]Take the higher P123 of cost as template, behind 240 ℃, the hydrothermal synthesis reaction of 72h, after drying is processed with the speed roasting of 1 ℃/min.Obtain having mesoporous CaO (257 m of high-specific surface area
2/ g), and show high CO
2Adsorption capacity.Yoosuk etc.
[10,11]By will calcite, obtain hydroxide after dolomite product of roasting and the water reaction, and the approach of again roasting is to the solid base catalyst of high-specific surface area, thereby improves the ester exchange activity of roasting calcite, dolomite.Though above method of modifying shows certain effect, there are severe reaction conditions, catalyst preparation process length, the shortcomings such as the reagent costliness of using, be difficult in the biodiesel industrialization, use.
Summary of the invention
The object of the invention is to: little for roasting direct natural calcium based solid alkali specific surface area of catalyst, the shortcoming that activity is low, catalytic performance is poor, a kind of simple, feasible, method is cheaply proposed, larger for the preparation of surface area, active high hole, natural calcium Quito solid base catalyst, and be used for biodiesel ester exchange catalysis.This preparation method is simple, cost is low, operability is high.Excessive aliphatic acid is recyclable and reuse in the Kaolinite Preparation of Catalyst process.The catalyst that application this method makes shows high catalytic performance than the catalyst that conventional method (roasting direct) makes, and can improve catalytic efficiency under the equal conditions more than 25%.
The present invention relates to a kind of preparation method of hole, the natural calcium Quito solid base catalyst for catalyzed transesterification, be particularly useful for preparing the catalyst of the ester exchange reaction of biodiesel, it is characterized in that to be rich in calcium, the natural calcium sill powder of magnesium carbonate, comprise dolomite, lime stone, birds, beasts and eggs shell and oyster shell and C12 ~ C22 aliphatic acid in mass ratio 1:1 ~ 1.2 ratios mix, add thermal agitation 0.2 ~ 3h in 100 ~ 300 ℃, then be transferred to while hot in the crucible, in 700 ~ 1000 ℃ of roasting 1 ~ 3h, cooling, be ground to 100 ~ 120 orders, namely get the porosu solid base catalyst with large surface area.
Relating to the natural calcium sill that is rich in calcium, magnesium carbonate in the invention is: a kind of, two or more mixtures in dolomite, calcite, lime stone, birds, beasts and eggs shell, oyster shell, the Carapax Eriocheir sinensis powder; Relate to C12 ~ C22 aliphatic acid in the invention and be one or more mixtures in laurate, lauroleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, peanut monoenoic acid, the erucic acid; Relating to calcination atmosphere in the invention is air stream, nitrogen stream.
Characterize (Fig. 1) as seen by SEM, the calcite of roasting direct, dolomite are the bulk graininess, and gained roasting porous calcite, dolomite particles obviously diminish, and show loose structure after stearic acid modified.N
2The adsorption-desorption characterization result shows that (Fig. 1, a) specific area is 4.1 m to the roasting calcite
2/ g, and roasting porous calcite (Fig. 1, b) specific area is 8.7 m
2/ g; Roasting dolomite (Fig. 1, c) specific area is 14.3 m
2/ g, and roasting porous calcite (Fig. 1, b) specific area is 22.1 m
2/ g.
As seen from Figure 2, under the equivalent responses condition, through the catalytic efficiency of fatty acid modified porous calcite, dolomite calcite, the dolomite apparently higher than roasting direct.
Description of drawings
Fig. 1 is the micro-Electronic Speculum figure of scanning: (a) roasting calcite; (b) through stearic acid modified gained roasting porous calcite; (c) roasting dolomite; (d) through stearic acid modified gained roasting porous dolomite;
Fig. 2 is that roasting calcite, dolomite, roasting porous calcite, dolomite are at the active comparison diagram (reaction condition: jatropha curcas oil 50.0g of Fig. 2 different catalysts ester exchange, catalyst amount: 0.5 g(1 wt.%) methyl alcohol/molar equivalent: 10:1, reaction time 1h), among the figure, 1, roasting calcite, 2, roasting dolomite, 3, roasting porous calcite, 4, roasting porous dolomite.
The specific embodiment
Embodiment one: the preparation of roasting porous calcite and the application for preparing in the catalysis of barbadosnut seed oil biodiesel
1. catalyst preparation: get calcite powder 100 g, stearic acid 600 g stir 1h in 170 ℃ after mixing.Pour into while hot in the crucible, under air stream, in 850 ℃ of roasting 1h, after the cooling, grind for subsequent use.
2 application in barbadosnut seed oil biodiesel catalysis preparation: take by weighing barbadosnut seed oil 50g, add 17.3g methyl alcohol, add the roasting porous calcite of oil quality 3 wt.%, return stirring 2h.Product after filtration, decompression distillation reclaims methyl alcohol, cooling, centrifugal biodiesel product 44.0g, and wherein fatty acid methyl ester reaches 98.0 wt.%.
Embodiment two: the preparation of roasting porous dolomite and the application for preparing in the catalysis of Euphorbia lathyris seed oil biodiesel
1. catalyst preparation: get dolomite powder 100 g, stearic acid 1200g stirs 3h in 100 ℃ after mixing.Pour into while hot in the crucible, under air stream, in 800 ℃ of roasting 3h, after the cooling, grind for subsequent use.
2. the application for preparing in the catalysis of Euphorbia lathyris seed oil biodiesel: take by weighing Euphorbia lathyris seed oil 50g, add 13.6g methyl alcohol, add the roasting porous calcite of oil quality 4 wt.%, return stirring 3h.Product after filtration, decompression distillation reclaims methyl alcohol, cooling, centrifugal biodiesel product 45.6g, and wherein fatty acid methyl ester reaches 98.5wt.%.
Embodiment three: the preparation of roasting porous egg shell/Carapax Eriocheir sinensis and the application for preparing in the oil biodiesel catalysis of Chinese tallow tree Chinese catalpa
1. catalyst preparation: get clean, dried egg shell, each 50g of Carapax Eriocheir sinensis powder, laurate 120g stirs 0.2h in 300 ℃ after mixing.Pour into while hot in the crucible, under air stream, in 700 ℃ of roasting 2h, after the cooling, grind for subsequent use.
2. the application for preparing in the oil biodiesel catalysis of Chinese tallow tree Chinese catalpa: take by weighing Chinese tallow tree Chinese catalpa oil 50g, add 19.3g methyl alcohol, add roasting porous egg shell/Carapax Eriocheir sinensis of oil quality 4 wt.%, return stirring 3h.Product after filtration, decompression distillation reclaims methyl alcohol, cooling, centrifugal biodiesel product 43.9g, and wherein fatty acid methyl ester reaches 98.2wt.%.
Embodiment four: the preparation of roasting porous egg shell/calcite and the application for preparing in the catalysis of barbadosnut seed oil biodiesel
1. catalyst preparation: get clean, dried lime stone/egg shell/oyster shell/dolomite/each 25g of calcite powder, laurate/oleic acid/each 60g of peanut monoenoic acid stirs 2h in 200 ℃ after mixing.Pour into while hot in the crucible, flow down in 1000 ℃ of roasting 1h in nitrogen, after cooling, the cooling, grind for subsequent use.
2. the application for preparing in the oil biodiesel catalysis of Chinese tallow tree Chinese catalpa: take by weighing barbadosnut seed oil 50g, add 19.3g methyl alcohol, roasting porous egg shell/oyster shell of adding oil quality 2 wt.%/dolomite, return stirring 2h.Product after filtration, decompression distillation reclaims methyl alcohol, centrifugal biodiesel product 46.1g, and wherein fatty acid methyl ester reaches 97.6wt.%.
List of references:
[1]?Ngamcharussrivichai,?C.,?Wiwatnimit,?W.,?Wangnoi,?S.?2007.?Journal?of?Molecular?Catalysis?a-Chemical,?276(1-2):?24-33.
[2]?Ngamcharussrivichai,?C.,?Nunthasanti,?P.,?Tanachai,?S.,?
et?al.?2010.?Fuel?Processing?Technology,?91(11):?1409-1415.
[3]?Viriya-empikul,?N.,?Krasae,?P.,?Puttasawat,?B.,?Yoosuk,?B.,?
et?al.?2010.?Bioresource?Technology,?101(10):?3765-3767.
[4]?Viriya-empikul,?N.,?Krasae,?P.,?Puttasawat,?B.,?
et?al.?2010.?Bioresource?Technology,?101(10):?3765-3767.
[5]?Boey,?P.-L.,?Maniam,?G.P.,?Hamid,?S.A.?2009.?Bioresource?Technology,?100(24):?6362-6368.
[6]?Liu,?X.,?He,?H.,?Wang,?Y.,?
et?al.?2008.?Fuel,?87(2):?216-221.
[7]?Demirbas,?A.?2007.?Energy?Conversion?and?Management,?48(3):?937-941.
[8]?Kouzu,?M.,?Kasuno,?T.,?Tajika,?M.,?et?al.?2008.?Fuel,?87(12):?2798-2806.
[9]?Liu,?C.X.,?Zhang,?L.,?Deng,?J.G.,?
et?al.?2008.?Journal?of?Physical?Chemistry?C,?112(49):19248-19256.
[10]?Yoosuk,?B.,?Udomsap,?P.,?Puttasawat,?B.,?
et?al.?2010.?Chemical?Engineering?Journal,?162(1):?135-141.
[11]?Yoosuk,?B.,?Udomsap,?P.,?Puttasawat,?B.?2011.?Applied?Catalysis?A:?General,?395(1-2):?87-94。
Claims (4)
1. preparation method who is used for hole, the natural calcium Quito solid base catalyst of ester exchange catalysis, make a kind of catalyst of the ester exchange reaction for the preparation of biodiesel, it is characterized in that to be rich in calcium, the natural calcium sill powder of magnesium carbonate and C12-C22 aliphatic acid in mass ratio 1:1.2-12 ratio mix, add thermal agitation 0.2-3h in 100-300 ℃, then be transferred to while hot in the crucible, in 700-1000 ℃ of roasting 1-3h, cooling, be ground to the 100-120 order, namely get solid base catalyst, the described calcium that is rich in, the natural calcium based powders of magnesium carbonate is: calcite, dolomite, lime stone, the birds, beasts and eggs shell, a kind of in the powder of oyster and Carapax Eriocheir sinensis, two or more mixture.
2. the preparation method of a kind of hole, natural calcium Quito solid base catalyst for ester exchange catalysis according to claim 1 is characterized in that C12-C22 aliphatic acid is a kind of, two or more fatty acid mixeds in laurate, lauroleic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, arachidic acid, peanut monoenoic acid, the erucic acid.
3. the preparation method of a kind of hole, natural calcium Quito solid base catalyst for ester exchange catalysis according to claim 1, the atmosphere that it is characterized in that roasting is air stream, nitrogen stream.
4. the application of a catalyst of producing for hole, the natural calcium Quito solid base catalyst preparation method of ester exchange catalysis claimed in claim 1, its feature is for the preparation of the catalyst in the ester exchange reaction of biodiesel.
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| CN102824903A (en) * | 2012-09-07 | 2012-12-19 | 贵州大学 | Porous solid alkali catalyst prepared by using dolomite as raw material and application of porous solid alkali catalyst |
| GB201315276D0 (en) * | 2013-08-28 | 2013-10-09 | Johnson Matthey Plc | Catalyst and process |
| US9834718B2 (en) * | 2014-05-06 | 2017-12-05 | Saudi Arabian Oil Company | Ecofriendly lubricating additives for water-based wellbore drilling fluids |
| CN108726901A (en) * | 2018-05-29 | 2018-11-02 | 丁嘉鹏 | A kind of preparation method of eggshell base porous solid alkali |
| CN110368977B (en) * | 2019-07-25 | 2022-04-19 | 广西科学院 | Preparation method and application of calcium-magnesium double-active-center catalyst |
| CN114805020B (en) * | 2021-11-18 | 2023-10-17 | 贵州大学 | Rapid synthesis method of biomass-based aromatic alcohol |
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| CN100586568C (en) * | 2007-12-07 | 2010-02-03 | 华东理工大学 | Preparation method for solid base catalyst for biological diesel oil synthesis |
| CN101811038A (en) * | 2010-04-30 | 2010-08-25 | 太原理工大学 | Method for synthesizing biodiesel solid base catalyst and application |
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