CN102154065A - Method for preparing methyl oleate from vegetable oil under catalysis of silicon dioxide-supported heteropolyacid - Google Patents
Method for preparing methyl oleate from vegetable oil under catalysis of silicon dioxide-supported heteropolyacid Download PDFInfo
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- CN102154065A CN102154065A CN2011100628229A CN201110062822A CN102154065A CN 102154065 A CN102154065 A CN 102154065A CN 2011100628229 A CN2011100628229 A CN 2011100628229A CN 201110062822 A CN201110062822 A CN 201110062822A CN 102154065 A CN102154065 A CN 102154065A
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Abstract
The invention discloses a method for preparing methyl oleate from vegetable oil under catalysis of silicon dioxide-supported heteropolyacid, which belongs to the technical field of fine chemical synthesis. In the invention, silicon dioxide is used as a solid phase carrier to support phosphotungstic acid to catalyze the reaction of the vegetable oil and methanol, and soybean oil, palm oil, colleseed oil, peanut oil, cottonseed oil and other vegetable oil are used as raw materials to be reacted with methanol to form methyl oleate. Compared with the conventional method using strong acid, strong alkali and the like as a catalyst, the reaction can be performed under normal pressure, acid-resistance and alkali-resistance equipment are not needed, the reaction conditions are mild, waste water, waste liquid and waste gas pollutants are not emitted, the silicon dioxide-supported heteropolyacid catalyst can be recycled and reused, and the method meets energy-conservation and environment-protection requirements.
Description
Technical field
The present invention relates to a kind of new catalyzer and be used for transesterification reaction, be specially that to relate to the immobilized phosphorus heteropoly tungstic acid of a kind of silicon-dioxide be catalyzer, soybean wet goods vegetables oil is a raw material, prepares the novel method of Witconol 2301 by ester-exchange technology.
Background technology
Witconol 2301 is a raw material with oleic acid and methyl alcohol generally in industrial preparation, with the liquid acid is that catalyzer obtains by esterification, not only need to use strongly acidic catalysts such as sulfuric acid, thionamic acid in the reaction, the temperature of reaction height, the reaction by product many, need corrosion resistant apparatus, and the reaction finish after, acid in the neutralized products such as needs use highly basic also need use dehydration and desalter that product is carried out aftertreatment.
Witconol 2301 uses in the industrial biofuel that also can be used as, therefore demand in recent years increases gradually, use utilizes soybean wet goods vegetables oil as the feedstock production Witconol 2301, be the main means of production biofuel in the present industry, promptly utilize the oleic acid in the vegetables oil, triolein and methyl alcohol are in acid, react under the catalyst actions such as alkali, obtain fatty acid methyl ester and glycerine, though this reaction catalytic efficiency is higher, but still need to use strong acid or highly basic etc. as catalyzer, after reaction finishes, need to adopt complicated neutralization, dewater, aftertreatment technologys such as desalination, therefore technology is comparatively complicated, energy consumption is higher, and the consumption of methyl alcohol is big, and the color and luster of product is darker, impurity is many, catalyzer and product separation difficulty are followed a large amount of waste water, waste liquid, three waste discharges such as waste gas are big to the pollution of environment.
Oarse-grained solid catalyst is to have the acid or the alkali of catalytic activity to be carried on surface of solid phase carriers, also possess bigger particle and specific surface area when making it catalytic activity that possesses acid or alkali, because this solid catalyst is not dissolved in reaction system, therefore after finishing, reaction can it be separated from reaction system by simple filtering, and the loss of its reactive behavior is very little, can reuse, when therefore having avoided use liquid strong acid or basic catalyst, the product aftertreatment the neutralization that must face, dewater, aftertreatment technologys such as desalination, therefore required equipment is simple, energy consumption is lower, no waste water, waste liquid, the discharge of the three wastes such as waste gas meets the requirement of energy-saving and emission-reduction.
Summary of the invention
The purpose of this invention is to provide a kind of is that solid catalyst substitutes traditional liquid strong acid or alkali catalyst with the silicon-dioxide solid-carrying heteropolyacid, under mild conditions comparatively, and the synthetic Witconol 2301 that obtains.
Technical scheme of the present invention: silicon-dioxide solid-carrying heteropolyacid solid catalysis vegetables oil prepares the method for Witconol 2301, adopt the carrier of silicon-dioxide as solid catalyst, adopt pickling process that phosphorus heteropoly tungstic acid is carried on silica sphere, obtain silicon dioxide carried phosphorus heteropoly tungstic acid solid catalyst through 100～180 ℃ of roastings; Use this catalyzer can be under condition of normal pressure, the oleic acid in the catalysis vegetables oil, triolein etc. react with methyl alcohol, obtain Witconol 2301; 60～100 ℃ of temperature of reaction, 2～8 hours reaction times.
Described vegetables oil is soybean oil, plam oil, rapeseed oil, peanut oil, Oleum Gossypii semen
The mol ratio of vegetables oil and methyl alcohol is 1: 1～1: 5;
Loading silicon dioxide with heteropoly acid solid catalyst and reactant total mass ratio are 1: 30～1: 1;
The preparation process of loading silicon dioxide with heteropoly acid solid catalyst ester:
Take by weighing an amount of carrier silicon-dioxide and phosphorus heteropoly tungstic acid and put into methyl alcohol, refluxed 1～5 hour in 50～80 ℃, cooling was left standstill 6 hours, rotary evaporation is removed methyl alcohol, drying is 24 hours under the vacuum, in retort furnace, after 1～3 hour, obtain the loading silicon dioxide with heteropoly acid solid catalyst in 100-180 ℃ of roasting.
The ratio of described silicon-dioxide and methyl alcohol is 5～15mL/g;
The mass ratio of described phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 50～1: 1;
The preparation process of Witconol 2301:
In the flask that stirring, thermometer, reflux condensate device are arranged, the vegetables oil, methyl alcohol and the solid catalyst that add certain proportioning, wherein the mol ratio of vegetables oil and methyl alcohol is 1: 1～1: 5, and loading silicon dioxide with heteropoly acid solid catalyst and reactant total mass ratio are 1: 30～1: 1.Stirring is warmed up to and picks up counting after temperature required, keeps transesterification reaction temperature stable in reflux course, stopped reaction after 1～8 hour reaction times, cooling, after removing by filter catalyzer with B, methyl alcohol is removed in underpressure distillation (0.09Mpa), obtains the product oleic acid methyl esters.
Embodiment
Below be specific embodiments of the invention, described embodiment is used to describe the present invention, rather than restriction the present invention.
Embodiment 1
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 50), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 30.2%.
Embodiment 2
3g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 50), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 38.3%.
Embodiment 3
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 10), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 52.3%.
Embodiment 4
6g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 10), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 61.8%.
Embodiment 5
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 5), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 58.2%.
Embodiment 6
10g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 5), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 74.6%.
Embodiment 7
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 2), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 76.8%.
Embodiment 8
6g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 2), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 80.5%.
Embodiment 9
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 70 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 71.7%.
Embodiment 10
1g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 80 ℃, and the reaction times is 3 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 81.6%.
Embodiment 11
5g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g soybean oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 80 ℃, and the reaction times is 5 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 88.3%.
Embodiment 12
5g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g plam oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 80 ℃, and the reaction times is 5 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 86.6%.
Embodiment 13
5g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g rapeseed oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 80 ℃, and the reaction times is 5 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 87.8%.
Embodiment 14
5g solid catalyst (mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 1), 30g peanut oil, 3g methyl alcohol are put into flask, stir, heating, temperature of reaction is 80 ℃, and the reaction times is 5 hours, and the reaction cooled and filtered is removed catalyzer, underpressure distillation, Witconol 2301 productive rate are 88.9%.
Claims (10)
1. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil prepares the method for Witconol 2301, it is characterized in that adopting the carrier of silicon-dioxide as solid catalyst, adopt pickling process that phosphorus heteropoly tungstic acid is carried on silica sphere, obtain silicon dioxide carried phosphorus heteropoly tungstic acid solid catalyst through 100～180 ℃ of roastings; Use this catalyzer can be under condition of normal pressure, the oleic acid in the catalysis vegetables oil, triolein etc. react with methyl alcohol, obtain Witconol 2301; 60～100 ℃ of temperature of reaction, 2～8 hours reaction times.
2. use silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that vegetables oil is soybean oil, plam oil, rapeseed oil, peanut oil, Oleum Gossypii semen.
3. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that methyl alcohol is raw material.
4. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that oleic acid is raw material.
5. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that triolein is a raw material.
6. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, and the mol ratio that it is characterized in that vegetables oil and methyl alcohol is 1: 1～1: 5.
7. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that being that silicon-dioxide is as carrier.
8. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, it is characterized in that being that phosphorus heteropoly tungstic acid is as catalytic active component.
9. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, and the mass ratio of phosphorus heteropoly tungstic acid and silicon-dioxide is 1: 50～1: 1.
10. silicon-dioxide catalyzed with solid supported heteropolyacid vegetables oil according to claim 1 prepares the method for Witconol 2301, and loading silicon dioxide with heteropoly acid solid catalyst and reactant total mass ratio are 1: 30～1: 1.
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Cited By (7)
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| CN105132191A (en) * | 2015-09-06 | 2015-12-09 | 哈尔滨工业大学 | Method for preparing biodiesel through solid acid catalytic method |
| CN105854939A (en) * | 2016-03-31 | 2016-08-17 | 江西理工大学 | Rare-earth-modified heteropolyacid catalyst, preparation method thereof and method for preparing biodiesel |
| CN106397191A (en) * | 2016-08-29 | 2017-02-15 | 吴琦琪 | Catalytic preparation method for methyl oleate |
| CN106984355A (en) * | 2017-05-25 | 2017-07-28 | 上海应用技术大学 | A kind of HPW/g C3N4 composites and its preparation method and application |
| CN107321390A (en) * | 2016-11-10 | 2017-11-07 | 东北林业大学 | A kind of preparation method of compound bio base solid-carrying type biodiesel catalyst |
| CN110205204A (en) * | 2018-11-29 | 2019-09-06 | 湖北工业大学 | Utilize the method for silica gel load heteropolyacid catalyst biodiesel synthesis |
| CN110295068A (en) * | 2018-11-29 | 2019-10-01 | 湖北工业大学 | Utilize the method for Catalyzed by Heteropolyacid Supported on Actived Carbon agent biodiesel synthesis |
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2011
- 2011-03-16 CN CN2011100628229A patent/CN102154065A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132191A (en) * | 2015-09-06 | 2015-12-09 | 哈尔滨工业大学 | Method for preparing biodiesel through solid acid catalytic method |
| CN105854939A (en) * | 2016-03-31 | 2016-08-17 | 江西理工大学 | Rare-earth-modified heteropolyacid catalyst, preparation method thereof and method for preparing biodiesel |
| CN105854939B (en) * | 2016-03-31 | 2019-02-05 | 江西理工大学 | The preparation method of rare earth modified heteropolyacid catalyst, preparation method and biodiesel |
| CN106397191A (en) * | 2016-08-29 | 2017-02-15 | 吴琦琪 | Catalytic preparation method for methyl oleate |
| CN107321390A (en) * | 2016-11-10 | 2017-11-07 | 东北林业大学 | A kind of preparation method of compound bio base solid-carrying type biodiesel catalyst |
| CN107321390B (en) * | 2016-11-10 | 2019-12-13 | 东北林业大学 | preparation method of composite bio-based immobilized biodiesel catalyst |
| CN106984355A (en) * | 2017-05-25 | 2017-07-28 | 上海应用技术大学 | A kind of HPW/g C3N4 composites and its preparation method and application |
| CN110205204A (en) * | 2018-11-29 | 2019-09-06 | 湖北工业大学 | Utilize the method for silica gel load heteropolyacid catalyst biodiesel synthesis |
| CN110295068A (en) * | 2018-11-29 | 2019-10-01 | 湖北工业大学 | Utilize the method for Catalyzed by Heteropolyacid Supported on Actived Carbon agent biodiesel synthesis |
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Application publication date: 20110817 |