CN105536766B - Nanometer calcium lanthanium complex oxide catalyst and its preparation method and application - Google Patents
Nanometer calcium lanthanium complex oxide catalyst and its preparation method and application Download PDFInfo
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- CN105536766B CN105536766B CN201510928423.4A CN201510928423A CN105536766B CN 105536766 B CN105536766 B CN 105536766B CN 201510928423 A CN201510928423 A CN 201510928423A CN 105536766 B CN105536766 B CN 105536766B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
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Abstract
The invention belongs to chemical industry catalysis technical field, specially a kind of nanometer calcium lanthanium complex oxide catalyst and its preparation method and application.The present invention is dissolved in the water after mixing the nitrate of calcium and lanthanum, citric acid is added as complexing agent, stirring at a certain temperature forms gel, ageing；Then it is roasted, is finally heat-treated in the presence of ethanol water in air atmosphere, nanometer calcium lanthanium complex oxide catalyst is made.The catalyst has very strong alkaline matter, surface hydrophilic and hydrophobic is suitable, excellent catalytic activity is shown in the reaction of glycerolysis synthetic glycerine monoesters, there are strong interactions between calcium lanthanum simultaneously, this synergistic effect is so that the loss of active component calcium in the reaction system greatly reduces, to enhance the stability of catalyst, it can be used for glycerolysis vegetable oil synthetic glycerine monoesters.Low raw-material cost used in the present invention, catalyst is environmental-friendly, and preparation method is simple.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of nanometer calcium lanthanum meets oxide and its preparation side
Method and the application on glycerolysis synthetic glycerine monoesters.
Background technology
Monoglyceride (monoglyceride, MG) is a kind of polyol-based non-ionic surfactant, is widely used in food
Processing industry, food processing technology can be effectively improved, product quality is improved, extend shelf life etc., it can be dropped completely
Solution be glycerine and aliphatic acid, it is safe to the human body, be mainly used in cake, bread, vermicelli, candy, ice cream and meat products, have
Very wide application prospect and huge market value.Monoglyceride also has extensively as emulsifier in household chemicals
Using.Such as emulsifier and dispersant are used as in cosmetics, toothpaste and hair conditioner, it is used as emulsifying in fiber finishing process
Antistatic agent etc. is made in agent in polyethylene, polypropylene etc., is the maximum fatty acid ester surfactant of consumption.In addition, sweet
Oily monoesters has good bio-compatibility, also has important application in pharmaceuticals industry, such as contains polyunsaturated fatty acid
The monoglyceride of (CLA, EPA, DHA) has prevention effect for angiocardiopathy.
The method of glycerolysis production monoglyceride mainly has chemical method and biological enzyme.Main useization industrial at present
Method.Glycerine is hydrophily, and animal and plant fat is hydrophobicity, and at room temperature, solubility of the glycerine in common grease is very low,
Only 4%, the solubility in cocoa butter is slightly larger, is also only 6%, thus, at room temperature, glycerine and be difficult reaction with grease needs
Temperature is improved to improve solubility of the glycerine in grease.The catalyst industrially used is mainly NaOH or KOH, reaction temperature
Degree is usually above 200 DEG C.In the food industry, Ca (OH)2It is common catalyst, this is because Ca (OH)2Under catalysis, product
Color and luster it is shallower, meet the requirement of food industry.Using homogeneous base catalysis glycerolysis, catalyst is difficult to recycle, and reaction terminates
After to neutralize base catalyst immediately, to prevent back reaction occur.Solid base catalyst can effectively solve product separation difficult problem,
Reduce environmental pollution.The hydrophilic and hydrophobic on solid base catalyst surface can seriously affect the alcohol oil rate of microenvironment near active sites, from
And significantly affect the performance of catalyst.In addition, the losing issue of calcium is one in glycerolysis influences its big problem used,
How difficult point that the stability of catalyst be research is improved.
Calcium lanthanium complex oxide has stronger alkaline matter, and good catalysis is shown in the reaction of Methanolysis vegetable oil
Activity.Such as Taufiq-Yap et al. is prepared for CaO-La using coprecipitation2O3Catalyst has studied CaLa molar ratios to first
The performance of alcohol alcoholysis Jatropha curcas oil influence (Energy Conversion and Management 2014,88,
1290-1296.).Catalyst granules is larger made from this method, and under 65 DEG C of reaction condition, and active constituent Ca has
Larger loss so that activity reduces, therefore can not be prepared using the method similar with the document and can be used for glycerolysis plant
The catalyst of oil reaction.
Invention content
The purpose of the present invention is to provide the nanometer calcium lanthanium complex oxide catalyst of a kind of high activity and high stability and
Preparation method, and it is applied to glycerolysis vegetable oil synthetic glycerine monoesters.
Strong phase interaction can occur when calcium oxide and lanthana form uniformly mixed composite oxides, between two oxides
With, this effect makes the alkalinity of calcium oxide further increase, to make catalytic activity get a promotion, meanwhile, it is this strong mutual
Effect can also significantly inhibit the loss of calcium oxide.The calcium lanthanium complex oxide of document report is prepared using coprecipitation, due to
The ionic product of calcium hydroxide and the ionic product of lanthanum hydroxide have a long way to go, and can not accomplish while homogeneous precipitation in precipitation.Therefore,
It is difficult to that uniform composite oxides are made.In addition, composite oxides obtained use high-temperature roasting, surface and glycerine it is affine
Property it is poor, cause react microenvironment in alcohol oil rate it is improper.The present invention provides a kind of collosol and gel burning of citric acid auxiliary
Method prepares mixed uniformly nanometer calcium lanthanium complex oxide, while improving the hydrophobe of oxide surface using ethyl alcohol heat treatment
Property, catalyst obtained has high glycerolysis vegetable oil synthetic glycerine monoesters catalytic activity and low calcium current vector.
The preparation method of nanometer calcium lanthanum catalyst provided by the invention, is as follows：
（1）Certain density calcium nitrate and lanthanum nitrate hexahydrate are configured, is mixed, the molar ratio of metal ion and water is 1:
(30-50);
（2）Citric acid, mole of citric acid and metal ion is added in heating stirring under the conditions of 70-90 DEG C while stirring
Than being 0.5:1-2:1；
（3）It is stirred continuously until the solution obtained by step (2) to form colloidal sol at 70-90 DEG C, it is then old at room temperature
Change 18-24 hours；
（4）Wet gel after ageing is 12-24 hours dry at 100-140 DEG C of temperature, air atmosphere, it is catalyzed
Agent presoma 1；
（5）After catalyst precursor 1 is ground, it is warming up to 500-600 DEG C with 1-3 DEG C/min in air atmosphere, is kept
1-5 hours, then it is warming up to 700-800 DEG C with 1-3 DEG C/min, it roasts 2-8 hours, is catalyzed under inert gas atmosphere
Agent presoma 2；
（6）Catalyst precursor 2 is mixed with the absolute ethyl alcohol of 2-5 times of weight, is placed in pressure vessel, in 120-150
Handled 2-3 hours at DEG C, it is cooling after under an inert atmosphere 80-120 DEG C dry 6-12 hours to get to required catalyst.
In the above method, the molar ratio of calcium lanthanum is 1:5-5:1.
In the above method, the mixing speed is 200-500rpm.
In the above method, the inert gas is nitrogen, argon gas or helium or their mixed gas.
The catalyst prepared by the method for the present invention, there are strong interactions, the base strength of catalyst to obtain between calcium lanthanum
Prodigious raising has been arrived, while there is good stability, the solubility in glycerine has substantial degradation compared with calcium oxide.
Above-mentioned calcium lanthanium complex oxide catalyst provided by the invention can be used for catalyzing glycerol alcoholysis vegetable oil synthetic glycerine
Monoesters, the specific steps are：
（1）Catalyst is added in vegetable oil, mixed liquor is formed, mixed liquor is heated to 180-240 DEG C；
（2）Glycerine is added into the mixed liquor of preheated vegetable oil and catalyst；At a temperature of 180-240 DEG C, with
The mixing speed of 300-1000 rpm reacts 10 min-300 min, obtains the product containing monoglyceride.
In the present invention, the vegetable oil can be soya-bean oil, corn oil, palm oil, cottonseed oil, rapeseed oil, olive oil, fiber crops
One or more kinds of mixtures of the vegetable oil such as crazy tree oil.
In the present invention, the usage amount of catalyst is the 0.1%-5% of oil weight.
In the present invention, the weight ratio of glycerine and vegetable oil is 1:5-1:1.
It is an advantage of the current invention that the catalyst used in preparation method is environmental-friendly, preparation method is simple, efficient,
Catalyst is easily isolated, and the catalytic activity higher than common calcium oxide can be obtained in the reaction of glycerolysis synthetic glycerine monoesters,
The losing issue of catalyst has obtained inhibiting significantly simultaneously.
Specific implementation mode
With reference to embodiment, invention is further described in detail.
Embodiment 1, catalyst preparation
(1) molar ratio of configuration calcium nitrate, lanthanum nitrate hexahydrate, metal ion and water is 1:40, by two kinds of solution according to calcium,
Lanthanum molar ratio 3:1 ratio mixing；
(2) mixed liquor that heating stepses (1) obtain under the conditions of 80 DEG C, is added citric acid, citric acid and gold while stirring
The molar ratio for belonging to ion is 1:1；
(3) solution obtained by step (2) is stirred under the conditions of 80 DEG C until formation colloidal sol, is then aged 18 at room temperature
Hour；
(4) 12 hours dry under air atmosphere by the wet gel after ageing at 110 DEG C, obtain catalyst precursor；
(5) after grinding catalyst precursor, 600 DEG C are warming up to 1 DEG C/min in air atmosphere, is kept for 2 hours, then
700 DEG C are warming up to 1 DEG C/min, roasts 5 hours under inert gas atmosphere, obtains catalyst precursor 2；
(6) catalyst precursor 2 is mixed with the absolute ethyl alcohol of 2 times of weight, is placed in pressure vessel, under the conditions of 120 DEG C
Processing 2 hours, it is cooling after again lower 100 DEG C of drying of inert atmosphere 8 hours to get to catalyst of the invention.
Embodiment 2, catalyst preparation
(1) molar ratio of configuration calcium nitrate, lanthanum nitrate hexahydrate, metal ion and water is 1:50, by two kinds of solution according to calcium,
Lanthanum molar ratio 2:1 ratio mixing；
(2) mixed liquor that heating stepses (1) obtain under the conditions of 90 DEG C, is added citric acid, citric acid and gold while stirring
The molar ratio for belonging to ion is 1:1；
(3) solution obtained by step (2) is stirred under the conditions of 90 DEG C until formation colloidal sol, is then aged 18 at room temperature
Hour；
(4) 12 hours dry under air atmosphere by the wet gel after ageing at 110 DEG C, obtain catalyst precursor 1；
(5) after grinding catalyst precursor, 600 DEG C are warming up to 1 DEG C/min in air atmosphere, is kept for 2 hours, then
700 DEG C are warming up to 1 DEG C/min, roasts 5 hours under inert gas atmosphere, obtains catalyst precursor 2；
(6) catalyst precursor 2 is mixed with 3 times of weight absolute ethyl alcohols, is placed in pressure vessel, under the conditions of 120 DEG C
Reason 2 hours, it is cooling after again under an inert atmosphere at 100 DEG C dry 8 hours to get to the catalyst of the present invention.
Embodiment 3, catalyst preparation
(1) molar ratio of configuration calcium nitrate, lanthanum nitrate hexahydrate, metal ion and water is 1:40, by two kinds of solution according to calcium,
Lanthanum molar ratio 1:1 ratio mixing；
(2) mixed liquor that heating stepses (1) obtain under the conditions of 80 DEG C, is added citric acid, citric acid and gold while stirring
The molar ratio for belonging to ion is 1.5:1；
(3) solution obtained by step (2) is stirred under the conditions of 80 DEG C until formation colloidal sol, is then aged 18 at room temperature
Hour；
(4) 12 hours dry under air atmosphere by the wet gel after ageing at 110 DEG C, obtain catalyst precursor；
(5) after grinding catalyst precursor, 600 DEG C are warming up to 1 DEG C/min in air atmosphere, is kept for 2 hours, then
700 DEG C are warming up to 1 DEG C/min, roasts 5 hours under inert gas atmosphere, obtains catalyst precursor 2；
(6) catalyst precursor 2 is mixed with 3 times of weight absolute ethyl alcohols, is placed in pressure vessel, under the conditions of 140 DEG C
Reason 2 hours, it is cooling after again under an inert atmosphere at 100 DEG C dry 8 hours to get to the catalyst of the present invention.
The application of catalyst prepared by embodiment 4, embodiment 1
Using catalyst made from embodiment 1,0.3 gram of catalyst is added in 10 grams of corn oils, forms mixed liquor；It will mix
It closes liquid and is heated to 220 DEG C；3.1 grams of glycerine are added into the mixed liquor of preheated vegetable oil and catalyst；It is anti-at 220 DEG C
Temperature, the mixing speed of 500 rpm is answered to react 1 hour；The product containing monoglyceride is made.The conversion ratio of corn oil is
94.9%, the yield of monoglyceride is 45.5%, and the number of dropouts of Ca is 320.5 ppm in product.
The application of catalyst prepared by embodiment 5, embodiment 2
Using catalyst made from embodiment 2,0.3 gram of catalyst is added in 10 grams of corn oils, forms mixed liquor；It will mix
It closes liquid and is heated to 220 DEG C；3.1 grams of glycerine are added into the mixed liquor of preheated vegetable oil and catalyst；It is anti-at 220 DEG C
Temperature, the mixing speed of 500 rpm is answered to react 2 hours；The product containing monoglyceride is made.The conversion ratio of corn oil is
94.9%, the yield of monoglyceride is 36.8%, and the number of dropouts of Ca is 234.9 ppm in product.
The application of catalyst prepared by embodiment 6, embodiment 3
Using catalyst made from embodiment 3,0.3 gram of catalyst is added in 10 grams of corn oils, forms mixed liquor；It will mix
It closes liquid and is heated to 220 DEG C；3.1 grams of glycerine are added into the mixed liquor of preheated vegetable oil and catalyst；It is anti-at 220 DEG C
Temperature, the mixing speed of 500 rpm is answered to react 2 hours；The product containing monoglyceride is made.The conversion ratio of corn oil is
95.4%, the yield of monoglyceride is 38.5%, and the number of dropouts of Ca is 159.2 ppm in product.
Claims (7)
1. a kind of preparation method of nanometer calcium lanthanium complex oxide catalyst, which is characterized in that using the colloidal sol of citric acid auxiliary
Micro-gel flooding, at the same using ethyl alcohol heat treatment improve oxide surface hydrophilic and hydrophobic, preparation the specific steps are：
(1) certain density calcium nitrate and lanthanum nitrate hexahydrate are configured, is mixed, the molar ratio of metal ion and water is 1: (30-
50)；
(2) heating stirring under the conditions of 70-90 DEG C, is added citric acid while stirring, and the molar ratio of citric acid and metal ion is
0.5:1-2:1；
(3) by step（2）The solution of gained is stirred continuously until to form colloidal sol at 70-90 DEG C, is then aged 18- at room temperature
24 hours；
(4) wet gel after ageing is 12-24 hours dry at 100-140 DEG C of temperature, air atmosphere, before obtaining catalyst
Drive body 1；
(5) after grinding catalyst precursor 1, it is warming up to 500-600 DEG C with 1-3 DEG C/min in air atmosphere, keeps 1-5
Hour, then it is warming up to 700-800 DEG C with 1-3 DEG C/min, it roasts 2-8 hours under inert gas atmosphere, before obtaining catalyst
Drive body 2；
(6) catalyst precursor 2 is mixed with the absolute ethyl alcohol of 2-5 times of weight, is placed in pressure vessel, at 120-150 DEG C
Processing 2-3 hour, after cooling down under an inert atmosphere 80-120 DEG C dry 6-12 hours to get to required catalyst；
Calcium in catalyst, lanthanum molar ratio be 1:5-5:1.
2. preparation method according to claim 1, it is characterised in that the inert gas is argon gas or helium, either
Their mixed gas.
3. a kind of nanometer calcium lanthanium complex oxide catalyst being prepared by preparation method described in claim 1.
4. nanometer calcium lanthanium complex oxide catalyst as claimed in claim 3 is in glycerolysis vegetable oil synthetic glycerine monoesters
Application, it is characterised in that using vegetable oil and glycerine as raw material, the specific steps are：
(1) catalyst is added in vegetable oil, forms mixed liquor, mixed liquor is heated to 180-240 DEG C；
(2) glycerine is added into the mixed liquor of preheated vegetable oil and catalyst；At a temperature of 180-240 DEG C, with 300-
The speed of 1000 rpm stirs, and reacts 10 min-300 min, obtains the product containing monoglyceride.
5. application according to claim 4, it is characterised in that the vegetable oil is soya-bean oil, corn oil, palm oil, cottonseed
Oil, rapeseed oil, olive oil, curcas oil or in which several mixtures.
6. application according to claim 4, it is characterised in that the weight ratio of the glycerine and vegetable oil is 1:5-1:1.
7. application according to claim 4, it is characterised in that the usage amount of the catalyst is the 0.1%- of plant weight of oil
5%。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897808A (en) * | 2014-03-11 | 2014-07-02 | 复旦大学 | Method for synthesizing monoglyceride by using glycerol alcoholysis vegetable oil |
| CN104525241A (en) * | 2014-12-18 | 2015-04-22 | 复旦大学 | Solid alkali catalyst as well as preparation method and application thereof in glycerinum alcoholysis reaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9089833B2 (en) * | 2008-11-05 | 2015-07-28 | Wayne State University | Calcium and lanthanum solid base catalysts for transesterification |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897808A (en) * | 2014-03-11 | 2014-07-02 | 复旦大学 | Method for synthesizing monoglyceride by using glycerol alcoholysis vegetable oil |
| CN104525241A (en) * | 2014-12-18 | 2015-04-22 | 复旦大学 | Solid alkali catalyst as well as preparation method and application thereof in glycerinum alcoholysis reaction |
Non-Patent Citations (2)
| Title |
|---|
| K2CO3/A12O3催化大豆油甘油解制备单甘酯的研究;张震 等;《中国油脂》;20131231;第38卷(第8期);第34-37页 * |
| Transesterification of Jatropha curcas crude oil to biodiesel on calcium lanthanum mixed oxide catalyst: Effect of stoichiometric composition;Yun Hin Taufiq-Yap et al.;《Energy Conversion and Management》;20140213;第88卷;第1290-1296页 * |
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