CN101722003B - Catalyst loaded on titanium dioxide for epoxidation of esters and preparation and application thereof - Google Patents
Catalyst loaded on titanium dioxide for epoxidation of esters and preparation and application thereof Download PDFInfo
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- CN101722003B CN101722003B CN2009103112968A CN200910311296A CN101722003B CN 101722003 B CN101722003 B CN 101722003B CN 2009103112968 A CN2009103112968 A CN 2009103112968A CN 200910311296 A CN200910311296 A CN 200910311296A CN 101722003 B CN101722003 B CN 101722003B
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Abstract
The invention relates to a catalyst loaded on titanium dioxide for epoxidation of esters and a preparation and an application thereof, which belong to the technical field of catalysts for epoxidation of the esters and can solve the problems of low catalytic activity, incapability of repeated utilization, complicated operation and the like of the catalysts. The catalyst contains oxides of one or more selected from Fe, Sn, Al or Zr elements, wherein the molar ratio of the sum of one or more of Fe, Sn, Al or Zn elements to Ti atoms is 0.05-0.30, the catalyst combines the oxides of the elements on titanium dioxide nanotubes through impregnation and calcination, thereby being used as the catalyst during the epoxidation of unsaturated fatty acid methyl esters taking hydrogen peroxide, organic peroxides and inorganic peroxides as oxidants, realizing high activity, being regenerated in the air at 500 DEG C and leading the active regeneration coefficient to be more than 94%.
Description
Technical field
The present invention is stated from ester class epoxidation catalyst and preparation and the application on the titanium dioxide, particularly relates to the synthetic and application in unrighted acid methyl esters epoxidation of the metal oxide-loaded catalysis material of titania nanotube.
Background technology
Titanium dioxide is a kind of important photoelectric material, and the preparation method mainly contains sol-gel method, electrodeposition process (Liu S Q, Huang K L, Sol.Energy Mat.Sol.C; 2005,85.125～131), anodizing (east, side, Liu Suqin; Chen Ruoyuan etc., Journal of Inorganic Materials, 2008; 23,647～651) etc., at solar cell, photocatalysis to degrade organic matter, photodissociation water prepares aspects such as hydrogen, lithium ion battery, hydrogenation catalyst that good application is all arranged.Titania nanotube duct external diameter 100～150 nanometers of nano-tube array type, wall thickness 10～25 nanometers have bigger specific area, and the particular field effect of nanoscale has improved titanium dioxide greatly in photoelectricity, electromagnetism and otherwise performance, at solar cell material (Mor G K; Shankar K, Paulose M, Nano Lett, 2006,6; 215～218), lithium ion battery material (Gregorio F.Ortiz, Lie Hanzu, Thierry Djenizian, Pedro Lavela; Jose L.Tiradoand Philippe Knaut, Chem.Mater.2009,21,63～67), biofiltration material (Gong D W; Yadavalli V, Paulose M, Biomed.Microdevices, 2003; 5,75～80) and sensing material (Varghese O K, Gong D W, Dreschel W R; Sens.Actuators B, 2003,94,27～35) etc. the field has broad application prospects.But titania nanotube is synthetic at catalyzing organic, and particularly the application of the epoxidation aspect of unrighted acid methyl esters still is not reported.
The unrighted acid methyl esters is a kind of important organic chemicals, and the acquisition of can from vegetable oil, deriving is nontoxic; Biodegradable, be a kind of eco-friendly material, but owing to contain two keys; Stability, weatherability, compatibility and compatibility are not good; Can improve performance through epoxidation, obtain good plasticizer, softening agent, surfactant, dispersant etc., can be widely used in function fine chemicals field.
At present to adopt hydrogen peroxide be epoxidizing agent for epoxy aliphatic acid methyl ester synthetic main, is catalyst with small molecular organic acids such as inorganic acid such as sulfuric acid, aluminum sulfate, ferric sulfate, heteropoly acid, solid super-strong acid or formic acid, acetate, and at normal pressure, temperature obtains (CN 1919905A down for 40～70 ℃; Nie Xiaoan, Jiang Jianchun, Chen Shuigen, chemistry of forest product and industry; 2008,28,48～52), used hydrogen peroxide must be excessive greatly and also concentration be not less than 25%; Need add stabilizing agent simultaneously and control hydrogen peroxide decomposes, in order to make the complete epoxidation of unrighted acid methyl esters, the reaction time is at (CN 1876639A, Yang Kunyu more than 5 hours; Ying Yu, unparalleled big, Sichuan chemical industry, 2009; 12,10～13), complicated operation; The used catalyst of this method is difficult to recycle, and generation has acid-bearing wastewater, the development of protection more and more like a fish out of water in a large number in the epoxidation process.
Summary of the invention
The objective of the invention is on existing technical foundation; Solve in the prior art such catalyst activity low, be difficult to problem such as recycling; Provide a kind of be different from present activity higher be stated from the ester class epoxidation catalyst on the titania nanotube; And after catalysis, can reuse environmentally safe; Second purpose of the present invention provides the synthetic method of this catalyst, solves the not good problem of catalyst performance in the prior art.The 3rd purpose of the present invention provides the application of this catalyst on unrighted acid methyl esters epoxidation.
The catalyst that the ester class epoxidation that is stated from the titanium dioxide of the present invention is used: said catalyst is carrier with the titania nanotube; Be loaded with one or more the oxide that is selected from Fe, Sn, Al or the Zr element, the summation of one or more in Fe, Sn, Al or the Zr element and the mol ratio of Ti element are 0.05～0.30; Through titanium dioxide nano-tube support being immersed in one or more the solution that contains among Fe, Sn, Al or the Zr, preparing said catalyst through roasting then.
Preparation of catalysts method of the present invention: according to said proportioning; Process metal salt solution in the aqueous solution that one or more nitrate or chloride in Fe, Sn, Al or the Zr element is dissolved in organic solvent, the gross mass percentage that this GOLD FROM PLATING SOLUTION belongs to salt is 5%～40%; Titanium dioxide nano-tube support is immersed in this metal salt solution; In closed container, flood, temperature is 50～150 ℃, and dip time carries out Separation of Solid and Liquid (conventional method after 0.5～72 hour; As filter, method such as centrifugal, film separation separates); Behind the solid drying with Separation of Solid and Liquid, in air,, obtain described catalyst with 350～550 ℃ of roasting temperatures 3～48 hours.
Catalyst of the present invention is used for unrighted acid methyl esters epoxidation reaction and makees catalyst.
Remarkable advantage of the present invention is:
(1) the present invention is on the basis of existing titania nanotube technology of preparing; Through load iron oxide on titania nanotube, aluminium oxide, tin oxide, zirconic compound; Make this material have good unrighted acid methyl esters epoxidation catalytic activity, environmental friendliness, no acid-bearing wastewater discharging in the reaction; Can reclaiming use, the active regeneration coefficient is greater than 94%.
(2) characteristic of titania nanotube is optimized and utilized to epoxidation catalyst provided by the present invention, with preferred metal oxide active component through the coordination of oxygen atom bridging; Combine with the Ti on titania nanotube surface; Obtained performance excellent catalytic activity component can be accomplished epoxidation reaction fast under temperate condition; And after catalysis, can reuse environmentally safe.
(3) catalyst of the present invention is done the purposes of catalyst in the unrighted acid methyl esters epoxidation reaction that with hydrogen peroxide, organic peroxide, inorganic peroxide is oxidant; Active high; And can in 500 ℃ of following air, regenerate, the active regeneration coefficient is greater than 94%.
(4) catalyst preparation process of the present invention is simply quick, is fit to large-scale promotion application.
The specific embodiment
The titania nanotube that the present invention adopts can be classical anodizing preparation (east, side, Liu Suqin, Chen Ruoyuan etc., Journal of Inorganic Materials, 2008,23,647～651), nanotube external diameter 100～150 nanometers, the cylindrical tube of wall thickness 10～25 nanometers.
Be loaded with on the titania nanotube in Fe, Sn, Al or the Zr element one or more oxide ratio according to: Fe: Sn: Al: the mol ratio between the Zr element is: 0～0.35: 0～0.45: 1: 0～0.2; The summation of one or more in Fe, Sn, Al or the Zr element and the mol ratio of Ti element are 0.05～0.30.
Used maceration extract generally adopts the nitrate or the chloride of these metals (one or more among Fe, Sn, Al or the Zr), and the mass percentage concentration of slaine is 5%～40% in the maceration extract.
The solvent of maceration extract is the aqueous solution of organic solvent, and said organic solvent is to be selected from ethanol, isopropyl alcohol and the acetone one or more, and the mass ratio of organic solvent and water is: 70-90: 10-30.
According to said proportioning, process metal salt solution in the aqueous solution that one or more nitrate or the chloride in Fe, Sn, Al or the Zr element is dissolved in organic solvent, the gross mass percentage that this GOLD FROM PLATING SOLUTION belongs to salt is 5%～40%; Titanium dioxide nano-tube support is immersed in this metal salt solution; Dipping temperature is 50～150 ℃, dip time after 0.5～72 hour with Separation of Solid and Liquid; Separation can be adopted filtration, centrifugal etc., can effectively isolate catalyst just, after conventional method separating solids drying, in air, with 350～550 ℃ of roasting temperatures 3～48 hours, obtains described catalyst.
The catalyst that obtains is done catalyst applications in the unrighted acid methyl esters epoxidation reaction that with hydrogen peroxide, organic peroxide, inorganic peroxide is oxidant, common oxidant is a hydrogen peroxide.Unrighted acid methyl esters epoxidation reaction condition is 40～110 ℃ of temperature; The mass percentage concentration 5～20% of peroxide; Catalyst quality percentage is 0.5～5%, and the mass percentage concentration of unrighted acid methyl esters is not less than 10%, and 1.5～5 hours reaction time can react completely.
This catalyst can react the centrifugal recovery in back, and 350～550 ℃ of roastings regeneration in 3～48 hours is reused in air, and the active regeneration coefficient can reach 94% (embodiment 1 is seen in actual conditions and definition).Described unrighted acid methyl esters refers to contain the unrighted acid methyl esters of carbon-carbon double bond, like the carbon enoic acid methyl esters of carbon 8 to carbon 20, preferably methyl oleate, methyl linoleate and methyl linolenate; The epoxidation effect is particularly remarkable; Need not stabilizing agent, effective utilization ratio of hydrogen peroxide is high, under 60 ℃; The conversion ratio of 3 hours methyl oleates is near 97%, and performance is superior to industry at present greatly and goes up the inorganic acid catalyst that uses.
Through embodiment the present invention is done further explanation below, but protection scope of the present invention does not receive the restriction of these embodiment.
In following each embodiment, agents useful for same is commercially available chemically pure reagent or industrial primes.
Embodiment 1
With aluminum nitrate (Al (NO
3)
39H
2O), stannous chloride (SnCl
2), ferric nitrate (Fe (NO
3)
39H
2O) be raw material, be mixed with Fe: Sn with ethanol water (wherein ethanol: the mass ratio of water is 80: 20): the Al mol ratio is 0.15: 0.25: 1, and total mol concentration is 0.5molL
-1Maceration extract.Get 20 gram titania nanotubes, adopt anodizing (east, side, Liu Suqin, Chen Ruoyuan etc., Journal of Inorganic Materials, 2008,23,647～651) to obtain, specific surface is 80m
2/ g.Maceration extract and the above-mentioned titania nanotube of 50mL is mixed, under 100 ℃ of conditions, flooded 48 hours, centrifugation then, washing, oven dry, calcining is 10 hours in 450 ℃ of following air, obtains epoxidation catalyst, and it is numbered T-1.
The activity rating method:
In the four-hole boiling flask that has agitator, thermometer, dropping funel and condenser pipe, add the 100g methyl oleate, start agitator; After being warming up to certain temperature, slowly drip hydrogen peroxide, control rate of addition and reaction temperature; Behind the reaction 3h; Product is poured in the separatory funnel, told lower floor's water, the epoxyoleic acid methyl esters on upper strata.
The formation reaction product is used gas chromatographic analysis, fid detector, Agilent 6890, the FFAP capillary column of 30m * 0.53mm * 1.00um; Temperature of vaporization chamber is 250 ℃, heating schedule: 130 ℃ of initial temperature keep 2min; With 4 ℃/min, rise to 215 ℃, keep 10min; Carrier gas is a high pure nitrogen, is internal standard compound with the methyl stearate, analyzes the conversion ratio of methyl oleate and the yield of epoxyoleic acid methyl esters.
The ratio of the epoxyoleic acid methyl esters productive rate under the standard reaction condition on the active regeneration coefficient, regenerated catalyst and fresh catalyst.
The standard reaction thing: the 100g methyl oleate, 20% hydrogen peroxide 57g,
Reaction condition: 60 ℃ of reaction temperatures, 3 hours reaction time, catalyst 2.0g.
The result of T-1 under the standard reaction condition is as shown in table 1.
Embodiment 2
With aluminum nitrate (Al (NO
3)
39H
2O), stannous chloride (SnCl
2), ferric nitrate (Fe (NO
3)
39H
2O), zirconium nitrate (Zr (NO
3) 43H
2O) be raw material, be mixed with Fe: Sn: Al with ethanol water (wherein ethanol: the quality ratio is 85: 15): the Zr mol ratio is 0.15: 0.25: 1: 0.05, and total mol concentration is 0.55molL
-1Maceration extract.Get 20 gram titania nanotubes (preparation method is with embodiment 1), maceration extract and the above-mentioned titania nanotube of 50mL is mixed, under 120 ℃ of conditions; Flooded centrifugation then, washing 36 hours; Oven dry; Calcining is 8 hours in 500 ℃ of following air, obtains epoxidation catalyst, and it is numbered T-2.
Reaction unit and analysis condition are with embodiment 1.
Reactant: the 100g methyl linoleate, 10% hydrogen peroxide 120g,
Reaction condition: 65 ℃ of reaction temperatures, 2.5 hours reaction time, catalyst 1.6g.
The reactivity result of T-2 is as shown in table 1.
Embodiment 3
With aluminum nitrate (Al (NO
3)
39H
2O), zirconium nitrate (Zr (NO
3) 43H
2O), ferric nitrate (Fe (NO
3)
39H
2O) be raw material, be mixed with Fe: Zr with ethanol water (ethanol: the quality ratio is 90: 10): the Al mol ratio is 0.3: 0.1: 1, and total mol concentration is 0.5molL
-1Maceration extract.Get 20 gram titania nanotubes (preparation method is with embodiment 1), maceration extract and the above-mentioned titania nanotube of 60mL is mixed, under 80 ℃ of conditions; Flooded centrifugation then, washing 60 hours; Oven dry; Calcining is 10 hours in 480 ℃ of following air, obtains epoxidation catalyst, and it is numbered T-3.
Reaction unit and analysis condition are with embodiment 1.
Reactant: the 100g methyl linolenate, 15% hydrogen peroxide 85g,
Reaction condition: 55 ℃ of reaction temperatures, 3 hours reaction time, catalyst 2.5g.
The reactivity result of T-3 is as shown in table 1.
Embodiment 4
With aluminum nitrate (Al (NO
3)
39H
2O) be raw material, being mixed with molar concentration with isopropanol water solution (isopropyl alcohol: the quality ratio is 80: 20) is 0.4molL
-1Maceration extract.Get 20 gram titania nanotubes (preparation method is with embodiment 1), maceration extract and the above-mentioned titania nanotube of 50mL is mixed, under 95 ℃ of conditions; Flooded centrifugation then, washing 24 hours; Oven dry; Calcining is 9 hours in 500 ℃ of following air, obtains epoxidation catalyst, and it is numbered T-4.
Reaction unit and analysis condition are with embodiment 1.
Reactant: the 90g methyl linolenate, 8% hydrogen peroxide 150g,
Reaction condition: 70 ℃ of reaction temperatures, 3 hours reaction time, catalyst 2.2g.
The reactivity result of T-4 is as shown in table 1.
Embodiment 5
With aluminum nitrate (Al (NO
3)
39H
2O), stannous chloride (SnCl
2), ferric nitrate (Fe (NO
3)
39H
2O) be raw material, be mixed with Fe: Sn with isopropanol water solution (isopropyl alcohol: the quality ratio is 70: 30): the Al mol ratio is 0.35: 0.05: 1, and total mol concentration is 0.5molL
-1Maceration extract.Get 20 gram titania nanotubes (preparation method is with embodiment 1), maceration extract and the above-mentioned titania nanotube of 50mL is mixed, under 85 ℃ of conditions; Flooded centrifugation then, washing 30 hours; Oven dry; Calcining is 10 hours in 520 ℃ of following air, obtains epoxidation catalyst, and it is numbered T-4.
Reaction unit and analysis condition are with embodiment 1.
Reactant: the 90g methyl linolenate, 8% hydrogen peroxide 150g,
Reaction condition: 70 ℃ of reaction temperatures, 2.5 hours reaction time, catalyst 3.0g.
The reactivity result of T-5 is as shown in table 1.
Embodiment 6
The catalyst of embodiment 1 preparation is used the back centrifugation, washing, oven dry is reclaimed, and calcining is 5 hours in 500 ℃ of following air, and the epoxidation catalyst after obtaining regenerating is numbered T-6 with it.
Reaction unit and analysis condition are with embodiment 1.
The reactivity result of T-6 is as shown in table 1.
Comparative Examples
Reaction unit and analysis condition are with embodiment 1.
Reaction condition: the 100g methyl oleate, 20% hydrogen peroxide 57g, 60 ℃ of reaction temperatures, in 3 hours reaction time, the concentrated sulfuric acid of getting with the amount of titanium dioxide same substance adds agitated reactor as catalyst (it is numbered BZ-1), is 2.5g.
The reactivity result of BZ-1 is as shown in table 1.
The epoxidation catalytic activity of table 1 unrighted acid methyl esters
| Numbering | Conversion ratio (%) | Selectivity (%) | The productive rate of epoxy aliphatic acid methyl ester (%) |
| T-1 | 98.2 | 97.7 | 95.9 |
| T-2 | 94.9 | 96.6 | 91.7 |
| T-3 | 95.5 | 95.8 | 91.5 |
| T-4 | 97.2 | 94.1 | 91.5 |
| T-5 | 99.2 | 96.1 | 95.3 |
| T-6 | 96.3 | 95.9 | 92.4 |
| BZ-1 | 38.9 | 84.3 | 32.8 |
The active regeneration coefficient of T-5 is: 96.3%
In table 1:
Molal quantity * 100% of unrighted acid methyl esters before molal quantity/reaction that the unrighted acid methyl esters reduces before and after conversion ratio=reaction
Molal quantity * 100% that the unrighted acid methyl esters reduces before and after the molal quantity of the epoxy aliphatic acid methyl ester of the selectivity=generation of epoxy aliphatic acid methyl ester/reaction
Can find out from The above results, compare with comparative catalyst BZ-1, the catalyst of the present invention's preparation and regeneration rear catalyst, the unrighted acid conversion ratio all is higher than Comparative Examples, has good epoxidation activity.
Claims (9)
1. catalyst that the ester class epoxidation that is stated from the titanium dioxide is used; It is characterized in that: said catalyst is carrier with the titania nanotube; Be loaded with one or more the oxide that is selected from Fe, Sn, Al or the Zr element, the summation of one or more in Fe, Sn, Al or the Zr element and the mol ratio of Ti element are 0.05～0.30; Described oxide is according to Fe: Sn: Al: the mol ratio of Zr element is: 0～0.35: 0～0.45: 1: 0～0.2; Described ester class is the unrighted acid methyl esters that contains carbon-carbon double bond.
2. the catalyst that the ester class epoxidation that is stated from the titanium dioxide according to claim 1 is used is characterized in that: said titania nanotube is external diameter 100～150 nanometers, the cylindrical tube of wall thickness 10～25 nanometers.
3. Preparation of catalysts method that the ester class epoxidation that is stated from the titanium dioxide as claimed in claim 1 is used; It is characterized in that: preparation process is: according to said proportioning; Process metal salt solution in the aqueous solution that one or more nitrate or chloride in Fe, Sn, Al or the Zr element is dissolved in organic solvent, the gross mass percentage that this GOLD FROM PLATING SOLUTION belongs to salt is 5%～40%; Titanium dioxide nano-tube support is immersed in this metal salt solution, in closed container, floods, temperature is 50～150 ℃, and dip time carries out Separation of Solid and Liquid after 0.5～72 hour; After the solid separated drying, in air,, obtain described catalyst with 350～550 ℃ of roasting temperatures 3～48 hours.
4. the Preparation of catalysts method that the ester class epoxidation that is stated from the titanium dioxide according to claim 3 is used; It is characterized in that: said organic solvent is to be selected from ethanol, isopropyl alcohol and the acetone one or more, and the mass ratio of organic solvent and water is in the aqueous solution of organic solvent: 70-90: 10-30.
5. the Preparation of catalysts method that the ester class epoxidation that is stated from the titanium dioxide according to claim 3 is used, it is characterized in that: described solid-liquid separating method is isolated by filtration or centrifugation.
6. the purposes of the catalyst used of an ester class epoxidation that is stated from the titanium dioxide as claimed in claim 1 is characterized in that: said catalyst is used for containing the unrighted acid methyl esters epoxidation reaction of carbon-carbon double bond and makees catalyst.
7. the purposes of the catalyst that the ester class epoxidation that is stated from the titanium dioxide according to claim 6 is used; It is characterized in that: the said unrighted acid methyl esters epoxidation reaction that contains carbon-carbon double bond is meant with hydrogen peroxide, organic peroxide, inorganic peroxide to be the unrighted acid methyl esters epoxidation reaction that contains carbon-carbon double bond of oxidant.
8. the purposes of the catalyst that the ester class epoxidation that is stated from the titanium dioxide according to claim 6 is used; It is characterized in that: in the said unrighted acid methyl esters epoxidation reaction that contains carbon-carbon double bond: 40～110 ℃ of reaction temperatures; The mass percentage concentration 5～20% of peroxide; Catalyst quality percentage is 0.5～5%, and the mass percentage concentration that contains the unrighted acid methyl esters of carbon-carbon double bond is not less than 10%, and 1.5～5 hours reaction time can react completely; The unrighted acid methyl esters of carbon-carbon double bond is the carbon enoic acid methyl esters of carbon 8 to carbon 20.
9. the purposes of the catalyst that the ester class epoxidation that is stated from the titanium dioxide according to claim 6 is used, it is characterized in that: catalyst is centrifugal recovery after reaction, and 350～550 ℃ of roastings regeneration in 3～48 hours is reused in air; Said carbon 8 is methyl oleate, methyl linoleate or methyl linolenate to the carbon enoic acid methyl esters of carbon 20.
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|---|---|---|---|
| CN2009103112968A CN101722003B (en) | 2009-12-12 | 2009-12-12 | Catalyst loaded on titanium dioxide for epoxidation of esters and preparation and application thereof |
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|---|---|---|---|
| CN2009103112968A CN101722003B (en) | 2009-12-12 | 2009-12-12 | Catalyst loaded on titanium dioxide for epoxidation of esters and preparation and application thereof |
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| CN101722003B true CN101722003B (en) | 2012-04-18 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132798A (en) * | 1994-12-29 | 1996-10-09 | 菲利普莫里斯生产公司 | Aluminum containing iron-base alloys useful as electricalresistance heating elements |
| CN1241564A (en) * | 1997-04-22 | 2000-01-19 | 环球油品公司 | Epoxidation of olefing using catalyst containing titanostannosilicalites |
| CN1406909A (en) * | 2001-08-10 | 2003-04-02 | 拜尔公司 | Hydrocarbon epoxidizing method |
-
2009
- 2009-12-12 CN CN2009103112968A patent/CN101722003B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1132798A (en) * | 1994-12-29 | 1996-10-09 | 菲利普莫里斯生产公司 | Aluminum containing iron-base alloys useful as electricalresistance heating elements |
| CN1241564A (en) * | 1997-04-22 | 2000-01-19 | 环球油品公司 | Epoxidation of olefing using catalyst containing titanostannosilicalites |
| CN1406909A (en) * | 2001-08-10 | 2003-04-02 | 拜尔公司 | Hydrocarbon epoxidizing method |
Non-Patent Citations (1)
| Title |
|---|
| 原宇航等.TiO2纳米管负载金催化剂催化丙烯直接环氧化反应.《华东理工大学学报（自然科学版）》.2008,第34卷(第1期),第16-18，65页. * |
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