CN101411974A - Process for synthesizing mesoporous magnesia catalyst and uses thereof - Google Patents
Process for synthesizing mesoporous magnesia catalyst and uses thereof Download PDFInfo
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- CN101411974A CN101411974A CNA2008102025900A CN200810202590A CN101411974A CN 101411974 A CN101411974 A CN 101411974A CN A2008102025900 A CNA2008102025900 A CN A2008102025900A CN 200810202590 A CN200810202590 A CN 200810202590A CN 101411974 A CN101411974 A CN 101411974A
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Abstract
The invention relates to a method for synthesizing a mesoporous magnesia catalyst and application thereof. The mesoporous magnesia catalyst is synthesized by a hard template copying method. Magnesium nitrate is used as a magnesium source; and mesoporous carbon is used as a template agent. The preparation method comprises the following steps: the mesoporous carbon is dispersed in a magnesium nitrate solution, is stirred, centrifugated and dried; and the obtained product is dispersed in the magnesium nitrate solution again, is stirred, centrifugated, dried and roasted to prepare the mesoporous magnesia catalyst. The method for catalyzing and oxidizing cyclic ketone to prepare lactone comprises the following steps: an aqueous hydrogen peroxide solution is used as an oxidant; a solvent is a mixed solution of cyanobenzene and 1, 4-dioxane; and the reaction time is between 2 and 10 hours. The catalyst has the advantages that the catalyst has high catalytic activity and high selectivity of a lactone product and is used for the reaction for synthesizing the lactone through the cyclic ketone; the transformation rate of cyclohexanone is 78 percent; the selectivity of caprolactone is 100 percent; the transformation rate of adamantane ketone is 100 percent; the selectivity of adamantane lactone is 100 percent; the transformation rate of cyclopentanone is 100 percent; the selectivity of valerolactone is 43 percent; and the catalyst has mild reaction condition, high efficiency and convenient production and control.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to synthesizing of a kind of mesoporous magnesia catalyst and uses thereof, be used for the reaction of Baeyer-Villiger catalytic oxidation cyclic ketones system lactone.
Background technology
Baeyer-Villiger (BV) oxidation reaction is the important reaction of a class that cyclic ketones or chain oxidation of ketones is become lactone or ester, can control the stereochemical structure of product in view of this reaction, therefore in organic synthesis the conversion of functional group and the expansion of ring is had important meaning.Used oxidant generally is peroxy acid (as trifluoro Peracetic acid, benzoyl hydroperoxide, a metachloroperbenzoic acid etc.) in traditional BV oxidation reaction.Used oxidant is chemical oxidizing agent, and there are some general shortcomings in these oxidants, and is serious as environmental pollution, acid pollution is big, quantity of three wastes is big, product is difficult to separate to purify etc., is unfavorable for technical scale production.Simultaneously because these oxidants of preparation must be used the H of high concentration
2O
2, and the H of high concentration
2O
2Dangerous in transportation and processing procedure, so this method is eliminated in industry gradually.At present, the oxidant of BV oxidation reaction employing has molecular oxygen (making co-oxidants with aldehyde) or H
2O
2, the main accessory substance of the latter is H
2O, therefore environmental friendliness, and cheap and easy to get has been subjected to people's extensive concern.
Above the purpose of described catalyst all be to strengthen the nucleophilicity of oxidant, thereby help the attack of oxidant to substrate (cyclic ketones), but productive rate and selectivity are not high.Corma etc. look for another way, and use H
2O
2As cleaning oxidizer, the purpose of carbonyl carbon from the activation ketone embeds tin and comes catalytic oxidation Baeyer-Villiger reaction in the β zeolite.Because have many apertures in the β zeolite, so just created condition for the embedding of tin, and tin is a good lewis acid, can strengthen the electropositive of carbonyl carbon on the ketone, thereby help oxidant attack carbonyl carbon, reach the purpose of activation carbonyl carbon, the oxidation of this reaction pair cyclohexanone has obtained very high selectivity (98%), and the water insoluble He all organic solvents of this catalyst, the research that changes into ester or lactone compound for catalytic oxidation ketone or cyclic ketones provides vast potential for future development.But in this kind method, the catalyst preparation process complexity, manufacturing cycle is long, and organotin costs an arm and a leg, and the repeatability of catalyst can not guarantee.Though higher to the oxidation reaction selectivity of cyclic ketones in addition, conversion ratio is lower, therefore pressing for more, suitable catalyst improves catalytic reaction efficient.
Recently, Ruiz etc. propose MgO, Mg (OH)
2, basic anhydride such as HT and hydroxide can be used as the good catalyst of Baeyer-Villiger reaction, prepare Mg (OH) by the precipitation method
2, obtain corresponding MgO by roasting again.Them have been investigated then with 30% H
2O
2The aqueous solution is oxidant, and benzonitrile is in the system of solvent, cyclohexanone is oxidized to the catalytic performance of the Baeyer-Villiger reaction of 6-caprolactone.Discovery has excellent catalytic activity.Cyclohexanone can reach and surpass 70% conversion ratio behind 70 ℃ of synthesis under normal pressure 6h.By relatively finding out, with the nitrile compounds is solvent, when metal oxide and hydroxide are catalyst, compare with other catalyst, not only the preparation method is simple, and the MgO catalyst demonstrates 100% catalytic activity in the BV of cyclohexanone oxidation reaction, helps the recycling that repeats of catalyst.But this catalytic body system is not used for the research of other lactone, and repeatability is not high, though the high energy of the conversion ratio of cyclohexanone BV oxidation reaction and selectivity reaches 100%, TON is less in reaction, and catalytic efficiency is lower.In addition because correlative study is less, the author does not attempt the influence of other Mg based compound to this reaction, particularly catalyst pattern the influence of catalytic activity is remained further research.
Summary of the invention
Technical problem to be solved by this invention is to provide the synthetic method of a kind of more environmental friendliness, efficient and practical mesoporous magnesia catalyst.
Another technical problem to be solved by this invention is to provide a kind of mesoporous magnesia catalyst of above-mentioned synthetic method acquisition, has special meso-hole structure, and higher specific surface is more conducive to improve catalytic reaction efficient.
Another technical problem to be solved by this invention is to provide a kind of purposes of above-mentioned mesoporous magnesia catalyst, is used for the catalytic oxidation cyclic ketones and prepares lactone.
A technical problem more to be solved by this invention is to provide a kind of above-mentioned mesoporous magnesia catalyst to be used for the method that the catalytic oxidation cyclic ketones prepares lactone.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of synthetic method of mesoporous magnesia catalyst, adopt the hard template clone method synthetic, with the magnesium nitrate is the magnesium source, mesoporous carbon is the masterplate agent, the preparation method is: be dispersed in mesoporous carbon in the magnesium nitrate solution first, stirring, centrifugal, drying is 1～4 hour under 373～773K, be dispersed in product in the magnesium nitrate solution once more, stirring, centrifugal, under 373～773K dry 1～4 hour, roasting 1～6 hour under 573～773K again made mesoporous magnesia catalyst.
Wherein, the mol ratio of described mesoporous carbon and magnesium nitrate is 25～4:1.The mol ratio of described mesoporous carbon and magnesium nitrate is specially: 25,22,21,18,15,12,10,7.25,4.75,4.2 or 4:1.
Dry temperature is specifically as follows 373,400,450,500,550,600,650,700,750,773K, and can be 1,2,3 or 4 hours drying time; The temperature of roasting can be 573,600,650,700,750 or 773K, and roasting time can be 1,2,3,4,5 or 6 hours.General sintering temperature is higher than baking temperature.
On the basis of such scheme, the molar concentration of described magnesium nitrate is 0.5～1.5mol/L.
Concrete, the molar concentration of magnesium nitrate is 0.5,1.0,1.5mol/L.
On the basis of such scheme, first described and be dispersed in once more in the magnesium nitrate solution, use the magnesium nitrate solution of same molar concentration.
At the mesoporous magnesia catalyst that above-mentioned synthetic method makes, the mesoporous aperture of described mesoporous magnesia catalyst is 3～10nm, and reference area is 100～300m
2/ g.Mesoporous magnesia catalyst of the present invention is different from before the tin loaded catalyst of report and common MgO catalyst, has special meso-hole structure, and higher specific surface is more conducive to improve catalytic reaction efficient.
At the purposes of above-mentioned mesoporous magnesia catalyst, be used for the catalytic oxidation cyclic ketones and prepare lactone.
On the basis of such scheme, described cyclic ketones is cyclopentanone, cyclohexanone or adamantane ketone.
Be used for the method that the catalytic oxidation cyclic ketones prepares lactone at above-mentioned mesoporous magnesia catalyst, with the aqueous hydrogen peroxide solution is oxidant, with benzonitrile and 1, the mixed liquor of 4-dioxane is a solvent, under 303～373K, with mesoporous magnesia catalyst catalytic oxidation cyclic ketones, the reaction time is 2～10 hours, and the mol ratio of described catalyst and cyclic ketones is 0.2～0.7:1.
The mol ratio of described catalyst and cyclic ketones is specially 0.2,0.3, and 0.4,0.5,0.6 or 0.7:1.
Wherein, catalytic temperature is specifically as follows 303,320, and 340,360 or 373K, the reaction time can be 2,4,6,8 or 10 hours.
The mass concentration of aqueous hydrogen peroxide solution is 10～50%, generally can be 10,20,30,40 or 50%.
On the basis of such scheme, in the solvent, benzonitrile and 1, the mol ratio of 4-dioxane is 1:0.5～2.5.Concrete, benzonitrile and 1, the mol ratio of 4-dioxane is 1:0.5,0.8,1.0,1.2,1.5,1.8,2.0,2.2 or 2.5.
Mesoporous magnesia catalyst of the present invention is applied to the synthetic lactone of catalytic oxidation cyclic ketones, catalyst by special hard template method preparation has meso-hole structure, can obviously improve catalytic reaction efficient, by research to the different rings reactive ketone, the optimization optimum reaction condition helps large-scale industrialization production.
The invention has the beneficial effects as follows:
1, the catalytic activity height of this catalyst, internally the selectivity height of ester products.The mesoporous magnesia catalyst that the present invention makes is applied in the reaction of the synthetic lactone of cyclic ketones, the conversion ratio of cyclohexanone can reach 78%, caprolactone selectivity 100%, the conversion ratio of adamantane ketone can reach 100%, and the selectivity of adamantane lactone is 100%, and the cyclopentanone conversion ratio can reach 100%, valerolactone selectivity 43%, it is catalyst based that catalytic reaction TON all is higher than the Mg that in the past reported, near the peroxy acid catalytic levels, has great industrial application value;
2, this catalyst reaction mild condition, the efficient height does not have decomposition to hydrogen peroxide, broad between the operating space, elasticity is big, is convenient to production control;
3, catalyst can adopt simple filtration to separate from reaction system after reaction, has simplified original homogeneous phase technology greatly, has improved efficient, has reduced cost;
4, the used oxidant of this technology is green H
2O
2, the reaction condition gentleness, simple to operate.Cost is low.
Description of drawings
Fig. 1 is the electron micrograph of the typical mesoporous magnesia catalyst of the present invention.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1
A kind of synthetic method of mesoporous magnesia catalyst adopts the hard template clone method synthetic, and the magnesium source is a magnesium nitrate, and the template agent is a mesoporous carbon, and the preparation method is:
The 0.021mol mesoporous carbon is dispersed in first the Mg (NO of 1mL (0.5mol/L)
3)
2In the solution, stirring, centrifugal at the dry 1h of 373K, is dispersed in product the Mg (NO of 1mL (0.5mol/L) once more
3)
2In the solution, stirring, centrifugal at the dry 1h of 373K, is warming up to 573 roasting 1h again to remove the agent of mesoporous carbon masterplate under air atmosphere, promptly obtain the 1# catalyst.
The 1# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 10wt% of 0.9mL
2O
2Be oxidant, 2.4ml mol ratio is 1:0.5 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 303K is bathed in control, with the 1# mesoporous magnesia catalyst 0.0029mol cyclohexanone is carried out catalytic oxidation, reaction time is 2 hours, and the mol ratio of catalyst and cyclohexanone is 0.2:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 2
A kind of synthetic method of mesoporous magnesia catalyst adopts the hard template clone method synthetic, and the magnesium source is a magnesium nitrate, and the template agent is a mesoporous carbon, and the preparation method is:
The 0.029mol mesoporous carbon is dispersed in first the Mg (NO of 2mL (1.0mol/L)
3)
2In the solution, stirring, centrifugal at the dry 2h of 473K, is dispersed in product the Mg (NO of 2mL (1.0mol/L) once more
3)
2In the solution, stirring, centrifugal at the dry 2h of 473K, is warming up to 673K roasting 2h to remove the agent of mesoporous carbon masterplate under air atmosphere, promptly get the 2# catalyst.
The 2# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 20wt% of 1.2ml
2O
2Be oxidant, 2.4ml mol ratio is 1:1.0 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 313K is bathed in control, with the 2# mesoporous magnesia catalyst 0.0029mol cyclohexanone is carried out catalytic oxidation, reacted 4 hours, the mol ratio of catalyst and cyclohexanone is 0.3:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 3
A kind of synthetic method of mesoporous magnesia catalyst adopts the hard template clone method synthetic, and the magnesium source is a magnesium nitrate, and the template agent is a mesoporous carbon, and the preparation method is:
The 0.038mol mesoporous carbon is dispersed in first the Mg (NO of 3mL (1.5moL/L)
3)
2In the solution, stirring, centrifugal at the dry 3h of 573K, is dispersed in product the Mg (NO of 3mL (1.5moL/L) once more
3)
2In the solution, stirring, centrifugal at the dry 3h of 573K, is warming up to 773K roasting 4h again to remove the agent of mesoporous carbon masterplate under air atmosphere, promptly get the 3# catalyst.
The 3# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 30wt% of 1.5ml
2O
2Be oxidant, 2.4ml mol ratio is 1:1.5 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 323K is bathed in control, with the 3# mesoporous magnesia catalyst 0.0029mol cyclohexanone is carried out catalytic oxidation, reacted 6 hours, the mol ratio of catalyst and cyclohexanone is 0.4:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 4
A kind of synthetic method of mesoporous magnesia catalyst adopts the hard template clone method synthetic, and the magnesium source is a magnesium nitrate, and the template agent is a mesoporous carbon, and the preparation method is:
The 0.038mol mesoporous carbon is dispersed in first the Mg (NO of 4mL (1.0moL/L)
3)
2In the solution, stir, centrifugal, the dry 3h of 673K is dispersed in product the Mg (NO of 4mL (1.0moL/L) once more
3)
2In the solution, stirring, centrifugal, the dry 3h of 673K is warming up to 773K roasting 5h again to remove the agent of mesoporous carbon masterplate under air atmosphere, promptly get the 4# catalyst.
The 4# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 40wt% of 1.8ml
2O
2Be oxidant, 2.4mL mol ratio is 1:2.0 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 333K is bathed in control, with the 4# mesoporous magnesia catalyst 0.0029mol cyclohexanone is carried out catalytic oxidation, reacted 8 hours, the mol ratio of catalyst and cyclohexanone is 0.5:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 5
A kind of synthetic method of mesoporous magnesia catalyst adopts the hard template clone method synthetic, and the magnesium source is a magnesium nitrate, and the template agent is a mesoporous carbon, and the preparation method is:
The 0.042mol mesoporous carbon is dispersed in first the Mg (NO of 5mL (1.0mol/L)
3)
2In the solution, stirring, centrifugal at the dry 4h of 773K, is dispersed in product the Mg (NO of 5mL (1.0moL/L) once more
3)
2In the solution, stirring, centrifugal at the dry 4h of 773K, is warming up to 773K roasting 6h again to remove the agent of mesoporous carbon masterplate under air atmosphere, promptly get the 5# catalyst.
The 5# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 50wt% of 2.1ml
2O
2Be oxidant, 2.4ml mol ratio is 1:2.0 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 343K is bathed in control, with the 5# mesoporous magnesia catalyst 0.0029mol cyclohexanone is carried out catalytic oxidation, reacted 10 hours, the mol ratio of catalyst and cyclohexanone is 0.6:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 6
The preparation of mesoporous magnesia catalyst is with implementing 1.
The 1# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 10wt% of 0.9mL
2O
2Be oxidant, 2.4ml mol ratio is 1:0.5 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 303K is bathed in control, with the 1# mesoporous magnesia catalyst 0.0029mol adamantane ketone is carried out catalytic oxidation, reacted 7 hours, the mol ratio of catalyst and adamantane ketone is 0.7:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 7
The preparation of mesoporous magnesia catalyst is with implementing 2.
The 2# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 20wt% of 1.2ml
2O
2Be oxidant, 2.4ml mol ratio is 1:1.0 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 313K is bathed in control, with the 2# mesoporous magnesia catalyst 0.0029mol adamantane ketone is carried out catalytic oxidation, reacted 7 hours, the mol ratio of catalyst and adamantane ketone is 0.3:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 8
The preparation of mesoporous magnesia catalyst is with implementing 1.
The 1# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 30wt% of 1.5mL
2O
2Be oxidant, 2.4ml mol ratio is 1:1.5 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 323K is bathed in control, with the 1# mesoporous magnesia catalyst 0.0029mol cyclopentanone is carried out catalytic oxidation, reacted 7 hours, the mol ratio of catalyst and cyclopentanone is 0.3:1, and reaction is finished post analysis and be the results are shown in Table 1.
Embodiment 9
The preparation of mesoporous magnesia catalyst is with implementing 2.
The 2# mesoporous magnesia catalyst is used for the method that the catalytic oxidation cyclic ketones prepares lactone:
H with the 30wt% of 1.5mL
2O
2Be oxidant, 2.4ml mol ratio is 1:1.5 benzonitrile and 1, the mixed solution of 4-dioxane is a solvent, warm 333K is bathed in control, with the 2# mesoporous magnesia catalyst 0.0029mol cyclopentanone is carried out catalytic oxidation, reacted 7 hours, the mol ratio of catalyst and cyclopentanone is 0.3:1, and reaction is finished post analysis and be the results are shown in Table 1.
Table 1 mesoporous magnesia catalyst is to the catalytic oxidation condition and the active result of cyclic ketones
| Catalyst | Temperature (K) | Cyclic ketones conversion ratio (%) | Lactone selectivity (%) | Lactone yield (%) |
| Embodiment 1 | 303 | 26 | 100 | 26 |
| Embodiment 2 | 313 | 98 | 100 | 98 |
| Embodiment 3 | 323 | 76 | 100 | 76 |
| Embodiment 4 | 333 | 100 | 100 | 100 |
| Embodiment 5 | 343 | 99 | 100 | 99 |
| Embodiment 6 | 303 | 42 | 100 | 42 |
| Embodiment 7 | 313 | 100 | 100 | 100 |
| Embodiment 8 | 323 | 100 | 43 | 43 |
| Embodiment 9 | 333 | 80 | 42 | 33 |
Claims (7)
1, a kind of synthetic method of mesoporous magnesia catalyst, adopt the hard template clone method synthetic, with the magnesium nitrate is the magnesium source, mesoporous carbon is the masterplate agent, the preparation method is: mesoporous carbon is dispersed in the magnesium nitrate solution, stirring, centrifugal, drying is 1～4 hour under 373～773K, once more with the gained sample dispersion in magnesium nitrate solution, stir, centrifugal under 373～773K dry 1～4 hour, roasting is 1～6 hour under 573～773K, make mesoporous magnesia catalyst, wherein, the mol ratio of described mesoporous carbon and magnesium nitrate is 25～4:1.
2, the synthetic method of mesoporous magnesia catalyst according to claim 1 is characterized in that: the molar concentration of described magnesium nitrate solution is 0.5～1.5mol/L.
3, the mesoporous magnesia catalyst that makes at claim 1 or 2 described synthetic methods, it is characterized in that: the mesoporous aperture of described mesoporous magnesia catalyst is 3～10nm, reference area is 100～300m
2/ g.
4,, be used for the catalytic oxidation cyclic ketones and prepare lactone at the purposes of the described mesoporous magnesia catalyst of claim 3.
5, the purposes of mesoporous magnesia catalyst according to claim 4, described cyclic ketones are cyclopentanone, cyclohexanone or adamantane ketone.
6, a kind ofly be used for the method that the catalytic oxidation cyclic ketones prepares lactone at claim 4 or 5 described mesoporous magnesia catalysts, with the aqueous hydrogen peroxide solution is oxidant, it is characterized in that: adopt benzonitrile and 1, the mixed liquor of 4-dioxane is a solvent, under 303～373K, with mesoporous magnesia catalyst catalytic oxidation cyclic ketones, the reaction time is 2～10 hours, wherein, the mol ratio of described catalyst and cyclic ketones is 0.2～0.7:1.
7, mesoporous magnesia catalyst according to claim 6 is used for the method that the catalytic oxidation cyclic ketones prepares lactone, is characterised in that: in the described solvent, and benzonitrile and 1, the mol ratio of 4-dioxane is 1:0.5～2.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440005A (en) * | 2014-08-18 | 2016-03-30 | 江苏扬农化工集团有限公司 | Method for preparation of epsilon-caprolactone by catalysis of cyclohexanone by MgO / Fe2O3 |
| CN113929653A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Method for co-producing epsilon-caprolactone and benzamide |
-
2008
- 2008-11-12 CN CNA2008102025900A patent/CN101411974A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440005A (en) * | 2014-08-18 | 2016-03-30 | 江苏扬农化工集团有限公司 | Method for preparation of epsilon-caprolactone by catalysis of cyclohexanone by MgO / Fe2O3 |
| CN113929653A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Method for co-producing epsilon-caprolactone and benzamide |
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Open date: 20090422 |