CN1329123C - System for catalyzing emulsion and method of use - Google Patents
System for catalyzing emulsion and method of use Download PDFInfo
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- CN1329123C CN1329123C CNB2004100067224A CN200410006722A CN1329123C CN 1329123 C CN1329123 C CN 1329123C CN B2004100067224 A CNB2004100067224 A CN B2004100067224A CN 200410006722 A CN200410006722 A CN 200410006722A CN 1329123 C CN1329123 C CN 1329123C
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Abstract
The present invention relates to a system for catalyzing emulsion and a using method thereof. The system is a catalyzed oxidation reacting system which uses water as solvent, hydrogen peroxide as an oxidizing agent and a heteropoly compound (Q 3 [XM [12] O [40]] or derivant thereof) as a catalyst. Formed emulsion can effectively select various types of molecules, such as catalyzed oxidation alcohol, organic sulfide, olefin, allyl alcohol, etc. under moderate conditions. The conversion rate of substrate is above 95%, product selectivity is larger than 99%, the emulsion is easily layered by emulsion breaking through standstill or centrifugation after reaction, the catalyst is suspended between the limiting surfaces of an oil phase and a water phases, and the catalyst and a product are easily separated and recovered. The recovered catalyst and be circularly used for many times.
Description
Technical field
The present invention relates to a kind of emulsion catalyst system and catalyzing that is used for the organic molecule oxidation that can be recycled.
The invention still further relates to the method for above-mentioned emulsion catalyst system and catalyzing catalytic oxidation organic molecule.
Background technology
During modern chemical industry is produced, even phase reaction system is because of having the reaction condition gentleness, high activity, plurality of advantages such as high selectivity and being widely adopted, but the difficult difficulty of bringing on the engineering that reclaims of the Separation ﹠ Purification of its end product and catalyst, while also might produce a large amount of waste liquids and environment is polluted, can be divided into two big classes for addressing these problems on even heterogeneousization of the phase catalysis methodological principle that adopts, one class is that the even phase catalyst of catalyst stationary on organic polymer or inorganic carrier (as silica gel or aluminium oxide) is immobilized, another kind of be with even phase catalyst dynamically " supporting " at liquid/liquid biphasic catalysis of implementing with the immiscible liquid phase of product.Immobilized even phase catalyst is not still realized commercial Application so far because of the losing issue that does not thoroughly solve active component as yet.And liquid/liquid biphasic catalysis system had both kept even phase catalytic reaction mild condition, catalytic activity height, advantage that selectivity is good, had the characteristics that heterogeneous catalysis technology is simple, catalyst is easy to be separated with product again, presented good prospects for application.
Liquid/liquid two-phase system is used in processes such as synthetic, separation, catalysis at present in a large number.Common liquid/liquid two-phase system is that a class is water/organic two-phase, promptly one is water mutually, another is organic solvent or other low polar solvent mutually, this system, reagent and catalyst dissolution are also reacted therein at aqueous phase, yet the range of application of water/organic biphasic catalysis system is subjected to water miscible restriction of reactant and reactant or reactant and meets problems such as water sensitive, the one, can not be used for catalyst, reactant or product to water sensitive; The 2nd, the reactant of poorly water-soluble should not use.The non-aqueous solution two-phase system can overcome this limitation to a certain extent.The fluorine two-phase system that developed recently gets up (Fluorous biphase system, FBS) be exactly a kind of non-water liquid-liquid two-phase reaction system, its unique distinction is under higher temperature, fluorous solvent in the fluorine two-phase system can dissolve each other into single phase mutually well with organic solvent, thereby for the chemical reaction that carries out therein provides good even phase reaction condition, after reaction finishes, reduce temperature, system reverts to two-phase again, and the fluorine that contains reactant and catalyst can separate easily with the organic facies that contains organic product.So only need be separated and catalyst need not be anchored on heterogeneousization or the immobilization that has just realized even phase catalyst on the fixed base (carrier).As the novel two-phase system of a class, the fluorine two-phase is specially adapted to control the reaction that is difficult in that water/organic two-phase system carries out because of mass transfer, but it should be noted that owing to use the harmful perfluoro alkane of atmospheric environment is solvent, the commercial Application possibility of fluorine two-phase is very little.
Biphasic catalysis is through nearly 20 years development, being substituted immobilized even phase catalysis becomes the main flow of even mutually heterogeneous change research field, comprise that water/organic two-phase system and the immobilized aqueous phase catalyst that emerges in large numbers recently, temperature control phase transfer catalysis (PTC), reaction-controlled phase transfer catalysis and fluorine two-phase system all can regard different point on the even phase catalysis of contact and the heterogeneous catalysis tie as, because they all have strict restriction to the synthetic design of catalyst, selected system, so applicable scope and field are narrow.Thereby, develop a kind of applied widely, catalyst easily separates with product and reclaim the catalyst system and catalyzing that uses, and is the common hope of people.
Emulsion is the important dispersion of a class, is widely used in fields such as the energy, chemical industry, food, medicine, agricultural chemicals, cosmetics.It is made up of two kinds of immiscible liquid and the amphiphatic surfactant of tool.Wherein one is made up of drop (decentralized photo), and another is called decentralized medium (continuous phase) mutually.Modal emulsion is that oil content is dispersed in system (being called oil-in-water O/W type) and the system (be called Water-In-Oil w/o type) of aqueous dispersion in oil in the water, can also be (O/O) of oily oil-in, the outward appearance of emulsion generally is milky, and is opaque, and the liquid pearl is generally greater than 0.1 μ m.Emulsion is the system of thermodynamic instability, it is by static or centrifugal, and two-phase is finally still wanted layering.We want this characteristic according to emulsion, and it is used on liquid/liquid biphasic catalysis.Reach catalyst separates and reclaim use with product purpose with this.
Emulsion is applied in the catalysis, catalyst can reclaim the patent of using and yet there are no report so far, and we want the oxidation of organic molecule with this characteristic and the prospect of emulsion applications in organic synthesis to be described as model reaction.
Summary of the invention
Purpose provided by the invention provides a kind of emulsion catalyst system and catalyzing, and this catalyst system and catalyzing can carry out organic synthesis in emulsion, and its catalyst easily separates with product and reclaims.
Another object of the present invention provides the method for above-mentioned catalyst system and catalyzing catalytic oxidation organic molecule.
In the emulsion catalyst system and catalyzing provided by the invention, by catalyst, oxidant and solvent composition.Catalyst wherein is amphiphatic quaternary ammonium salt heteropoly compound (Q
3[XM
12O
40] or derivatives thereof), wherein Q is meant cationic surfactant, is generally quaternary ammonium salt cationic (C
8H
17)
4N
+, (C
12H
25) N
+(CH
3)
3, (C
16H
33) N
+(CH
3)
3, (C
18H
37) N
+(CH
3)
3, (π-C
5H
5) N
+C
16H
33, (C
14H
29)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2Or/and (C
18H
37)
2N
+(CH
3)
2, (C wherein
12H
25)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2, (C
18H
37)
2N
+(CH
3)
2In reaction, has good effect; Described quaternary ammonium salt cationic is: (C
16H
33) N
+(CH
3)
3, (π-C
5H
5) N
+C
16H
33, (C
12H
25)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2Or/and (C
18H
37)
2N
+(CH
3)
2Heteropolyanion generally is the compound or derivatives thereof with Keggin structure of Keggin structure or omission, and hetero atom X can be P (phosphorus), Si (silicon), As (arsenic) etc., and coordination atom M can be Mo (molybdenum), W (tungsten) etc.And coordination atom M wherein can partly replace with transition metal such as Cr, Mn, Fe, Co, Ni, Nb, Rb, Ru, V, Ti etc., the compound or derivatives thereof of the Keggin structure of the mixed type that obtains, all has good catalytic oxidation effect, mostly more than 95%, product selectivity is greater than 99% for the conversion ratio of reactant.
Oxidant selected in the catalyst system and catalyzing can also be iodosobenzene (C except that hydrogen peroxide
6H
5IO), organic peroxide (ROOH), periodate or oxygen etc.
Solvent in the catalyst system and catalyzing is a water.
Above-mentioned catalyst system and catalyzing is used for the method for catalytic oxidation organic molecule, and its key step is:
1) solvent and oil and oxidant are put into reactor, add reactant (as alcohol, organic sulfur compound) and catalyst again, 50-80 ℃ is stirred down, forms emulsion; Wherein solvent is as continuous phase, and its volume fraction is 26～74%, and solvent is 5～20: 1 with the volume ratio of oil in the reaction, and the mol ratio of oxidant and reactant is 1～2: 1;
2) reaction certain hour takes out reactant liquor and carries out chromatography, after the question response balance, stops to stir, and emulsion is reduced to room temperature;
3) by static or centrifugal breakdown of emulsion, the profit layering, the oil on upper strata and the catalyst recovery on the two-phase interface are used.
Catalyst system and catalyzing of the present invention is when the catalytic oxidation organic molecule, comprise immiscible two-phase liquid, amphiphatic catalyst and reactant etc., above-mentioned mixed liquor is by stirring or ultrasonic, can form the emulsion of oil-in-water (O/W) or Water-In-Oil (W/O) under certain condition: a form with drop be scattered in another mutually in, parents' catalyst is self-assembled to two-phase interface, reaction occurs in the interface of two-phase, after question response is finished, the reaction emulsion can be passed through static or centrifugal breakdown of emulsion, two phase stratification, catalyst be present in two-phase interface or with product immiscible one mutually in, catalyst easily separates recovery with product, the catalyst of recovery can repeatedly recycle.
In above-mentioned emulsion reaction system, amphiphatic catalyst is to form emulsion and can reclaim the key of use.When designing amphiphatic catalyst, can be according to the characteristic of catalyst, itself and amphiphatic surfactant and catalyst junction altogether, selected surfactant, the surfactant of the surfactant of ionic, nonionic or high molecular surfactant, also fluorine surfactant, for the organic catalyst of solid, can combine the amphiphatic hybrid inorganic-organic materials of formation at the organic molecule of the suitable oleophylic of finishing or with itself and high molecular surfactant.The hydrophilic-lipophilic balance (HLB) of catalyst can be regulated by the quantity of the organic molecule of modifying or by surfactant structure and carbochain length according to the characteristics of reaction system, and catalyst can be joined and design at the enterprising luggage of molecular level.
For the selection of two-phase liquid, generally be water/oily two-phase, also available fluorine two-phase or other immiscible oil/oily two-phase.One form with drop be scattered in another mutually in, the volume fraction of general continuous phase will reach 26% at least, i.e. during the tightst arrangement of decentralized photo, volume fraction is at most 74%, reaction occurs in boundary, because the high-specific surface area of decentralized photo, emulsion catalysis is similar to even phase catalytic reaction.
In above-mentioned organic molecule catalytic oxidation system, and the emulsion of oil-in-water type that selected is (with water is solvent, chloralkane that need not be poisonous or aromatic hydrocarbons, process is economical, environmental protection).The a small amount of nontoxic oil of wherein selecting for use (for forming O/w emulsion) can be nonpolar alkane (as hexadecane, dodecane, normal heptane etc.), also fluorocarbons or other and water and the immiscible oil of product.The back breakdown of emulsion is finished in reaction, reacts creaming of emulsion, and the upper strata is an oil phase, and lower floor is a water, wherein catalyst boundary or existence and product immiscible one mutually in, can reach the purpose that catalyst separates with product by simple decant.The oil on isolated catalyst and upper strata can directly recycle.
The present invention is not limited only to the oxidation of organic molecule, also can expand to emulsion fields such as other organic synthesis, in multiple organic chemical reactionses such as esterification, alkylation, isomerization, rearrangement, acid catalysis.As long as the design reaction system in immiscible two-phase, carry out, with suitable amphiphatic compound as catalyst, in the course of reaction, all might form the emulsion of high-ratio surface, after the reaction, by static or centrifugal breakdown of emulsion, catalyst is separable and reclaims.
Conclusion is got up, and emulsion is applied in the organic synthesis field, and it has the following advantages:
1. the hydrophilic-lipophilic balance (HLB) of amphiphilic catalyst can be regulated by the quantity of the organic molecule of modifying or by surfactant structure and carbochain length according to the characteristics of reaction system, and catalyst can be joined and design at the enterprising luggage of molecular level.
The emulsion of Xing Chenging be a form with drop be scattered in another mutually in, parents' catalyst self-association is in two-phase interface, reaction occurs in the interface of two-phase because the high-specific surface area of decentralized photo, the reaction rate of emulsion catalysis is near even phase catalytic reaction.
3. but selected emulsion type is a modulation in synthetic, according to the characteristics of reaction, can be oil-in-water type (O/W), water-in-oil type (W/O), and also oily oil-in (O/O) is gone back multiple emulsion, i.e. W/O/W type and O/W/O type.
4. the emulsion of Xing Chenging is after reaction, can carry out breakdown of emulsion by the method for physics or chemistry, makes two phase stratification, catalyst be present in two-phase interface or with product immiscible one mutually in, easily separate to reclaim and use with product.
5. the emulsion scope in the organic synthesis that is applied in is very wide, is not limited only to the oxidation of organic molecule, also can expand to fields such as other organic synthesis, in multiple organic chemical reactionses such as esterification, alkylation, isomerization, rearrangement, acid catalysis.
The specific embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.Such as, the used reactant of the present invention can be isopropyl alcohol, sec-butyl alcohol, 2-amylalcohol, cyclopentanol, cyclohexanol, ring octanol, dimethyl sulfide, diethyl sulfide, benzothiophene, dibenzothiophenes, 4, the 6-dimethyl Dibenzothiophene.
Embodiment 1
Catalyst [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] preparation:
As an illustrative examples, catalyst [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] can prepare as follows: 3.05 gram dioctadecyl dimethyl ammonium chlorides are added in the beaker fill the 150ml deionized water be heated to 30 ℃, under vigorous stirring, in this beaker, drip and be dissolved with 5 gram H
3[PW
12O
40] the 10ml aqueous solution, generate white precipitate immediately.Behind continuous stirring 3～4h, white pulpous state liquid after filtration, deionized water washing, vacuum drying obtain white solid (6.7 gram), and yield is about 85%.This catalyst is represented with A.
Embodiment 2
Catalyst [(π-C
5H
5) N
+C
16H
33]
3[PW
12O
40] preparation.
As an illustrative examples, catalyst [(π-C
5H
5) N
+C
16H
33]
3[PW
12O
40] can prepare as follows: 1.77 gram cetylpyridinium chlorides are added in the beaker fill the 75ml deionized water be heated to 30 ℃, under vigorous stirring, in this beaker, drip the 10ml aqueous solution that is dissolved with 5 gram 12-phosphotungstic acids, generate a white precipitate immediately.Behind continuous stirring 3～4h, after filtration, deionized water washing, vacuum drying obtain a white solid (5.7 gram), yield is 87%.This catalyst is represented with B.
Embodiment 3
Catalyst [(C
16H
33) N
+(CH
3)
3]
3[PW
12O
40] preparation.
As an illustrative examples, catalyst [(C
16H
33) N
+(CH
3)
3]
3[PW
12O
40] can prepare as follows: 2.61 gram hexadecyltrimethylammonium chlorides are added in the beaker fill the 100ml deionized water be heated to 30 ℃, under vigorous stirring, in this beaker, drip the 10ml aqueous solution that is dissolved with 5 grams, 12 phosphotungstic acids, generate a white precipitate immediately.Behind continuous stirring 3～4h, after filtration, deionized water washing, vacuum drying obtain a white solid (6.1 gram), yield is 82%.This catalyst is represented with C.
Embodiment 4
Three kinds of catalyst A, each 6.6 μ mol of B, C of getting above-mentioned preparation are added to respectively in three triangular flasks, add reactant sec-butyl alcohol 0.05mol, 30% H then in each bottle respectively
2O
20.06mol, add 5ml water and 1ml hexadecane (for forming oil-in-water emulsion) again, reactant liquor under the vigorous stirring, forms milky liquid in 80 ℃ oil bath, continue to stir 24h, reduce to room temperature, by static or centrifugal, creaming of emulsion, the upper strata is oil phase (hexadecane), lower floor is water and product, is the catalyst of solid in the middle of the two-phase.Chromatography is carried out in water intaking mutually, and the test result of three kinds of catalyst is listed in the table 1.
Embodiment 5
Get commercial catalyst H
3[PW
12O
40] 6.6 μ mol are added in the triangular flask, add reactant sec-butyl alcohol 0.05mol then, 30% H
2O
20.06mol, adding 5ml water again, reactant liquor is vigorous stirring 24h in 80 ℃ oil bath, reacts to be even phase reaction, and chromatography is carried out in the water intaking of reaction back mutually, and its test result is listed in the table 1.
Table 1
| Catalyst | Time (h) | Conversion ratio (%) | Selectivity (%) |
| H 3PW 12O 40 [(C 18H 37) 2N(CH 3) 2] 3[PW 12O 40] [π-C 5H 5N(C 16H 33)] 3[PW 12O 40] [(CH 3) 3N(C 16H 33)] 3[PW 12O 40] | 24 24 24 24 | 82 85 62 58 | 100 100 100 100 |
Can find out from above, with [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] can reach the reaction result of sparing phase catalysis for the emulsion catalysis of catalyst.Because of the high-specific surface area of the drop in emulsion, instead give birth at the interface that is reflected at " little heterogeneous ", is similar to even phase catalysis.
Embodiment 6
The purpose of present embodiment is to investigate the variation of the conversion ratio of sec-butyl alcohol with the reaction time.
With [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] investigate sec-butyl alcohol conversion ratio in time for catalyst.Get catalyst 6.6 μ mol (0.03g) and be added in 4 triangular flasks, add reactant sec-butyl alcohol 0.05mol then respectively, 30% H
2O
20.06mol (hydrogen peroxide/reactant=1.2/1, mol ratio), add 5ml water and 1ml hexadecane (for forming oil-in-water emulsion) again, 4 reactant liquors are respectively in 80 ℃ oil bath behind vigorous stirring 12h, 18h, 24h, the 36h, reduce to room temperature, by static or centrifugal, creaming of emulsion, chromatography is carried out in water intaking mutually, and the result is as shown in Figure 2 over time for the conversion ratio of sec-butyl alcohol.
Table 2
| Time (h) | Selectivity (%) | Conversion ratio (%) |
| 12 | 70 | 100 |
| 18 | 75 | 100 |
| 24 | 85 | 100 |
| 36 | 84 | 100 |
As can be seen from the table, be reacted to 12 hours after, after the conversion ratio of sec-butyl alcohol reaches 70%, 24 hour, the reaction reach balance, conversion ratio is about 85%.
Embodiment 7
Reaction condition is with embodiment 6, with [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] be catalyst.The amount of oil (hexadecane) is 2ml, and sec-butyl alcohol is a reactant, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 8
Reaction condition is with embodiment 6, with [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] be catalyst.The mol ratio of hydrogen peroxide/reactant is 2: 1, and sec-butyl alcohol is a reactant, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 9
Reaction condition is with embodiment 6, with [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] be catalyst.(hexadecane 1ml) changes normal heptane into to oil, and sec-butyl alcohol is a reactant, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 10
With embodiment 7, just catalyst is 0.07g, and the water intaking of reaction back is analyzed mutually, obtains that the results are shown in Table 2.From table 3, the amount that can see catalyst is not very big to the conversion ratio influence of sec-butyl alcohol, and sec-butyl alcohol conversion ratio with this understanding is all about 82%.
Embodiment 11
With embodiment 6, catalyst is 0.03g, and reactant sec-butyl alcohol 0.05mol just changes oxidant into iodosobenzene (C
6H
5IO), the reaction time is 24h, other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 12
With embodiment 6, wherein catalyst is changed into [(C
18H
37)
2N
+(CH
3)
2]
3[SiW
12O
40] (its preparation method is with [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40]), get catalyst 6.6 μ mol, reactant sec-butyl alcohol 0.05mol, the reaction time is 24h, other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 13
With embodiment 6, catalyst [(C wherein
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] in coordination atom W partly replace with Ti, obtain the compound [(C of the Keggin structure of mixed type
18H
37)
2N
+(CH
3)
2]
3+2n[PW
12-nO
40] (n=1,2).Getting catalyst is 6.6 μ mol, reactant sec-butyl alcohol 0.05mol, and the reaction time is 24h, other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 14
With embodiment 6, catalyst is 0.03g, just reactant is changed into isopropyl alcohol 0.05mol, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 15
With embodiment 6, catalyst is 0.03g, just reactant is changed into cyclohexanol 0.05mol, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 16
With embodiment 6, catalyst is 0.03g, just reactant is changed into cyclopentanol 0.05mol, and the reaction time is 24h, and other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 17
Get catalyst [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] 6.6 μ mol (0.03g) are added in the triangular flask, add reactant dimethyl sulfide 0.05mol then respectively, add 5ml water and 1ml hexadecane again, under stirring at room, slowly drip 30% H then
2O
2(0.05mol hydrogen peroxide/reactant=1/1, mol ratio), the reaction very exothermic after dropwising, continues to stir 20 minutes.Reduce to room temperature, by centrifugal, creaming of emulsion, chromatography is carried out in water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 18
With embodiment 17, catalyst is 0.03g, and reactant is diethyl sulfide 0.05mol, and 50 ℃ are reacted 4h down, and other condition is identical.Chromatography is carried out in reaction back water intaking mutually, obtains that the results are shown in Table 3.
Embodiment 19
Get [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] catalyst 0.03g be added in the triangular flask, add reactant benzothiophene 0.18g (0.001mol) then respectively, add the H of 5ml n-hexane, 10ml water and 30% again
2O
20.003mol then at 50 ℃, vigorous stirring 2h, the solid of separating out after the reaction are dissolved in and carry out chromatography in the acetone by centrifugal, obtain that the results are shown in Table 3.
Embodiment 20
With embodiment 19, catalyst is 0.03g, and reactant is dibenzothiophenes 0.001mol, and other condition is identical.The solid of separating out after the reaction is dissolved in and carries out chromatography in the acetone by centrifugal, obtains that the results are shown in Table 3.
Table 3
| Embodiment | Product | Time (h) | Conversion ratio (%) | Selectivity (%) |
| Embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 embodiment 20 | Butanone butanone butanone butanone butanone butanone butanone acetone cyclohexanone cyclopentanone dimethyl sulfoxide (DMSO) diethyl sulfone benzothiophene sulfone dibenzothiophenes sulfone | 24 24 24 24 24 24 24 24 24 24 0.5 4 2 2 | 80 90 82 83 80 81 83 48 ～100 ～100 ＞99 100 ＞99 ＞99 | 100 100 100 100 100 100 100 100 100 100 ＞99 100 ＞99 ＞99 |
Embodiment 21
The purpose of present embodiment is to investigate the rate of recovery of catalyst.
Get catalyst [(C
18H
37)
2N
+(CH
3)
2]
3[PW
12O
40] 6.6 μ mol (0.03g) add in the triangular flask, add reactant sec-butyl alcohol 0.05mol then respectively, 30% H
2O
20.06mol, adding 5ml water and 1ml hexadecane again, reactant liquor behind the vigorous stirring 12h, is reduced to room temperature in 80 ℃ oil bath, by static or centrifugal, creaming of emulsion, the elementary analysis of W is carried out in water intaking mutually.Find that the loss of catalyst in water is 6%, the rate of recovery that is to say catalyst is 94%.This may be because heteropolyacid catalyst and hydroperoxidation, and degraded forms micromolecular species and due to being dissolved in the water.
Embodiment 22
The purpose of present embodiment is to investigate the oxidation activity that reclaims catalyst.
Get oil phase and middle solid catalyst layer behind the creaming of emulsion, directly add in the triangular flask, add reactant sec-butyl alcohol 0.05mol then respectively, 30% H without any processing
2O
20.06mol, adding 5ml water and 1ml hexadecane again, reactant liquor behind the vigorous stirring 12h, is reduced to room temperature in 80 ℃ oil bath, by static or centrifugal, creaming of emulsion, chromatography is carried out in water intaking mutually.The results are shown in Table 4 in the catalyst circulation use.
Table 4
| Cycle-index | Conversion ratio (%) | Selectivity (%) |
| 1 2 3 | 65 56 34 | 100 100 100 |
Because the degraded of catalyst has some species to be dissolved in the water, and oil phase and catalyst more or less some loss in transfer process, when the recycling of catalyst, the conversion ratio of reactant decreases.As catalyst, may avoid this class situation to take place with other.
Claims (7)
1. the method for a catalytic oxidation organic molecule, its key step is:
A) solvent and oil and oxidant are put into reactor, add reactant and catalyst again, 50-80 ℃ is stirred down, forms emulsion; Wherein solvent is as continuous phase, and its volume fraction is no less than 26～74%, and solvent is 5～20: 1 with the volume ratio of oil in the reaction, and the mol ratio of oxidant and reactant is 1～2: 1;
B) behind the molecular balance, stop to stir, emulsion is reduced to room temperature;
C) by static or centrifugal breakdown of emulsion, the profit layering, the oil on upper strata and the catalyst recovery on the two-phase interface are used;
Described oil is nonpolar alkane, fluorocarbons or other and water and the immiscible organic matter of reactant;
Described reactant is alcohol or organic sulfur compound.
Described catalyst is the quaternary ammonium salt heteropoly compound, and this compound expression formula is Q
3[XM
12O
40], Q is a quaternary ammonium salt cationic in the formula, and hetero atom X is phosphorus, silicon or/and arsenic, and coordination atom M is that molybdenum is or/and tungsten;
Described oxidant is hydrogen peroxide, iodosobenzene, periodate, TBHP or oxygen;
Described solvent is a water.
2. the method for claim 1 is characterized in that, described quaternary ammonium salt cationic is: (C
8H
17)
4N
+, (C
12H
25) N
+(CH
3)
3, (C
16H
33) N
+(CH
3)
3, (C
18H
37) N
+(CH
3)
3, (π-C
5H
5) N
+C
16H
33, (C
14H
29)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2Or/and (C
18H
37)
2N
+(CH
3)
2
3. the method for claim 1 is characterized in that, described quaternary ammonium salt cationic is: (C
16H
33) N
+(CH
3)
3, (π-C
5H
5) N
+C
16H
33, (C
12H
25)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2Or/and (C
18H
37)
2N
+(CH
3)
2
4. the method for claim 1 is characterized in that, described quaternary ammonium salt cationic is: (C
12H
25)
2N
+(CH
3)
2, (C
16H
33)
2N
+(CH
3)
2Or/and (C
18H
37)
2N
+(CH
3)
2
5. the method for claim 1 is characterized in that, described coordination atom M with transition metal Cr, Mn, Fe, Co, Ni, Nb, Ru, V or/and Ti partly replace.
6. the method for claim 1 is characterized in that, described nonpolar alkane, fluorocarbons or other and water and the immiscible organic matter of reactant are hexadecane, dodecane, normal heptane.
7. the method for claim 1, it is characterized in that, described reactant is isopropyl alcohol, sec-butyl alcohol, 2-amylalcohol, cyclopentanol, cyclohexanol, ring octanol, dimethyl sulfide, diethyl sulfide, benzothiophene, dibenzothiophenes or 4, the 6-dimethyl Dibenzothiophene.
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| CN101173179B (en) | 2007-10-24 | 2010-09-29 | 中国科学院大连化学物理研究所 | Catalyst for diesel oil oxidation distillation ultra-deepness desulfurization and desulfurization method |
| CN105541680B (en) * | 2016-02-16 | 2017-12-22 | 重庆硕奥科技有限公司 | A kind of synthetic method of Bicalutamide |
| CN106631996A (en) * | 2016-12-20 | 2017-05-10 | 新疆大学 | Preparation method of organic-inorganic hybrid polyoxometallate nanorod |
| CN107188804B (en) * | 2017-07-09 | 2021-01-26 | 邵阳学院 | Method for catalytically synthesizing methyl oleate by using composite phosphotungstate |
| CN107626201B (en) * | 2017-09-19 | 2020-09-04 | 北京理工大学 | Chemical warfare agent simulant catalytically degraded by amphiphilic multi-niobium oxygen cluster emulsion |
| JP7336541B2 (en) | 2019-06-12 | 2023-08-31 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Process for producing diacyl peroxide |
| BR112021024870A2 (en) * | 2019-06-12 | 2022-01-18 | Nouryon Chemicals Int Bv | Method for isolating carboxylic acid from an aqueous side stream of an organic peroxide production process |
| JP7335362B2 (en) | 2019-06-12 | 2023-08-29 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Process for producing diacyl peroxide |
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| JPH04120043A (en) * | 1990-09-07 | 1992-04-21 | Mitsubishi Petrochem Co Ltd | Production of alpha-hydroxyketones |
| CN1355067A (en) * | 2000-11-29 | 2002-06-26 | 中国科学院大连化学物理研究所 | Reaction control phase transferring catalyst for oxidizing reaction and its oxidizing reaction process |
| CN1401640A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene |
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| JPH04120043A (en) * | 1990-09-07 | 1992-04-21 | Mitsubishi Petrochem Co Ltd | Production of alpha-hydroxyketones |
| CN1355067A (en) * | 2000-11-29 | 2002-06-26 | 中国科学院大连化学物理研究所 | Reaction control phase transferring catalyst for oxidizing reaction and its oxidizing reaction process |
| CN1401640A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene |
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