CN107586270A - The method that cyclohexyl benzene catalysis oxidation produces cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol - Google Patents
The method that cyclohexyl benzene catalysis oxidation produces cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol Download PDFInfo
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Abstract
The present invention relates to organic synthesis applied technical field, disclose a kind of method that a kind of method of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxidation Decomposition prepare cyclohexanone and phenol, wherein, the method for cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide includes：(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein, the catalyst is the manganese dioxide of floriform appearance；(2) mixture of reaction products for obtaining step (1) carries out separation of solid and liquid, obtains catalyst manganese dioxide and the reaction product (CHBHP) containing cyclohexyl benzene hydrogen peroxide.The method of the present invention need not add CHBHP or azo-based compound as initiator, in the catalytic oxidation of cyclohexyl benzene, you can obtain greater activity and compared with high selectivity, and technique is simple.
Description
Technical field
The invention belongs to organic synthesis applied technical field, in particular it relates to a kind of cyclohexyl benzene catalysis oxidation
Produce a kind of method that the method for cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxidation Decomposition prepare cyclohexanone and phenol.
Background technology
Phenol and cyclohexanone are important basic organic chemical industry raw materials.Phenol be prepare phenolic resin and bisphenol-A and
The important intermediate of medicine, world demand amount is up to 11,000,000 tons/year；And cyclohexanone is prepare caprolactam and nylon important
Intermediate, while be also a kind of important Chemical Solvents, world demand amount has then reached 4,900,000 tons/year.
Production phenol conventional method mainly have sulfonation method, chlorobenzene method, cyclohexanone-cyclohexanol method, toluol-benzene formic acid method and
Cumene method etc..This several method is by benzene phenol processed indirectly, the shortcomings of production procedure is long, production cost is high all be present.It is different
Propyl benzene method is the oxidative decomposition process (Hock methods) of isopropylbenzene, is current most important phenol production method, and production capacity accounts for benzene
More than the 90% of phenol total productive capacity.But there is flow complexity, seriously corroded, accessory substance is more, yield is low (phenol one way in the technique
The shortcomings of 5%) yield is less than.In addition, the substantial amounts of acetone of cumene method coproduction, and the price fluctuation of acetone seriously constrains production
The overall economy quality of device.
The production of cyclohexanone mainly has cyclohexane oxidation decomposition method and cyclohexene hydration-dehydriding, wherein cyclohexane oxidation
The deficiencies of conversion per pass low (4-6%), poor selectivity and three wastes discharge amount are big be present in decomposition method.Cyclohexene hydration-dehydriding
Although the problem of cyclohexane oxidation decomposition method can be avoided, the higher, work low with reaction conversion per pass of cyclohexene cost is still suffered from
The problems such as skill long flow path.
Phenol can also be prepared by the reaction of cyclohexyl benzene oxidation Decomposition, and react the accessory substance and isopropylbenzene of generation
Oxidation is different, is the cyclohexanone of high added value.Phenol is produced to isopropylbenzene and acetone process is similar, and cyclohexyl benzene technique provides
The process route of one alternative production phenol, while the problem of acetone by-product surplus is not present, there is good hair
Exhibition prospect.
Cyclohexyl benzene oxidation Decomposition, which generates cyclohexanone and phenol, includes two reactions：(1) in the presence of a catalyst and oxygen
In the presence of gas, cyclohexyl benzene peroxidization generation cyclohexyl benzene hydrogen peroxide (CHBHP)；(2) in acid condition, hexamethylene
Base benzene hydrogen peroxide decomposes to obtain phenol and cyclohexanone.Wherein, it is radical reaction to react (1), the cyclohexyl benzene peroxidating
Reaction efficiency is minimum, is to play a conclusive step during cyclohexyl benzene oxidation Decomposition phenol and cyclohexanone.At present, Exxon
Common technology (such as CN 104030892A, US3959381) disclosed in a series of patent applications of XOM includes：With
Air or oxygen is oxidant, adds a small amount of initiator, such as CHBHP and azo isobutyronitrile, with N- hydroxyl O-phthalic bases
Acid imide (NHPI) is catalyst, is 95-120 DEG C, under normal pressure in reaction temperature, reacts 3-8 hours.Although urging based on NHPI
Oxidation, cyclohexyl benzene has preferable conversion ratio, and the selectivity of cyclohexyl benzene hydrogen peroxide is also preferable, still, one
Aspect, the reaction of the step need to carry out in the presence of initiator, and on the other hand, catalyst n HPI not only hold high by price
It is expensive, and be difficult to reclaim and recycle.In addition, cyclohexyl benzene oxidation prepares the catalyst of cyclohexyl benzene hydrogen peroxide step
NHPI residuals can influence next to decompose the experimental result of preparing cyclohexanone and phenol, and catalyst n HPI separation process is very
It is cumbersome.Therefore, it is cyclohexyl to develop a kind of catalyst that is cheap, being easily isolated, have the preferably reusable edible of activity
One recent studies on point of benzene oxidatoin reaction.
The content of the invention
The purpose of the present invention is to overcome the drawbacks described above of prior art, and providing a kind of utilize has preferably activity and be beneficial to
The method that the catalyst cyclohexylbenzene hydroperoxide production cyclohexyl benzene hydrogen peroxide of simultaneously reusable edible is separated with reaction product,
And the method that cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol, meanwhile, cyclohexyl benzene has higher conversion ratio, catalysis
Oxidation product cyclohexyl benzene hydrogen peroxide has higher selectivity, and technique is simple.
To achieve these goals, the present invention provides a kind of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide
Method, wherein, this method comprises the steps：
(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein, the catalyst is flower-shaped
The manganese dioxide of pattern；
(2) mixture of reaction products for obtaining step (1) carries out separation of solid and liquid, obtains catalyst manganese dioxide and contains
The reaction product of cyclohexyl benzene hydrogen peroxide.
Present invention also offers a kind of method that cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol, this method includes：
Cyclohexyl benzene peroxidating is obtained into cyclohexyl benzene hydrogen peroxide, then in acid condition, cyclohexyl benzene hydrogen peroxide decomposed
To phenol and cyclohexanone, wherein, it is provided by the invention by the method that cyclohexyl benzene peroxidating obtains cyclohexyl benzene hydrogen peroxide
Method.
In recent years, metal oxide is simple because preparing, cheap, environment-friendly and have catalytic activity, is closed extensively
Note.It was found by the inventors of the present invention that at different conditions, the manganese dioxide of flower-shaped micro nano structure can be prepared.This hair
Bright inventor is used as heterogeneous catalysis, catalysis oxidation cyclohexyl benzene by the use of the micro-nano structure manganese dioxide with floriform appearance
CHBHP techniques are prepared, obtain preferable effect.
Compared with prior art, the present invention is using the manganese dioxide of floriform appearance as catalyst, catalysis cyclohexyl benzene oxidation
Prepare the reaction of cyclohexyl benzene peroxide so that post catalyst reaction and reaction product can directly be isolated by filtration, separation
Obtained manganese dioxide is also recyclable to be used as catalyst, and manganese dioxide wide material sources, the manganese dioxide system of floriform appearance
It is standby simple, special appearance building-up process is controllable, environment-friendly.The key that method of the present invention is different from tradition reaction also exists
In without adding CHBHP or azo-based compound as initiator, in the catalytic oxidation of cyclohexyl benzene, you can obtain
Greater activity and compared with high selectivity, and technique is simple.Compared to the copper oxide catalyst reported before, manganese oxide catalyst is in high temperature
Under, higher selectivity can be kept；Under identical selective conditions, possesses higher conversion ratio.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the manganese dioxide stereoscan photograph for the floriform appearance that the specific embodiment of the invention provides；
Fig. 2 is commercially available manganese dioxide powder stereoscan photograph.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the present invention, the method for the cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide includes following steps
Suddenly：
(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein, the catalyst is flower-shaped
The manganese dioxide of pattern；
(2) mixture of reaction products for obtaining step (1) carries out separation of solid and liquid, obtains catalyst manganese dioxide and contains
The reaction product of cyclohexyl benzene hydrogen peroxide.
It was found by the inventors of the present invention that there is micro-nano flower-like structure using different from conventional powders shape manganese dioxide
Manganese dioxide prepares the catalyst of cyclohexyl benzene hydrogen peroxide as cyclohexylbenzene hydroperoxide, is not only able to simplify technique, i.e., need not
As traditional handicraft, CHBHP or azo-based compound are added as initiator, you can greater activity and selectivity are obtained, this
Outside, mixture of reaction products can be separated by simple separation of solid and liquid, isolated solid-phase catalyst manganese dioxide
It can recycle.
According to the present invention, the manganese dioxide of the floriform appearance is assembled by flat banded structure manganese dioxide monomer, flower
The flower diameter of shape pattern manganese dioxide is 3-5 microns, and the flat banded structure manganese dioxide monomer is the homogeneous dioxy of single dispersing
Change manganese, the width of the flat banded structure manganese dioxide monomer is preferably 500-700 nanometers, and length is preferably 600-1000 nanometers.
According to the present invention, the preparation method of the manganese dioxide of the floriform appearance includes：
Solution containing water-soluble manganese salt is added in the aqueous solution of persulfuric acid compound, be uniformly dispersed, and in closed loop
Hydro-thermal reaction is carried out in border；One or more of the water-soluble manganese salt in manganese nitrate, manganese sulfate and manganese carbonate, it is preferably
Manganese sulfate；One or more of the persulfuric acid compound in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate, preferably over cure
Sour ammonium；The mol ratio of water-soluble manganese salt and persulfuric acid compound is 1:0.2-5, preferably 1:0.5-2；The condition of hydro-thermal reaction includes
Temperature is 60-120 DEG C, preferably 90-120 DEG C；Time is 20-30 hours, preferably 22-26 hours.
According to the specific embodiment of the present invention, the preparation method of the floriform appearance manganese dioxide includes：Will
0.8M manganese sulfate solution is added dropwise in 0.8M ammonium persulfate aqueous solution, after mixing completely, is moved in water heating kettle and is sealed, and
Reacted 24 hours at 110 DEG C -120 DEG C, obtain product.
According to the present invention, in step (1), the catalyst manganese dioxide is floriform appearance.As long as although with above-mentioned
In the presence of the catalyst manganese dioxide of pattern, it can be achieved in reactant cyclohexyl benzene and oxidant haptoreaction and is catalyzed oxygen
Change obtains cyclohexyl benzene hydrogen peroxide, however, it is preferred in the case of, the weight of the manganese dioxide-catalyst and reactant cyclohexyl benzene
It is 0.0002-0.005 to measure ratio:1, more preferably 0.001-0.004:1.
Under preferable case, fully contacted with reactant cyclohexyl benzene in order that obtaining catalyst manganese dioxide and give full play to it
Catalytic activity, reactant cyclohexyl benzene and manganese dioxide can be mixed and sonicated for forming suspension in the reactor.
The key of the present invention is to prepare hexamethylene by the use of the manganese dioxide with floriform appearance as catalysis cyclohexyl benzene oxidation
The catalyst of base benzene hydrogen peroxide, therefore, the oxidant in the catalytic oxidation can be oxidations commonly used in the art
Agent, for example, the oxidant can be oxygen-containing gas, such as can be air or oxygen, preferably oxygen.With in oxygen-containing gas
The quality meter of oxygen, the amount of the oxygen-containing gas contacted with reactant cyclohexyl benzene are cyclohexyl benzene is aoxidized oxygen demand theoretical value
1.05-1.2 again.Further preferably, when using oxygen as oxidant, in terms of every milliliter of cyclohexyl benzene, the dosage of oxygen can be with
For 0.2-2mL.
Further preferably, in order that oxidant contact with reactant cyclohexyl benzene it is more abundant, oxygen-containing gas, preferably
Oxygen is passed through in a manner of bubbling, and in terms of every milliliter of cyclohexyl benzene, the speed that is passed through of oxygen is 0.2-2mL/min.
I.e., to sum up, under most preferred case, cyclohexyl benzene and the catalytic mode of oxidant are included：By catalyst with
Cyclohexyl benzene is mixed to form suspension, and oxygen is passed through in a manner of bubbling, and in terms of every milliliter of cyclohexyl benzene, oxygen is passed through speed
Rate is 0.2-2mL/min.
According to the present invention, cyclohexyl benzene includes reaction temperature and reaction time with the catalytic condition of oxidant, reacts
Temperature can be 95-150 DEG C, and preferably 100-110 DEG C, the reaction time can be 3-12 hours, preferably 9-11 hours, react
Pressure is normal pressure.
The separation of catalyst and reaction product in reactant mixture can be realized well using the method for the present invention, according to
The present invention, after the reaction of step (1) terminates, the mixture of reaction products that step (1) is obtained carries out separation of solid and liquid, you can
Contain the reaction product of cyclohexyl benzene hydrogen peroxide to solid-phase catalyst manganese dioxide and liquid phase.Meanwhile by step (2) through solid
The isolated solid-phase catalyst manganese dioxide of liquid can also be circulated in step (1), being recycled as catalyst.Its
In, the method for the separation of solid and liquid is known to those skilled in the art, such as the methods of filtering, sedimentation, centrifugation.Preferable case
Under, this method also includes the catalyst manganese dioxide obtained after separation of solid and liquid is washed and dried, and washs solvent used
It is known to those skilled in the art, such as ethanol；Dry condition and method may be referred to the conventional drying condition in this area
And method, for example, drying temperature is not higher than 120 DEG C, preferably 80-100 DEG C, drying time can be 8-24 hours.
According to the present invention, for the reaction product purified, this method also includes containing hexamethylene by what step (2) obtained
The reaction product purifying of base benzene hydrogen peroxide, obtains purified product cyclohexyl benzene hydrogen peroxide.It is described to contain cyclohexyl benzene mistake
The method of the reaction product purifying of hydrogen oxide is known to those skilled in the art, repeats no more herein.
Present invention also offers a kind of method that cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol, this method includes：
Cyclohexyl benzene peroxidating is obtained into cyclohexyl benzene hydrogen peroxide, then in acid condition, cyclohexyl benzene hydrogen peroxide decomposed
To phenol and cyclohexanone, wherein, it is provided by the invention by the method that cyclohexyl benzene peroxidating obtains cyclohexyl benzene hydrogen peroxide
Method.The condition that cyclohexyl benzene hydrogen peroxide is decomposed to obtain to phenol and cyclohexanone may be referred to bar well known in the art
Part, for example, the acid condition is generally the certain density sulfuric acid solution by dilution, it is directly added into peroxide solutions
In, the reaction time can proper extension reaction time, generally 2-5h according to peroxide solutions.
According to the present invention, one-step method, the cyclohexyl benzene hydrogen peroxide that cyclohexyl benzene peroxidating is obtained can be directly used
Directly decomposed to obtain phenol and cyclohexanone, can also obtain the method according to the present invention contains cyclohexyl benzene peroxidating
The reaction product of hydrogen is first purified, and obtains after purified product cyclohexyl benzene hydrogen peroxide that decomposition prepares benzene in acid condition again
Phenol and cyclohexanone.The method that the reaction product by containing cyclohexyl benzene hydrogen peroxide purifies by those skilled in the art public affairs
Know, it is for instance possible to use the method for distillation, is repeated no more herein.
In the present invention, the pressure refers both to gauge pressure.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
The present invention will be described in detail by way of examples below.
In embodiment, if not otherwise specified, used reagent is AR.
In embodiment, reactant cyclohexyl benzene is purchased from lark prestige.
In embodiment, the preparation method of the manganese dioxide of floriform appearance is as follows：
0.8M manganese sulfate solution is added dropwise in 0.8M ammonium persulfate aqueous solution, after being uniformly dispersed, moves to hydro-thermal
Sealed in kettle, reacted 24 hours at 110 DEG C -120 DEG C, obtain product.The flower diameter of floriform appearance manganese dioxide is 3-5 microns,
The width of the flat banded structure manganese dioxide monomer is 500-700 nanometers, and length is 600-1000 nanometers.
Manganese dioxide powder is purchased from Chinese medicines group chemical reagent Beijing Co., Ltd, AR100g.
Measure and computational methods about cyclohexyl benzene conversion ratio (%) and CHBHP selectivity (%) in example below
(normalization method) is as follows：
Liquid mixture of the gained containing CHBHP, is weighed two parts (every part of 0.8g) after separation.A copy of it is surveyed with iodimetric titration
Fixed all CHBHP content：M is added in iodine flask1G reaction gained liquid mixtures, add 20mL glacial acetic acid solutions, then add
2gNaHCO3Solid powder, gently shaking is well mixed solid powder and liquid；Then 10mL saturation KI solution, reaction are added
To when not producing bubble substantially, it is water-cooled, adds 100mL distilled water；It is c with concentration1, unit mol/L's (0.15mol/L)
Standard Na2S2O3Standardization of solution to solution is in light yellow, adds 2mL starch indicators (such as mass fraction is 5%), continues to titrate
It is changed into milky, as titration end-point to solution from blueness, writes down the standard Na of consumption2S2O3Liquor capacity is VmL.
Claim a reaction gained liquid mixture, quality m in addition2G, add m3G (0.4g) naphthalene makees internal standard, after shaking up, adds
Enter excessive triphenylphosphine reduction, 2mL dilution in acetonitrile is added, then with gas-chromatography (200 DEG C of column temperature, injector and detector temperature
Degree is 300 DEG C) amount of the material of cyclohexyl benzene, phenylcyclohexanol, benzene hexanone etc. is n in every gram of liquid mixture of measure1, n2,
n3(mol)。
The amount of CHBHP material is in every gram of liquid mixture of iodometric determination：
NCHBHP (mol)=c1×V×0.5/(m1×1000)
Conversion ratio (%)=100 × (n of cyclohexyl benzene2+n3)/(n1+n2+n3)
CHBHP selectivity (%)=100 × nCHBHP/ (n2+n3)
CHBHP yield (%)=100 × nCHBHP/ (n1+n2+n3)
Embodiment 1-4
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and the flower-shaped manganese dioxide of catalyst (pattern is as shown in Figure 1), urge
Agent is 0.0021 with cyclohexyl benzene weight ratio:1,250mL three-necked flask is added to, is ultrasonically treated 2min, forms suspension.
Then under magnetic stirring, by the mixed liquor as oil bath heating to predetermined reaction temperature (being shown in Table 1) after, with 100mL/ under normal pressure
Min (with every gram of catalyst gauge, the speed that is passed through of oxygen is 1000mL/min/g) is passed through oxygen, reacts 9h.After reaction terminates, institute
Mixed liquor is filtered obtains manganese dioxide-catalyst and the liquid mixture containing CHBHP.Liquid mixture is analyzed,
The conversion ratio of cyclohexyl benzene and CHBHP selectivity are measured, as a result as shown in table 1.
Table 1
| Embodiment is numbered | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Reaction temperature (DEG C) | 90 | 100 | 110 | 120 |
| Cyclohexyl benzene conversion ratio (%) | 8.5% | 14.8% | 35% | 46% |
| CHBHP selectivity (%) | 97.8% | 93.1% | 88.4% | 82% |
From the results shown in Table 1, temperature rise is advantageous to the oxidation of cyclohexyl benzene, but when temperature reaches 120 DEG C,
CHBHP, which is decomposed, to be accelerated, and while conversion ratio significantly improves, CHBHP selectively decreases, and therefore, reaction temperature is preferably
100-110℃。
Embodiment 5-8
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and the flower-shaped manganese dioxide of catalyst (pattern is as shown in Figure 1), urge
Agent is 0.0021 with cyclohexyl benzene weight ratio:1,250mL three-necked flask is added to, is ultrasonically treated 2min, forms suspension.
Then under magnetic stirring, by the mixed liquor as oil bath heating to 100 DEG C (being shown in Table 2) after, under normal pressure with 100mL/min (with
Every gram of catalyst gauge, the speed that is passed through of oxygen is 1000mL/min/g) oxygen is passed through, react certain time.After reaction terminates, institute
Mixed liquor is filtered obtains manganese dioxide-catalyst and the liquid mixture containing CHBHP.Liquid mixture is analyzed, measured
The conversion ratio of cyclohexyl benzene and CHBHP selectivity, as a result as shown in table 2.
Table 2
| Embodiment is numbered | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Reaction time (h) | 8 | 10 | 11 | 12 |
| Cyclohexyl benzene conversion ratio (%) | 9.1% | 21.5% | 36.9% | 47% |
| CHBHP selectivity (%) | 98.1% | 87.5% | 81.7% | 77.1% |
From the results shown in Table 2, with the increase in reaction time, CHBHP is selectively on a declining curve, especially exists
After reaction was more than 11 hours, its speed declined is accelerated suddenly.Therefore in the reaction time range that table 2 is studied, comparative example
2, the preferable reaction time is 9-11 hours.
Embodiment 9-10
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and the flower-shaped manganese dioxide of catalyst (pattern is as shown in Figure 1),
Catalyst is 0.0021 with cyclohexyl benzene weight ratio:1,250mL three-necked flask is added to, is ultrasonically treated 2min, is formed and suspended
Liquid.Then under magnetic stirring, by the mixed liquor as oil bath heating to 110 DEG C (being shown in Table 3) after, led under normal pressure with given pace
Enter oxygen, react 9h.After reaction terminates, gained mixed liquor is filtered to obtain manganese dioxide-catalyst and the liquid containing CHBHP
Mixture.Liquid mixture is analyzed, measures the conversion ratio of cyclohexyl benzene and CHBHP selectivity, as a result as shown in table 3.
Table 3
| Embodiment is numbered | Embodiment 9 | Embodiment 10 |
| Oxygen gas flow rate (mL/min/g catalyst) | 500 | 5000 |
| Cyclohexyl benzene conversion ratio (%) | 30% | 47.1% |
| CHBHP selectivity (%) | 85.4% | 86.2% |
From the results shown in Table 3, comparative example 9,3,10, in the range of research, oxygen gas flow rate increase starts
It is favourable to reacting, but as oxygen gas flow rate is excessive, there is certain influence on selectivity, but influence little.
Embodiment 11-13
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and the flower-shaped manganese dioxide of catalyst (pattern is as shown in Figure 1) with one
Three-necked flask of the fixed weight than being added to 250mL, 2min is ultrasonically treated, forms suspension.Then under magnetic stirring, by this
After mixed liquor is as oil bath heating to 100 DEG C (being shown in Table 4), (in terms of every milliliter of cyclohexyl benzene, oxygen is passed through speed to 100mL/min
Rate is 2mL/min) oxygen is passed through, react 9h.After reaction terminates, gained mixed liquor is filtered to be obtained manganese dioxide-catalyst and contains
There is CHBHP liquid mixture.Liquid mixture is analyzed, measures the conversion ratio of cyclohexyl benzene and CHBHP selectivity, as a result
As shown in table 4.
Table 4
| Embodiment is numbered | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Catalyst and cyclohexyl benzene weight ratio | 0 | 0.001 | 0.003 | 0.004 |
| Cyclohexyl benzene conversion ratio (%) | 1 | 11.2 | 17.2 | 21.8 |
| CHBHP selectivity (%) | 97 | 95 | 86.8 | 82 |
From the results shown in Table 4, comparative example 10,2,11,12,13, it can be clearly seen that manganese dioxide is catalyzed
Agent has preferable catalytic activity to cyclohexyl benzene oxidation reaction, while catalyst and cyclohexyl benzene weight are than preferably 0.001-
0.004:1。
Comparative example 1
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and commercial powder shape manganese dioxide (pattern is as shown in Figure 2), urge
Agent is with cyclohexyl benzene weight than 0.0021:1,250mL three-necked flask is added to, is ultrasonically treated 2min, forms suspension.So
Afterwards under magnetic stirring, by the mixed liquor as oil bath heating to after 100 DEG C, with 100mL/min (with every gram of catalyst under normal pressure
Meter, the speed that is passed through of oxygen is 1000mL/min/g) oxygen is passed through, react 10h.After reaction terminates, gained mixed liquor is filtered
Obtain manganese dioxide-catalyst and the liquid mixture containing CHBHP.Liquid mixture is analyzed, measures the conversion of cyclohexyl benzene
The selectivity of rate and CHBHP, as a result as shown in table 5.
Table 5
| Embodiment is numbered | Comparative example 1 |
| Catalyst type | Commercially available manganese dioxide |
| Cyclohexyl benzene conversion ratio (%) | 20 |
| CHBHP selectivity (%) | 78.9 |
From the results shown in Table 5, the catalytic effect of commercially available manganese dioxide powder foot couple cyclohexyl benzene oxidation reaction is contrasted,
It can be seen that：Relatively commercially available manganese dioxide powder is made by receiving the flower-shaped manganese dioxide of micron (compared with Example 6) as catalyst
For catalyst, the conversion ratio of cyclohexyl benzene and CHBHP selectivity are more excellent, are embodied especially in CHBHP selectivity obvious.
Embodiment 14
The present embodiment is used for the side for illustrating cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzenes (density 0.94g/mL) and the flower-shaped manganese dioxide of catalyst (pattern is as shown in Figure 1),
Catalyst is with cyclohexyl benzene weight than 0.0021:1,250mL three-necked flask is added to, supersound process forms suspension.Then
Under magnetic stirring, by the mixed liquor as oil bath heating to 110 DEG C, under normal pressure with 100mL/min (with every gram of catalyst gauge,
The speed that is passed through of oxygen is 1000mL/min/g) oxygen is passed through, react 9h.After reaction terminates, gained mixed liquor is filtered to be obtained
Manganese dioxide-catalyst and the liquid mixture containing CHBHP.To liquid mixture analyze, measure cyclohexyl benzene conversion ratio and
CHBHP selectivity, gained solid catalyst dry 12h at 110 DEG C.
By step (1) dried manganese dioxide, again as catalyst, carried out under the same conditions with step (1)
Reaction, yield is determined with identical method.So three times, as a result as shown in table 6 this catalyst is recycled.
Table 6
| Access times | 0 | 1 | 2 | 3 |
| CHBHP yields (mol, %) | 30.9 | 31.5 | 30.8 | 29.6 |
From the results shown in Table 6, separated during catalyst manganese dioxide is mixed from reaction product and reuse three
Secondary, CHBHP yield change is little, illustrates that the stability of manganese dioxide-catalyst is good, can recycle, and can be significantly
Reduce the cost of catalyst.
Claims (9)
- A kind of 1. method of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide, it is characterised in that under this method includes State step：(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein, the catalyst is floriform appearance Manganese dioxide；(2) mixture of reaction products for obtaining step (1) carries out separation of solid and liquid, obtains catalyst manganese dioxide and contains hexamethylene The reaction product of base benzene hydrogen peroxide.
- 2. according to the method for claim 1, wherein, the manganese dioxide of the floriform appearance is by flat banded structure manganese dioxide Monomer assembles, a diameter of 3-5 microns of the manganese dioxide of floriform appearance, the width of the flat banded structure manganese dioxide monomer It is 600-1000 nanometers to spend for 500-700 nanometers, length.
- 3. method according to claim 1 or 2, wherein,The preparation method of the manganese dioxide of the floriform appearance includes：Solution containing water-soluble manganese salt is added in the aqueous solution of persulfuric acid compound, be uniformly dispersed, and in closed environment Carry out hydro-thermal reaction；One or more of the water-soluble manganese salt in manganese nitrate, manganese sulfate and manganese carbonate, preferably manganese sulfate；The mistake Hydrosulphate is the one or more in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate, preferably ammonium persulfate；Water-soluble manganese salt Mol ratio with persulfuric acid compound is 1:0.2-5, preferably 1:0.5-2；It is 60-120 DEG C that the condition of hydro-thermal reaction, which includes temperature, Preferably 90-120 DEG C；Time is 20-30 hours, preferably 22-26 hours.
- 4. according to the method for claim 1, wherein, the weight ratio of manganese dioxide and cyclohexyl benzene is 0.0002-0.005: 1, preferably 0.001-0.004:1.
- 5. according to the method described in any one in claim 1-4, wherein, the oxidant is oxygen-containing gas, with oxygenous The quality meter of oxygen in body, the amount of the oxygen-containing gas contacted with cyclohexyl benzene are cyclohexyl benzene is aoxidized oxygen demand theoretical value 1.05-1.2 times, it is preferable that the oxidant is oxygen, and in terms of every milliliter of cyclohexyl benzene, the dosage of oxygen is 0.2-2mL.
- 6. according to the method for claim 5, wherein, in the presence of a catalyst, cyclohexyl benzene is contacted instead with oxidant The mode answered includes：Catalyst and cyclohexyl benzene are mixed to form suspension, and oxygen is passed through in a manner of bubbling, with every milliliter Cyclohexyl benzene meter, the speed that is passed through of oxygen is 0.2-2mL/min.
- 7. according to the method described in any one in claim 1-4, wherein, by cyclohexyl benzene and the catalytic bar of oxidant Part includes：Reaction temperature is 95-150 DEG C, and preferably 100-110 DEG C, the reaction time is 3-12 hours, preferably 9-11 hours.
- 8. according to the method described in any one in claim 1-4, wherein, the catalysis that step (2) is obtained through separation of solid and liquid Agent manganese dioxide is circulated in step (1).
- 9. a kind of method that cyclohexyl benzene oxidation Decomposition prepares cyclohexanone and phenol, this method include：By cyclohexyl benzene peroxidating Cyclohexyl benzene hydrogen peroxide is obtained, then in acid condition, cyclohexyl benzene hydrogen peroxide is decomposed to obtain phenol and cyclohexanone, its It is characterised by, is any one institute in claim 1-8 by the method that cyclohexyl benzene peroxidating obtains cyclohexyl benzene hydrogen peroxide The method stated.
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