CN106631954B - The method that cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxygenolysis prepare cyclohexanone and phenol - Google Patents
The method that cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide and cyclohexyl benzene oxygenolysis prepare cyclohexanone and phenol Download PDFInfo
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Abstract
The present invention relates to organic synthesis applied technical fields, disclose the method and a kind of method that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol of a kind of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide, wherein, cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide method include: (1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein, the catalyst is the copper oxide of Rod-like shape and/or floriform appearance；(2) mixture of reaction products that step (1) obtains is separated by solid-liquid separation, obtains catalyst copper oxide and the reaction product containing cyclohexyl benzene hydrogen peroxide.Method of the invention is without being added CHBHP or azo-based compound as initiator, and in the catalytic oxidation of cyclohexyl benzene, greater activity and more highly selective, and simple process can be obtained.
Description
Technical field
The invention belongs to organic synthesis applied technical fields, in particular it relates to a kind of cyclohexyl benzene catalysis oxidation
Produce the method and a kind of method that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol of cyclohexyl benzene hydrogen peroxide.
Background technique
Phenol and cyclohexanone are important basic organic chemical industry raw material.Phenol be prepare phenolic resin and bisphenol-A and
The important intermediate of drug, world demand amount is up to 11,000,000 tons/year；And cyclohexanone is prepare caprolactam and nylon important
Intermediate, while being 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..These types of method is all there is the disadvantages of long production procedure, high production cost by benzene phenol processed indirectly.It is different
Propyl benzene method, that is, isopropylbenzene oxidative decomposition process (Hock method), is current most important phenol production method, and production capacity accounts for about benzene
90% or more of phenol total productive capacity.But there are process complexity, seriously corroded, by-product is more, yield is low (phenol one way for the technique
Yield less than 5%) the disadvantages of.In addition, a large amount 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
There is the deficiencies of conversion per pass is low (4-6%), poor selectivity and three wastes discharge amount are big in decomposition method.Cyclohexene hydration-dehydriding
Although the problem of can avoid cyclohexane oxidation decomposition method, there are still cyclohexene higher costs, and conversion per pass is low, work with reaction
The problems such as skill long flow path.
Phenol can also be prepared by the reaction of cyclohexyl benzene oxygenolysis, and reacts the by-product and isopropylbenzene generated
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.
It includes two reactions that cyclohexyl benzene oxygenolysis, which generates cyclohexanone and phenol: (1) in the presence of a catalyst and oxygen
Under the action of gas, cyclohexyl benzene peroxidization generates cyclohexyl benzene hydrogen peroxide (CHBHP)；(2) in acid condition, hexamethylene
Base benzene hydrogen peroxide decomposes to obtain phenol and cyclohexanone.Wherein, reaction (1) is radical reaction, the cyclohexyl benzene peroxidating
Reaction efficiency is minimum, is a conclusive step during cyclohexyl benzene oxygenolysis phenol and cyclohexanone.Currently, Exxon
Common technology disclosed in a series of patent applications of Mobil Corporation (such as CN 104030892A, US3959381) include: with
Air or oxygen is oxidant, and a small amount of initiator, such as CHBHP and azo isobutyronitrile is added, with N- hydroxyl O-phthalic base
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
The reaction needs of aspect, the step just can be carried out in the presence of initiator, and on the other hand, not only price is high by catalyst n HPI
It is expensive, and be difficult to realize recycle and recycle.In addition, cyclohexyl benzene oxidation prepares the catalyst of cyclohexyl benzene hydrogen peroxide step
NHPI residual will affect the experimental result for next decomposing preparing cyclohexanone and phenol, and the separation process of catalyst n HPI is very
It is cumbersome.Therefore, develop it is a kind of it is cheap, be easily isolated, be cyclohexyl with preferable active recyclable catalyst
One recent studies on point of benzene oxidatoin reaction.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, and providing a kind of utilize has preferably activity and is conducive to
Separated with reaction product and can be recycled catalyst cyclohexylbenzene hydroperoxide production cyclohexyl benzene hydrogen peroxide method,
And the method that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol, meanwhile, cyclohexyl benzene conversion ratio with higher, catalysis
Oxidation product cyclohexyl benzene hydrogen peroxide selectivity with higher, and simple process.
To achieve the goals above, the present invention provides a kind of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide
Method, wherein this method includes the following steps:
(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein the catalyst is rodlike
The copper oxide of pattern and/or floriform appearance；
(2) mixture of reaction products that step (1) obtains is separated by solid-liquid separation, obtains catalyst copper oxide and contains ring
The reaction product of hexyl benzene hydrogen peroxide.
The present invention also provides a kind of methods that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol, this method comprises:
Cyclohexyl benzene peroxidating is obtained into cyclohexyl benzene hydrogen peroxide, then in acid condition, cyclohexyl benzene hydrogen peroxide is decomposed
To phenol and cyclohexanone, wherein it is provided by the invention that cyclohexyl benzene peroxidating, which is obtained the method for cyclohexyl benzene hydrogen peroxide,
Method.
In recent years, copper oxide is simple because preparing, cheap, environmental-friendly and have catalytic activity, by extensive concern.This
Invention inventors have found that at different conditions, can be prepared different sizes, pattern micro nano structure copper oxide.
The present inventor is using the copper oxide with different-shape as heterogeneous catalysis, the preparation of catalysis oxidation cyclohexyl benzene
CHBHP technique obtains preferable effect.
Compared with prior art, the present invention is catalyzed ring using the copper oxide of Rod-like shape and/or floriform appearance as catalyst
Hexyl benzene oxidatoin prepares the reaction of cyclohexyl benzene peroxide, so that post catalyst reaction and reaction product can directly pass through filtering
Separation, isolated copper oxide is also recyclable to be used as catalyst, and catalyst copper oxide is from a wealth of sources, preparation is simple,
Different-shape synthesis process is controllable, environmental-friendly.The key that method of the present invention is different from tradition reaction also resides in, and is not necessarily to
CHBHP or azo-based compound, which is added, as initiator can be obtained greater activity in the catalytic oxidation of cyclohexyl benzene
It is more highly selective, and simple process.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 copper oxide stereoscan photograph of floriform appearance；
Fig. 2 is the copper oxide stereoscan photograph of Rod-like shape；
Fig. 3 is commercially available cupric oxide powder stereoscan photograph.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the present invention, the method for the cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide includes following steps
It is rapid:
(1) in the presence of a catalyst, by cyclohexyl benzene and oxidant haptoreaction, wherein the catalyst is rodlike
The copper oxide of pattern and/or floriform appearance；
(2) mixture of reaction products that step (1) obtains is separated by solid-liquid separation, obtains catalyst copper oxide and contains ring
The reaction product of hexyl benzene hydrogen peroxide.
It was found by the inventors of the present invention that using the micro-nano knot with certain pattern for being different from conventional powders shape copper oxide
The copper oxide of structure prepares the catalyst of cyclohexyl benzene hydrogen peroxide as cyclohexylbenzene hydroperoxide, be not only able to simplify technique, i.e., without
CHBHP or azo-based compound need to be added as initiator, greater activity and selectivity can be obtained as traditional handicraft,
In addition, mixture of reaction products can be separated by being simply separated by solid-liquid separation, isolated solid-phase catalyst copper oxide
It can recycle.
According to the present invention, the length of the copper oxide of the Rod-like shape is preferably 200-1000 nanometers, and width is preferably 50-
200 nanometers；The copper oxide of the floriform appearance is assembled by flat club shaped structure copper oxide monomer, the flower of floriform appearance copper oxide
Diameter is preferably 3-8 microns, and the flat club shaped structure copper oxide monomer is the uniform copper oxide of monodisperse, the flat club shaped structure oxygen
The length for changing copper monomer is preferably 500-800 nanometers, and width is preferably 200-400 nanometers.
According to the present invention, the preparation method of the copper oxide of the Rod-like shape includes:
Unitary alcoholic solution containing water-soluble copper salt is mixed with inorganic base aqueous solution, and carries out hydro-thermal in closed environment
Reaction；The water-soluble copper salt is selected from one of copper nitrate, copper sulphate and copper chloride or a variety of, preferably copper nitrate；It is described
Monohydric alcohol is selected from one of methanol, ethyl alcohol and propyl alcohol or a variety of, preferably ethyl alcohol；The inorganic base be selected from sodium hydroxide and/
Or potassium hydroxide, preferably sodium hydroxide；Water-soluble copper salt and the molar ratio of inorganic base are 1:18-22；The hydro-thermal reaction
Condition includes: that temperature is 100-120 DEG C, and the time is 10-15 hours.In addition, concentration of the water-soluble copper salt in unitary alcoholic solution
Typically 0.45-0.55 mol/L.In order to preferably disperse, assemble, the unitary alcoholic solution containing water-soluble copper salt
The mode mixed with inorganic base aqueous solution is preferred are as follows: it is water-soluble that inorganic base is added dropwise in the unitary alcoholic solution containing water-soluble copper salt
In liquid.
A specific embodiment according to the invention, the preparation method of the copper oxide of the Rod-like shape include: by
The copper nitrate ethanol solution of 0.5M is added dropwise in the sodium hydrate aqueous solution of 10M, after mixing completely, moves to close in water heating kettle
Envelope, and reacted 12 hours at 110 DEG C -120 DEG C, obtain product.
According to the present invention, the preparation method of the copper oxide of the floriform appearance includes:
Unitary alcoholic solution containing water-soluble copper salt is mixed with inorganic base aqueous solution, and carries out hydro-thermal in closed environment
Reaction；The water-soluble copper salt is selected from one of copper nitrate, copper sulphate and copper chloride or a variety of, preferably copper nitrate；It is described
Monohydric alcohol is selected from one of methanol, ethyl alcohol and propyl alcohol or a variety of, preferably ethyl alcohol；The inorganic base be selected from sodium hydroxide and/
Or potassium hydroxide, preferably sodium hydroxide；Water-soluble copper salt and the molar ratio of inorganic base are 1:8-12；The item of the hydro-thermal reaction
Part includes: that temperature is 100-120 DEG C, and the time is 20-30 hours.In addition, concentration of the water-soluble copper salt in unitary alcoholic solution is logical
It often can be 0.4-0.65 mol/L.In order to preferably disperse, assemble, the unitary alcoholic solution containing water-soluble copper salt with
The mode of inorganic base aqueous solution mixing is preferred are as follows: inorganic base aqueous solution is added dropwise in the unitary alcoholic solution containing water-soluble copper salt
In.
A specific embodiment according to the invention, the preparation method of the copper oxide of the floriform appearance include: by
The copper nitrate ethanol solution of 0.5M is added dropwise in the sodium hydrate aqueous solution of 5M, after mixing completely, moves in water heating kettle and seals,
And reacted 24 hours at 110 DEG C -120 DEG C, obtain product.
According to the present invention, in step (1), the catalyst copper oxide is Rod-like shape and/or floriform appearance, is preferably spent
Shape pattern.As long as although in the presence of the catalyst copper oxide with above-mentioned pattern, by reactant cyclohexyl benzene and oxidant
Haptoreaction can be realized its catalysis oxidation and obtain cyclohexyl benzene hydrogen peroxide, however, it is preferred in the case of, the copper oxide catalyzation
The weight ratio of agent and reactant cyclohexyl benzene is 0.0002-0.005:1, further preferably 0.001-0.004:1.
Under preferable case, in order to enable catalyst copper oxide comes into full contact with reactant cyclohexyl benzene and gives full play to it and urge
Change activity, reactant cyclohexyl benzene and copper oxide can be mixed and sonicated to form suspension in the reactor.
Key of the invention, which is to use, has rodlike and/or floriform appearance copper oxide as catalysis cyclohexyl benzene oxidation system
The catalyst of standby cyclohexyl benzene hydrogen peroxide, therefore, the oxidant in the catalytic oxidation can be commonly used in the art
Oxidant, for example, the oxidant can be oxygen-containing gas, such as can be air or oxygen, preferably oxygen.With oxygen-containing
The quality meter of oxygen in gas, the amount of the oxygen-containing gas contacted with reactant cyclohexyl benzene are that cyclohexyl benzene is made to aoxidize oxygen demand reason
By 0.5-1.5 times of value.Further preferably, when using oxygen as oxidant, in terms of every milliliter of cyclohexyl benzene, the dosage of oxygen
It can be 0.2-2mL.
Further preferably, in order to enable oxidant and the contact of reactant cyclohexyl benzene are more abundant, oxygen-containing gas, preferably
Oxygen is passed through in a manner of being bubbled, and in terms of every milliliter of cyclohexyl benzene, the rate that is passed through of oxygen is 0.2-2mL/min.
According to the present invention, cyclohexyl benzene and the catalytic condition of oxidant include reaction temperature and reaction time, reaction
Temperature can be 100-150 DEG C, preferably 100-110 DEG C, the reaction time can be 3-12 hours, preferably 9-11 hours, instead
Answering pressure is normal pressure.
The separation that can realize catalyst and reaction product in reaction mixture well using method of the invention, according to
The mixture of reaction products that step (1) obtains after reaction to step (1) is separated by solid-liquid separation, can obtain by the present invention
Contain the reaction product of cyclohexyl benzene hydrogen peroxide to solid-phase catalyst copper oxide and liquid phase.Meanwhile by step (2) through solid-liquid
Isolated solid-phase catalyst copper oxide can also be recycled for being used in step (1) as catalyst circulation.Wherein, institute
The method for stating separation of solid and liquid is known to those skilled in the art, such as the methods of filtering, sedimentation, centrifugation.It, should under preferable case
Method further includes that the catalyst copper oxide obtained after being separated by solid-liquid separation is washed and dried, and washing solvent used is this field
It well known to technical staff, such as can be ethyl alcohol；Dry condition and method can with reference to this field routine drying condition with
Method, for example, drying temperature is not higher than 120 DEG C, preferably 80-100 DEG C, drying time can be 8-24 hours.
The present invention also provides a kind of methods that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol, this method comprises:
Cyclohexyl benzene peroxidating is obtained into cyclohexyl benzene hydrogen peroxide, then in acid condition, cyclohexyl benzene hydrogen peroxide is decomposed
To phenol and cyclohexanone, wherein it is provided by the invention that cyclohexyl benzene peroxidating, which is obtained the method for cyclohexyl benzene hydrogen peroxide,
Method.The condition for decomposing to obtain phenol and cyclohexanone for cyclohexyl benzene hydrogen peroxide can refer to item well known in the art
Part is added directly into the cyclohexyl benzene for example, the acid condition generally passes through diluted certain density sulfuric acid solution
In hydrogenperoxide steam generator, reaction time, generally 2-5h can be appropriately extended according to peroxide solutions in the reaction time.
According to the present invention, one-step method can be directly used, the cyclohexyl benzene hydrogen peroxide that cyclohexyl benzene peroxidating is obtained
It directly is decomposed to obtain phenol and cyclohexanone, what the method according to the invention can also be obtained 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.It is described by the method purified containing the reaction product of cyclohexyl benzene hydrogen peroxide by those skilled in the art public affairs
Know, for example, can be repeated no more herein using the method for distillation.
In the present invention, the pressure refers both to gauge pressure.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 also be regarded as the disclosure of the present invention.
The present invention will be described in detail by way of examples below.
In embodiment, if not otherwise specified, used reagent is analytical reagents.
In embodiment, reactant cyclohexyl benzene is purchased from lark prestige.
In embodiment, rodlike copper oxide the preparation method is as follows:
The copper nitrate ethanol solution of 0.5M is added dropwise in the sodium hydrate aqueous solution of 10M, after mixing completely, moves to water
It is sealed in hot kettle, is reacted 12 hours at 110 DEG C -120 DEG C, obtain product.The length of the copper oxide of the Rod-like shape is 700
Nanometer, width are 50 nanometers.
In embodiment, flower-shaped copper oxide the preparation method is as follows:
The copper nitrate ethanol solution of 0.5M is added dropwise in the sodium hydrate aqueous solution of 5M, after mixing completely, moves to water
It is sealed in hot kettle, is reacted 24 hours at 110 DEG C -120 DEG C, obtain product.The flower diameter of floriform appearance copper oxide is 3-5 microns,
The length of the flat club shaped structure copper oxide monomer is 400-600 nanometers, and width is 400-500 nanometers.
Cupric oxide powder is purchased from Chinese medicines group chemical reagent Beijing Co., Ltd, AR100g.
Measurement and calculation method in following example in relation to cyclohexyl benzene conversion ratio (%) and CHBHP selectivity (%)
(normalization method) is as follows:
Liquid mixture of the gained containing CHBHP, weighs two parts (every part of 0.8g) after separation.A copy of it is surveyed with iodimetric titration
The content of fixed all CHBHP: m is added in iodine flask1G reaction gained liquid mixture, addition 20mL glacial acetic acid solution, then plus
2g NaHCO3Solid powder, gently shaking is uniformly mixed solid powder and liquid；Then 10mL is added and is saturated KI solution, instead
It should be water-cooled to when not generating bubble substantially, 100mL distilled water is added；It is c with concentration1, unit mol/L (0.15mol/L)
Standard Na2S2O3Standardization of solution in light yellow, be added 2mL starch indicator (such as mass fraction is 5%), continue to drip to solution
It is fixed to become milky, as titration end-point to solution from blue, write down the standard Na of consumption2S2O3Liquor capacity is VmL.
In addition claim a reaction gained liquid mixture, quality m2M is added in g3G (0.4g) naphthalene makees internal standard, after shaking up, adds
Enter the reduction of excessive triphenylphosphine, 2mL dilution in acetonitrile be added, then with gas-chromatography (200 DEG C of column temperature, sample injector and detector temperature
Degree is 300 DEG C) amount of the substance of cyclohexyl benzene, phenylcyclohexanol, benzene hexanone etc. in every gram of liquid mixture is measured as n1, n2,
n3(mol)。
The amount of the substance of CHBHP in every gram of liquid mixture of iodometric determination are as follows:
NCHBHP (mol)=c1×V×0.5/(m1×1000)
Conversion ratio (%)=100 × (n of cyclohexyl benzene2+n3)/(n1+n2+n3)
Selectivity (%)=100 × nCHBHP/ (n of CHBHP2+n3)
Yield (%)=100 × nCHBHP/ (n of CHBHP1+n2+n3)
Embodiment 1-4
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the flower-shaped copper oxide of 0.01g catalyst (pattern is as shown in Figure 1),
Catalyst and cyclohexyl benzene weight ratio are 0.0021:1, are added to the three-necked flask of 250mL, are ultrasonically treated 2min, are formed and are suspended
Liquid.Then again under magnetic agitation, by the mixed liquor as oil bath heating to predetermined reaction temperature (being shown in Table 1) after, under normal pressure with
25mL/min (in terms of every milliliter of cyclohexyl benzene, the rate that is passed through of oxygen is 0.5mL/min) is passed through oxygen, reacts 9h.Reaction knot
Copper oxide catalyst and the liquid mixture containing CHBHP is obtained by filtration in Shu Hou, gained mixed liquor.Liquid mixture is carried out
Analysis, measures the conversion ratio of cyclohexyl benzene and the selectivity of CHBHP, the results are shown in Table 1.
Table 1
| Embodiment number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Reaction temperature (DEG C) | 90 | 100 | 110 | 120 |
| Cyclohexyl benzene conversion ratio (%) | 25.5% | 29.8% | 33.9% | 43% |
| CHBHP selectivity (%) | 87.8% | 86.1% | 83.7% | 77.9% |
From the results shown in Table 1, temperature increases the oxidation for being conducive to cyclohexyl benzene, but works as temperature and reach 120 DEG C,
CHBHP, which is decomposed, to be accelerated, and while conversion ratio significantly improves, CHBHP selectively slightly decreases, and therefore, reaction temperature is preferably
100-110℃。
Embodiment 5-8
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the flower-shaped copper oxide of 0.01g catalyst (pattern is as shown in Figure 1),
Catalyst and cyclohexyl benzene weight ratio are 0.0021:1, are added to the three-necked flask of 250mL, are ultrasonically treated 2min, are formed and are suspended
Liquid.Then again under magnetic agitation, by the mixed liquor as oil bath heating to after 100 DEG C (being shown in Table 2), with 25mL/min under normal pressure
(in terms of every milliliter of cyclohexyl benzene, the rate that is passed through of oxygen is 0.5mL/min) is passed through oxygen, reacts certain time.Reaction terminates
Afterwards, copper oxide catalyst and the liquid mixture containing CHBHP is obtained by filtration in gained mixed liquor.Liquid mixture is analyzed,
The conversion ratio of cyclohexyl benzene and the selectivity of CHBHP are measured, the results are shown in Table 2.
Table 2
| Embodiment number | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Reaction time (h) | 8 | 10 | 11 | 12 |
| Cyclohexyl benzene conversion ratio (%) | 24.5% | 34.8% | 39.9% | 45% |
| CHBHP selectivity (%) | 86.9% | 81.5% | 77% | 73.7% |
From the results shown in Table 2, with the increase in reaction time, CHBHP is selectively on a declining curve, therefore in table 2
In the reaction time range of research, comparative example 2, the preferred reaction time is 9-11 hours.
Embodiment 9-10
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the flower-shaped copper oxide of 0.01g catalyst (pattern such as 1 institute of attached drawing
Show), catalyst and cyclohexyl benzene weight ratio are 0.0021:1, are added to the three-necked flask of 250mL, are ultrasonically treated 2min, are formed
Suspension.Then again under magnetic agitation, by the mixed liquor as oil bath heating to after 100 DEG C (being shown in Table 3), with a constant speed under normal pressure
Rate is passed through oxygen, reacts 9h.After reaction, copper oxide catalyst and the liquid containing CHBHP is obtained by filtration in gained mixed liquor
Body mixture.Liquid mixture is analyzed, measures the conversion ratio of cyclohexyl benzene and the selectivity of CHBHP, the results are shown in Table 3.
Table 3
| Embodiment number | Embodiment 9 | Embodiment 10 |
| Oxygen gas flow rate (mL/min/mL cyclohexyl benzene) | 0.2 | 2 |
| Cyclohexyl benzene conversion ratio (%) | 23.5% | 31.9% |
| CHBHP selectivity (%) | 81.2% | 83% |
From the results shown in Table 3, comparative example 2, embodiment 9 and 10, in the range of research, oxygen gas flow rate increases
Start greatly to reacting advantageous, but as oxygen gas flow rate is excessive, has certain influence to selectivity, but influence little.
Embodiment 11-13
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the flower-shaped copper oxide of catalyst (pattern is as shown in Figure 1) with certain
Weight ratio be added to the three-necked flask of 250mL, be ultrasonically treated 2min, form suspension.Then this is mixed under magnetic agitation again
Liquid is closed as oil bath heating to after 100 DEG C (being shown in Table 4), under normal pressure by 25mL/min (in terms of every milliliter of cyclohexyl benzene, oxygen it is logical
Entering rate is 0.5mL/min) it is passed through oxygen, react 9h.After reaction, gained mixed liquor is through being obtained by filtration copper oxide catalyst
With the liquid mixture containing CHBHP.Liquid mixture is analyzed, the conversion ratio of cyclohexyl benzene and the selectivity of CHBHP are measured,
The results are shown in Table 4.
Comparative example 1
The method that this comparative example is used to illustrate reference cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide.
Cyclohexyl benzene hydrogen peroxide is produced according to the method for embodiment 11-13, unlike, it is added without catalyst oxidation
Copper, the results are shown in Table 4.
Table 4
| Embodiment number | Embodiment 11 | Embodiment 12 | Embodiment 13 | Comparative example 1 |
| Catalyst and cyclohexyl benzene weight ratio | 0.001 | 0.003 | 0.004 | 0 |
| Cyclohexyl benzene conversion ratio (%) | 18.2 | 31 | 34 | 1 |
| CHBHP selectivity (%) | 90 | 79.8 | 71 | 97 |
From the results shown in Table 4, comparative example 2, embodiment 11,12 and 13 and comparative example 1, can obviously see
Copper oxide catalyst has preferable catalytic activity, while catalyst and cyclohexyl benzene weight ratio to cyclohexyl benzene oxidation reaction out
Preferably 0.001-0.004:1.
Embodiment 14
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the rodlike copper oxide of 0.01g catalyst (pattern is as shown in Figure 2),
Catalyst and cyclohexyl benzene weight ratio 0.0021:1 are added to the three-necked flask of 250mL, are ultrasonically treated 2min, form suspension.
Then again under magnetic agitation, by the mixed liquor as oil bath heating to after 100 DEG C, under normal pressure with 25mL/min (with every milliliter
The rate that is passed through of cyclohexyl benzene meter, oxygen is 0.5mL/min) it is passed through oxygen, react 9h.After reaction, gained mixed liquor passes through
Copper oxide catalyst and the liquid mixture containing CHBHP is obtained by filtration.Liquid mixture is analyzed, turning for cyclohexyl benzene is measured
The selectivity of rate and CHBHP, the results are shown in Table 5.
Comparative example 2
The method that this comparative example is used to illustrate reference cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide.
Cyclohexyl benzene hydrogen peroxide is produced according to the method for embodiment 14, unlike, catalyst uses commercial powder shape
Copper oxide (pattern is as shown in Figure 3), the results are shown in Table 5.
Table 5
| Embodiment number | Embodiment 14 | Comparative example 2 |
| Catalyst type | Nano bar-shape copper oxide | Commercially available copper oxide |
| Cyclohexyl benzene conversion ratio (%) | 27 | 24.5 |
| CHBHP selectivity (%) | 81 | 73.2 |
From the results shown in Table 5, the copper oxide and commercially available cupric oxide powder of different-shape provided by the invention are compared
The catalytic effect of foot couple cyclohexyl benzene oxidation reaction: it is assembled using rodlike copper oxide (embodiment 14) and by nanometer rods copper oxide
At the flower-shaped copper oxide of micron (embodiment 2) is received as catalyst, the conversion ratio of cyclohexyl benzene and the selectivity of CHBHP are obviously excellent
In the effect using commercially available cupric oxide powder (comparative example 2) as catalyst.
Embodiment 15
The present embodiment is used to illustrate the side of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide provided by the invention
Method.
By 50mL cyclohexyl benzene (density 0.94g/mL) and the flower-shaped copper oxide of 0.01g catalyst (pattern such as 1 institute of attached drawing
Show), catalyst and cyclohexyl benzene weight ratio 0.0021:1 are added to the three-necked flask of 250mL, and ultrasonic treatment forms suspension.
Then again under magnetic agitation, by the mixed liquor as oil bath heating to 100 DEG C, under normal pressure with 25mL/min (with every milliliter of ring
The rate that is passed through of hexyl benzene meter, oxygen is 0.5mL/min) it is passed through oxygen, react 9h.After reaction, gained mixed liquor passes through
Filter obtains copper oxide catalyst and the liquid mixture containing CHBHP.Liquid mixture is analyzed, the conversion of cyclohexyl benzene is measured
The selectivity of rate and CHBHP, obtained solid catalyst dry 12h at 110 DEG C.
By the copper oxide of step (1) after dry, it is used as catalyst again, is being carried out under the same conditions with step (1) instead
It answers, measures yield with identical method.So by this catalyst circulation using three times, the results are shown in Table 6.
Table 6
| Access times | 0 | 1 | 2 | 3 |
| CHBHP yield (mol, %) | 20.9 | 23.2 | 23.7 | 21.6 |
From the results shown in Table 6, catalyst copper oxide is separated from reaction product mixing and is reused three times,
The yield variation of CHBHP less, illustrates that the stability of the copper oxide catalyst is good, can be recycled, and can be significantly
Reduce the cost of catalyst.
Claims (10)
1. a kind of method of cyclohexyl benzene catalysis oxidation production cyclohexyl benzene hydrogen peroxide, which is characterized 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 Rod-like shape
And/or the copper oxide of floriform appearance；
(2) mixture of reaction products that step (1) obtains is separated by solid-liquid separation, obtains catalyst copper oxide and contains cyclohexyl
The reaction product of benzene hydrogen peroxide；
The preparation method of the copper oxide of the Rod-like shape includes:
Unitary alcoholic solution containing water-soluble copper salt is added dropwise in inorganic base aqueous solution, and carries out hydro-thermal in closed environment
Reaction；
The water-soluble copper salt is copper nitrate；The monohydric alcohol is ethyl alcohol；The inorganic base is sodium hydroxide；Water-soluble copper salt with
The molar ratio of inorganic base is 1:18-22；The condition of hydro-thermal reaction includes: that temperature is 100-120 DEG C, and the time is 10-15 hours；Water
Concentration of the dissolubility mantoquita in unitary alcoholic solution is 0.45-0.55 mol/L；
The length of the copper oxide of obtained Rod-like shape is 700 nanometers, and width is 50 nanometers；
The preparation method of the copper oxide of the floriform appearance includes:
Unitary alcoholic solution containing water-soluble copper salt is added dropwise in inorganic base aqueous solution, and carries out hydro-thermal in closed environment
Reaction；
The water-soluble copper salt is copper nitrate；The monohydric alcohol is ethyl alcohol；The inorganic base is sodium hydroxide；Water-soluble copper salt with
The molar ratio of inorganic base is 1:8-12；The condition of hydro-thermal reaction includes: that temperature is 100-120 DEG C, and the time is 20-30 hours；Water
Concentration of the dissolubility mantoquita in unitary alcoholic solution is 0.4-0.65 mol/L；
The flower diameter of obtained floriform appearance copper oxide is 3-5 microns, and the length of flat club shaped structure copper oxide monomer is 400-600
Nanometer, width are 400-500 nanometers.
2. according to the method described in claim 1, wherein, the weight ratio of copper oxide and cyclohexyl benzene is 0.0002-0.005:1.
3. according to the method described in claim 2, wherein, the weight ratio 0.001-0.004:1 of copper oxide and cyclohexyl benzene.
4. method described in any one of -3 according to claim 1, 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 that cyclohexyl benzene is made to aoxidize oxygen demand theoretical value
0.5-1.5 times.
5. the oxidant is oxygen according to the method described in claim 4, wherein, in terms of every milliliter of cyclohexyl benzene, oxygen
Dosage is 0.2-2mL.
6. according to the method described in claim 5, wherein, in the presence of a catalyst, cyclohexyl benzene is contacted instead with oxidant
The mode answered includes: catalyst and cyclohexyl benzene to be mixed to form suspension, and oxygen is passed through in a manner of being bubbled, with every milliliter
The rate that is passed through of cyclohexyl benzene meter, oxygen is 0.2-2mL/min.
7. method described in any one of -3 according to claim 1, wherein by cyclohexyl benzene and the catalytic item of oxidant
Part includes: that reaction temperature is 100-150 DEG C, and the reaction time is 3-12 hours.
8. the reaction time is 9-11 hours according to the method described in claim 7, wherein, reaction temperature is 100-110 DEG C.
9. method described in any one of -3 according to claim 1, wherein by step (2) through being separated by solid-liquid separation obtained catalysis
Agent copper oxide circulation is in step (1).
10. a kind of method that cyclohexyl benzene oxygenolysis prepares cyclohexanone and phenol, this method comprises: by cyclohexyl benzene peroxidating
Cyclohexyl benzene hydrogen peroxide is obtained, then in acid condition, decomposes cyclohexyl benzene hydrogen peroxide to obtain phenol and cyclohexanone,
It is characterized in that, cyclohexyl benzene peroxidating is obtained into the method for cyclohexyl benzene hydrogen peroxide as any one of claim 1-9 institute
The method stated.
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