CN107586270B - Method for producing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene and preparing cyclohexanone and phenol by oxidative decomposition of cyclohexylbenzene - Google Patents
Method for producing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene and preparing cyclohexanone and phenol by oxidative decomposition of cyclohexylbenzene Download PDFInfo
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Abstract
The invention relates to the technical field of organic synthesis application, and discloses a method for producing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene and a method for preparing cyclohexanone and phenol by oxidative decomposition of cyclohexylbenzene, wherein the method for producing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene comprises the following steps: (1) in the presence of a catalyst, carrying out contact reaction on cyclohexylbenzene and an oxidant, wherein the catalyst is manganese dioxide with flower-like morphology; (2) and (2) carrying out solid-liquid separation on the reaction product mixture obtained in the step (1) to obtain catalyst manganese dioxide and a reaction product (CHBHP) containing cyclohexylbenzene hydroperoxide. The method of the invention can obtain higher activity and higher selectivity in the catalytic oxidation reaction of the cyclohexylbenzene without adding CHBHP or azo compounds as an initiator, and has simple process.
Description
Technical Field
The invention belongs to the technical field of organic synthesis application, and particularly relates to a method for producing cyclohexylbenzene hydrogen peroxide by catalytic oxidation of cyclohexylbenzene and a method for preparing cyclohexanone and phenol by oxidative decomposition of cyclohexylbenzene.
Background
Phenol and cyclohexanone are important basic organic chemical raw materials. Phenol is an important intermediate for preparing phenolic resin, bisphenol A and medicines, and the world demand has reached 1100 million tons/year; cyclohexanone is an important intermediate for preparing caprolactam and nylon and is an important chemical solvent, and the world demand reaches 490 ten thousand tons per year.
The conventional methods for producing phenol mainly include a sulfonation method, a chlorobenzene method, a cyclohexanone-cyclohexanol method, a toluene-benzoic acid method, an cumene method, and the like. The methods for preparing phenol from benzene indirectly have the defects of long production flow, high production cost and the like. The cumene process, the oxidative decomposition of cumene (Hock process), is currently the predominant phenol production process, with a capacity of about 90% or more of the total phenol production capacity. But the process has the defects of complex flow, serious corrosion, more byproducts, low yield (the one-way yield of the phenol is less than 5 percent) and the like. In addition, a large amount of acetone is co-produced by the cumene method, and the price fluctuation of the acetone seriously restricts the overall economy of a production device.
The production of cyclohexanone mainly adopts cyclohexane oxidation decomposition method and cyclohexene hydration-dehydrogenation method, wherein the cyclohexane oxidation decomposition method has the defects of low single pass conversion rate (4-6%), poor selectivity, large discharge amount of three wastes and the like. Although the cyclohexene hydration-dehydrogenation method can avoid the problem of the cyclohexane oxidative decomposition method, the problems of high cyclohexene cost, low reaction single-pass conversion rate, long process flow and the like still exist.
Phenol can also be produced by the oxidative decomposition of cyclohexylbenzene, and a by-product produced by the reaction is cyclohexanone having a high added value, unlike cumene oxidation. Similar to the process of producing phenol and acetone by cumene, the cyclohexylbenzene process provides an alternative process route for producing phenol, does not have the problem of excess acetone by-products, and has good development prospect.
The oxidation and decomposition of cyclohexyl benzene to produce cyclohexanone and phenol involves two reactions: (1) under the action of oxygen and in the presence of a catalyst, cyclohexyl benzene peroxidation is carried out to generate cyclohexyl benzene hydroperoxide (CHBHP); (2) under acidic conditions, cyclohexyl benzene hydroperoxide decomposes to yield phenol and cyclohexanone. Wherein, the reaction (1) is a free radical reaction, the cyclohexyl benzene peroxidation reaction has the lowest efficiency, and the reaction is a decisive step in the process of oxidizing and decomposing phenol and cyclohexanone by the cyclohexyl benzene. Currently, a common process disclosed in a series of patent applications by exxon mobil corporation (e.g., CN 104030892A, US3959381) includes: air or oxygen is used as an oxidant, a small amount of initiator such as CHBHP, azoisobutyronitrile and the like is added, N-hydroxyphthalimide (NHPI) is used as a catalyst, and the reaction is carried out for 3 to 8 hours at the reaction temperature of 95 to 120 ℃ and under normal pressure. Although the catalytic oxidation reaction based on NHPI has a better conversion rate of cyclohexylbenzene and a better selectivity of cyclohexylbenzene hydroperoxide, on the one hand, the reaction of this step needs to be carried out in the presence of an initiator, and on the other hand, the catalyst NHPI is expensive and difficult to recover and recycle. In addition, the catalyst NHPI residue in the step of oxidizing cyclohexylbenzene to prepare cyclohexylbenzene hydroperoxide affects the experimental results of the subsequent decomposition to cyclohexanone and phenol, and the separation process of the catalyst NHPI is very complicated. Therefore, the development of a recyclable catalyst which is cheap, easy to separate and has better activity is a new research point of the oxidation reaction of the cyclohexylbenzene.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for producing cyclohexylbenzene hydroperoxide by catalytic oxidation of cyclohexylbenzene by using a catalyst which has better activity, is beneficial to separation from reaction products and can be recycled, and a method for preparing cyclohexanone and phenol by oxidative decomposition of cyclohexylbenzene.
In order to achieve the above object, the present invention provides a method for producing cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene, wherein the method comprises the steps of:
(1) in the presence of a catalyst, carrying out contact reaction on cyclohexylbenzene and an oxidant, wherein the catalyst is manganese dioxide with flower-like morphology;
(2) and (2) carrying out solid-liquid separation on the reaction product mixture obtained in the step (1) to obtain a catalyst manganese dioxide and a reaction product containing cyclohexylbenzene hydroperoxide.
The invention also provides a method for preparing cyclohexanone and phenol by oxidizing and decomposing cyclohexylbenzene, which comprises the following steps: and (2) oxidizing the cyclohexylbenzene to obtain cyclohexylbenzene hydroperoxide, and decomposing the cyclohexylbenzene hydroperoxide to obtain phenol and cyclohexanone under an acidic condition, wherein the method for oxidizing the cyclohexylbenzene to obtain the cyclohexylbenzene hydroperoxide is the method provided by the invention.
In recent years, metal oxides have attracted much attention because of their simple preparation, low price, environmental friendliness, and catalytic activity. The inventor of the invention finds that manganese dioxide with flower-shaped micro-nano structure can be prepared under different conditions. The inventor of the invention utilizes micro-nano structure manganese dioxide with flower-shaped morphology as a heterogeneous catalyst to catalyze and oxidize cyclohexylbenzene to prepare CHBHP, and obtains better effect.
Compared with the prior art, the manganese dioxide with flower-shaped morphology is used as the catalyst to catalyze the reaction of preparing the cyclohexyl benzene peroxide by oxidizing the cyclohexyl benzene, so that the catalyst and a reaction product after the reaction can be directly filtered and separated, the separated manganese dioxide can be recycled as the catalyst, the manganese dioxide is wide in source, the preparation of the manganese dioxide with flower-shaped morphology is simple, the synthesis process with special morphology is controllable, and the environment is friendly. The method is different from the traditional reaction and has the key points that CHBHP or azo compounds are not required to be added as an initiator, higher activity and higher selectivity can be obtained in the catalytic oxidation reaction of the cyclohexylbenzene, and the process is simple. Compared with the copper oxide catalyst reported before, the manganese oxide catalyst can keep higher selectivity at high temperature; under the same selectivity condition, the conversion rate is higher.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a scanning electron micrograph of manganese dioxide in flower-like morphology according to an embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a commercially available manganese dioxide powder.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to the present invention, the method for producing cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene comprises the steps of:
(1) in the presence of a catalyst, carrying out contact reaction on cyclohexylbenzene and an oxidant, wherein the catalyst is manganese dioxide with flower-like morphology;
(2) and (2) carrying out solid-liquid separation on the reaction product mixture obtained in the step (1) to obtain a catalyst manganese dioxide and a reaction product containing cyclohexylbenzene hydroperoxide.
The inventor of the invention finds that the manganese dioxide which is different from the conventional powdery manganese dioxide and has a micro-nano flower-shaped structure is used as the catalyst for preparing the cyclohexylbenzene hydrogen peroxide, so that the process can be simplified, namely, CHBHP or azo compounds are not required to be added as an initiator as in the conventional process, so that higher activity and selectivity can be obtained, in addition, a reaction product mixture can be separated through simple solid-liquid separation, and the separated solid-phase catalyst manganese dioxide can be recycled.
According to the invention, the manganese dioxide with flower-like morphology is assembled by manganese dioxide monomers with flat-ribbon-like structure, the flower diameter of the manganese dioxide with flower-like morphology is 3-5 microns, the manganese dioxide monomers with flat-ribbon-like structure are monodispersed uniform manganese dioxide, the width of the manganese dioxide monomers with flat-ribbon-like structure is preferably 500-700 nm, and the length of the manganese dioxide monomers with flat-ribbon-like structure is preferably 600-1000 nm.
According to the invention, the preparation method of the manganese dioxide with flower-like morphology comprises the following steps:
adding a solution containing water-soluble manganese salt into an aqueous solution of persulfate, uniformly dispersing, and carrying out hydrothermal reaction in a closed environment; the water-soluble manganese salt is selected from one or more of manganese nitrate, manganese sulfate and manganese carbonate, and is preferably manganese sulfate; the persulfate is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate, and is preferably ammonium persulfate; the molar ratio of the water-soluble manganese salt to the persulfate is 1:0.2-5, preferably 1: 0.5-2; the conditions of the hydrothermal reaction include a temperature of 60 to 120 ℃, preferably 90 to 120 ℃; the time is 20 to 30 hours, preferably 22 to 26 hours.
According to a specific embodiment of the present invention, the preparation method of the manganese dioxide with flower-like morphology comprises the following steps: dropwise adding 0.8M manganese sulfate solution into 0.8M ammonium persulfate aqueous solution, completely mixing, transferring to a hydrothermal kettle, sealing, and reacting at 110-120 ℃ for 24 hours to obtain the product.
According to the invention, in the step (1), the catalyst manganese dioxide has a flower-like morphology. Although catalytic oxidation of the reactant cyclohexylbenzene to cyclohexylbenzene hydroperoxide can be achieved by contacting it with an oxidizing agent in the presence of manganese dioxide, which is a catalyst having the above morphology, it is preferable that the weight ratio of the manganese dioxide catalyst to the reactant cyclohexylbenzene is from 0.0002 to 0.005:1, and more preferably from 0.001 to 0.004: 1.
Preferably, in order to allow the catalyst manganese dioxide to sufficiently contact the reactant cyclohexylbenzene to sufficiently exert its catalytic activity, the reactants cyclohexylbenzene and manganese dioxide are mixed in a reactor and sonicated to form a suspension.
The key point of the present invention is that manganese dioxide with flower-like morphology is used as catalyst for preparing cyclohexylbenzene hydrogen peroxide by catalyzing cyclohexylbenzene oxidation, therefore, the oxidant in the catalytic oxidation reaction can be oxidant which is conventionally used in the field, for example, the oxidant can be oxygen-containing gas, such as air or oxygen, preferably oxygen. The amount of the oxygen-containing gas which is in contact with the reactant cyclohexylbenzene is 1.05 to 1.2 times the theoretical value of the oxygen demand for oxidizing cyclohexylbenzene, based on the mass of the oxygen in the oxygen-containing gas. Further preferably, when oxygen is used as the oxidizing agent, the amount of oxygen may be 0.2 to 2mL per mL of cyclohexylbenzene.
Further preferably, in order to allow more sufficient contact of the oxidant with the reactant cyclohexylbenzene, the oxygen-containing gas, preferably oxygen, is bubbled at a rate of 0.2 to 2mL/min per mL of cyclohexylbenzene.
In summary, the most preferred method for contacting cyclohexylbenzene with the oxidizing agent comprises: the catalyst is mixed with cyclohexylbenzene to form a suspension and oxygen is bubbled in at a rate of 0.2-2mL/min per mL of cyclohexylbenzene.
According to the present invention, the conditions for the contact reaction of cyclohexylbenzene with an oxidant include a reaction temperature and a reaction time, the reaction temperature may be 95 to 150 ℃, preferably 100 ℃ to 110 ℃, the reaction time may be 3 to 12 hours, preferably 9 to 11 hours, and the reaction pressure is normal pressure.
According to the method, the separation of the catalyst and the reaction product in the reaction mixture can be well realized, and according to the method, after the reaction in the step (1) is finished, the reaction product mixture obtained in the step (1) is subjected to solid-liquid separation, so that the solid-phase catalyst manganese dioxide and the liquid-phase reaction product containing the cyclohexylbenzene hydroperoxide can be obtained. Meanwhile, the solid-phase catalyst manganese dioxide obtained by solid-liquid separation in the step (2) can be recycled in the step (1) and used as a catalyst for recycling. The solid-liquid separation method is well known to those skilled in the art, and examples thereof include filtration, sedimentation, and centrifugation. Preferably, the method further comprises washing and drying the catalyst manganese dioxide obtained after solid-liquid separation, wherein the solvent used for washing is well known to those skilled in the art, such as ethanol; the drying conditions and methods can be those conventional in the art, for example, the drying temperature is not higher than 120 ℃, preferably 80 to 100 ℃, and the drying time can be 8 to 24 hours.
According to the present invention, in order to obtain a purified reaction product, the method further comprises purifying the reaction product containing cyclohexylbenzene hydroperoxide obtained in step (2) to obtain a purified product cyclohexylbenzene hydroperoxide. Such methods for purifying the reaction product containing cyclohexylbenzene hydroperoxide are well known to those skilled in the art and will not be described herein.
The invention also provides a method for preparing cyclohexanone and phenol by oxidizing and decomposing cyclohexylbenzene, which comprises the following steps: and (2) oxidizing the cyclohexylbenzene to obtain cyclohexylbenzene hydroperoxide, and decomposing the cyclohexylbenzene hydroperoxide to obtain phenol and cyclohexanone under an acidic condition, wherein the method for oxidizing the cyclohexylbenzene to obtain the cyclohexylbenzene hydroperoxide is the method provided by the invention. The conditions for decomposing cyclohexylbenzene hydroperoxide to obtain phenol and cyclohexanone can refer to the conditions known in the art, for example, the acidic conditions are usually diluted sulfuric acid solution with a certain concentration, and the diluted sulfuric acid solution is directly added into the peroxide solution, and the reaction time can be prolonged appropriately according to the peroxide solution, and is usually 2-5 h.
According to the invention, the one-step method can be directly adopted to decompose the cyclohexylbenzene hydroperoxide obtained by the cyclohexylbenzene peroxidation to obtain the phenol and the cyclohexanone, or the reaction product containing the cyclohexylbenzene hydroperoxide obtained by the method of the invention can be purified to obtain the purified product of the cyclohexylbenzene hydroperoxide and then is decomposed under the acidic condition to prepare the phenol and the cyclohexanone. The method for purifying the reaction product containing cyclohexylbenzene hydroperoxide is well known to those skilled in the art, and for example, a distillation method may be used, and will not be described herein.
In the present invention, the pressures are gauge pressures.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The present invention will be described in detail below by way of examples.
In the examples, the reagents used were all analytical reagents, unless otherwise specified.
In the examples, the reactant cyclohexylbenzene was purchased from carbofuran.
In the examples, the preparation method of manganese dioxide with flower-like morphology is as follows:
dropwise adding 0.8M manganese sulfate solution into 0.8M ammonium persulfate aqueous solution, uniformly dispersing, transferring to a hydrothermal kettle, sealing, and reacting at 110-120 ℃ for 24 hours to obtain a product. The flower diameter of the manganese dioxide with flower-like morphology is 3-5 microns, the width of the flat band-shaped structure manganese dioxide monomer is 500-700 nanometers, and the length of the flat band-shaped structure manganese dioxide monomer is 600-1000 nanometers.
Manganese dioxide powder was purchased from Beijing, Inc., national pharmaceutical group chemical, AR100 g.
The following examples are presented for the determination and calculation of cyclohexylbenzene conversion (%) and CHBHP selectivity (%) as follows (normalization):
after separation, the resulting liquid mixture containing CHBHP was weighed in two portions (0.8 g each). One of the fractions was iodometric for all CHBHP contents: adding m into an iodine measuring flask1g liquid mixture from the reaction, 20mL glacial acetic acid solution was added, and 2g NaHCO was added3Solid powder, and gently shaking to uniformly mix the solid powder and the liquid; then adding 10mL of saturated KI solution, cooling with water when the reaction is carried out until no bubbles are generated, and adding 100mL of distilled water; with a concentration of c1Standard Na in mol/L (0.15mol/L)2S2O3Calibrating the solution until the solution is light yellow, adding 2mL of starch indicator (such as 5% by mass), continuously titrating until the solution is changed from blue to milky white, namely, the titration end point, and recording the consumed standard Na2S2O3The volume of the solution was VmL.
Another portion of the liquid mixture obtained in the reaction is weighed out, the mass m2g, adding m3Using g (0.4g) of naphthalene as an internal standard, shaking uniformly, adding excessive triphenylphosphine for reduction, adding 2mL of acetonitrile for dilution, and then measuring the amount of substances such as cyclohexylbenzene, phenylcyclohexanol, phenylhexanone and the like in each gram of liquid mixture to be n by using gas chromatography (the column temperature is 200 ℃, and the temperatures of a sample injector and a detector are both 300 ℃)1，n2，n3(mol)。
The mass of CHBHP per gram of liquid mixture as determined by iodometry was:
nCHBHP(mol)＝c1×V×0.5/(m1×1000)
conversion (%) of cyclohexylbenzene 100 × (n)2+n3)/(n1+n2+n3)
Selectivity (%) of CHBHP of 100 × nhchbhp/(n)2+n3)
The yield (%) of CHBHP was 100 XnCHBHP/(n)1+n2+n3)
Examples 1 to 4
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and catalyst flower-like manganese dioxide (morphology as shown in FIG. 1), with a catalyst to cyclohexylbenzene weight ratio of 0.0021:1, were added to a 250mL three-necked flask and sonicated for 2min to form a suspension. Then, after the mixture was heated in an oil bath to a predetermined reaction temperature (see Table 1) under magnetic stirring, oxygen was introduced at 100mL/min (the introduction rate of oxygen per gram of catalyst was 1000mL/min/g) under normal pressure, and the reaction was carried out for 9 hours. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed and the cyclohexylbenzene conversion and the CHBHP selectivity were determined and are shown in Table 1.
TABLE 1
| Example numbering | Example 1 | Example 2 | Example 3 | Example 4 |
| Reaction temperature (. degree.C.) | 90 | 100 | 110 | 120 |
| Cyclohexylbenzene conversion (%) | 8.5％ | 14.8％ | 35％ | 46％ |
| CHBHP selectivity (%) | 97.8％ | 93.1％ | 88.4％ | 82％ |
As can be seen from the results in Table 1, the temperature increase favors the oxidation of cyclohexylbenzene, but when the temperature reaches 120 ℃, the CHBHP decomposition is accelerated, the conversion rate is remarkably improved, and the CHBHP selectivity is reduced, therefore, the reaction temperature is preferably 100-.
Examples 5 to 8
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and catalyst flower-like manganese dioxide (morphology as shown in FIG. 1), with a catalyst to cyclohexylbenzene weight ratio of 0.0021:1, were added to a 250mL three-necked flask and sonicated for 2min to form a suspension. Then, the mixture was heated in an oil bath to 100 ℃ with magnetic stirring (see Table 2), and then oxygen was introduced at 100mL/min (the introduction rate of oxygen per gram of catalyst was 1000mL/min/g) under normal pressure for a certain period of time. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed, and the cyclohexylbenzene conversion and the CHBHP selectivity were measured, and the results are shown in Table 2.
TABLE 2
| Example numbering | Example 5 | Example 6 | Example 7 | Example 8 |
| Reaction time (h) | 8 | 10 | 11 | 12 |
| Cyclohexylbenzene conversion (%) | 9.1％ | 21.5％ | 36.9％ | 47％ |
| CHBHP selectivity (%) | 98.1％ | 87.5％ | 81.7％ | 77.1％ |
From the results in Table 2, it can be seen that the CHBHP selectivity tended to decrease with increasing reaction time, and particularly, after more than 11 hours of reaction, the rate of decrease was abruptly increased. Therefore, in the reaction time range studied in Table 2, the preferred reaction time for comparative example 2 is 9 to 11 hours.
Examples 9 to 10
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and catalyst flower-like manganese dioxide (morphology as shown in FIG. 1), with a catalyst to cyclohexylbenzene weight ratio of 0.0021:1, were added to a 250mL three-necked flask and sonicated for 2min to form a suspension. Then, the mixture was heated to 110 ℃ in an oil bath with magnetic stirring (see Table 3), and then oxygen was introduced at a constant rate under normal pressure to react for 9 hours. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed, and the cyclohexylbenzene conversion and the CHBHP selectivity were measured, and the results are shown in Table 3.
TABLE 3
| Example numbering | Example 9 | Example 10 |
| Oxygen flow rate (mL/min/g catalyst) | 500 | 5000 |
| Cyclohexylbenzene conversion (%) | 30％ | 47.1％ |
| CHBHP selectivity (%) | 85.4％ | 86.2％ |
As can be seen from the results in Table 3, in comparative examples 9, 3 and 10, in the range studied, the increase in the oxygen flow rate initially had a favorable effect on the reaction, but with an excessively large oxygen flow rate, the selectivity was somewhat affected, but not so much.
Examples 11 to 13
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and the catalyst flower-like manganese dioxide (morphology shown in FIG. 1) were added in a weight ratio to a 250mL three-necked flask and sonicated for 2min to form a suspension. Then, after the mixture was heated to 100 ℃ in an oil bath with magnetic stirring (see Table 4), 100mL/min (oxygen introduction rate: 2mL/min per mL of cyclohexylbenzene) was introduced and reacted for 9 hours. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed, and the cyclohexylbenzene conversion and the CHBHP selectivity were measured, and the results are shown in Table 4.
TABLE 4
| Example numbering | Example 10 | Example 11 | Example 12 | Example 13 |
| Catalyst to cyclohexylbenzene weight ratio | 0 | 0.001 | 0.003 | 0.004 |
| Cyclohexylbenzene conversion (%) | 1 | 11.2 | 17.2 | 21.8 |
| CHBHP selectivity (%) | 97 | 95 | 86.8 | 82 |
From the results in Table 4, it is apparent that the manganese dioxide catalyst has a better catalytic activity for the oxidation reaction of cyclohexylbenzene as compared with examples 10, 2, 11, 12, 13, and the weight ratio of the catalyst to cyclohexylbenzene is preferably 0.001 to 0.004: 1.
Comparative example 1
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and commercially available powdered manganese dioxide (morphology as shown in FIG. 2), in a catalyst to cyclohexylbenzene weight ratio of 0.0021:1, were added to a 250mL three-necked flask and sonicated for 2min to form a suspension. Then, the mixture was heated in an oil bath to 100 ℃ under magnetic stirring, and then oxygen was introduced at 100mL/min (the rate of introduction of oxygen per gram of catalyst was 1000mL/min/g) under normal pressure to react for 10 hours. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed, and the cyclohexylbenzene conversion and the CHBHP selectivity were measured, and the results are shown in Table 5.
TABLE 5
| Example numbering | Comparative example 1 |
| Kind of catalyst | Commercially available manganese dioxide |
| Cyclohexylbenzene conversion (%) | 20 |
| CHBHP selectivity (%) | 78.9 |
As can be seen from the results in table 5, comparing the catalytic effect of the commercially available manganese dioxide powder on the oxidation reaction of cyclohexylbenzene, it can be seen that: compared with the commercial manganese dioxide powder as the catalyst, the nano-micron flowerlike manganese dioxide (compared with the manganese dioxide powder in example 6) as the catalyst has better conversion rate of the cyclohexylbenzene and selectivity of the CHBHP, and particularly, the selectivity of the CHBHP is obviously reflected.
Example 14
This example illustrates the present invention for the production of cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene.
50mL of cyclohexylbenzene (density 0.94g/mL) and catalyst flower-like manganese dioxide (morphology as shown in FIG. 1), in a catalyst to cyclohexylbenzene weight ratio of 0.0021:1, were added to a 250mL three-necked flask and sonicated to form a suspension. Then, the mixture was placed in an oil bath and heated to 110 ℃ under magnetic stirring, and oxygen was introduced at 100mL/min (the introduction rate of oxygen per gram of catalyst was 1000mL/min/g) under normal pressure for 9 hours. After the reaction is finished, filtering the obtained mixed solution to obtain the manganese dioxide catalyst and a liquid mixture containing CHBHP. The liquid mixture was analyzed to determine the cyclohexylbenzene conversion and the CHBHP selectivity, and the resulting solid catalyst was dried at 110 ℃ for 12 hours.
The manganese dioxide dried in the step (1) was reacted again as a catalyst under the same conditions as in the step (1), and the yield was measured by the same method. This catalyst was thus recycled three times, and the results are shown in Table 6.
TABLE 6
| Number of times of use | 0 | 1 | 2 | 3 |
| CHBHP yield (mol,%) | 30.9 | 31.5 | 30.8 | 29.6 |
As can be seen from the results of table 6, when the catalyst manganese dioxide is separated from the reaction product mixture and reused three times, the yield of CHBHP does not change much, which indicates that the manganese dioxide catalyst has good stability, can be recycled, and can greatly reduce the cost of the catalyst.
Claims (11)
1. A method for producing cyclohexylbenzene hydroperoxide by the catalytic oxidation of cyclohexylbenzene, which is characterized by comprising the following steps:
(1) in the presence of a catalyst, carrying out contact reaction on cyclohexylbenzene and an oxidant, wherein the catalyst is manganese dioxide with flower-like morphology;
the manganese dioxide with the flower-like morphology is assembled by manganese dioxide monomers with a flat band-like structure, the diameter of the manganese dioxide with the flower-like morphology is 3-5 micrometers, the width of the manganese dioxide monomers with the flat band-like structure is 500-700 nanometers, and the length of the manganese dioxide monomers with the flat band-like structure is 600-1000 nanometers;
the preparation method of the manganese dioxide with flower-like morphology comprises the following steps:
adding a solution containing water-soluble manganese salt into an aqueous solution of persulfate, uniformly dispersing, and carrying out hydrothermal reaction in a closed environment;
the water-soluble manganese salt is selected from one or more of manganese nitrate, manganese sulfate and manganese carbonate; the persulfate is one or more of ammonium persulfate, potassium persulfate and sodium persulfate; the molar ratio of the water-soluble manganese salt to the persulfate is 1: 0.2-5; the hydrothermal reaction conditions include temperature of 60-120 deg.c and time of 20-30 hr;
(2) and (2) carrying out solid-liquid separation on the reaction product mixture obtained in the step (1) to obtain a catalyst manganese dioxide and a reaction product containing cyclohexylbenzene hydroperoxide.
2. The method of claim 1, wherein the water-soluble manganese salt is manganese sulfate; the persulfate is ammonium persulfate; the molar ratio of the water-soluble manganese salt to the persulfate is 1: 0.5-2; the hydrothermal reaction conditions include a temperature of 90-120 deg.C and a time of 22-26 hours.
3. The method of claim 1, wherein the weight ratio of manganese dioxide to cyclohexylbenzene is from 0.0002 to 0.005: 1.
4. The process of claim 3, wherein the weight ratio of manganese dioxide to cyclohexylbenzene is from 0.001 to 0.004: 1.
5. The process according to any one of claims 1 to 4, wherein the oxidizing agent is an oxygen-containing gas, and the amount of the oxygen-containing gas contacted with the cyclohexylbenzene is 1.05 to 1.2 times the theoretical value of the oxygen demand for oxidizing the cyclohexylbenzene, based on the mass of oxygen in the oxygen-containing gas.
6. The process of claim 5, wherein the oxidant is oxygen in an amount of 0.2-2mL per mL of cyclohexylbenzene.
7. The process of claim 5, wherein the cyclohexylbenzene is reacted in contact with the oxidant in the presence of a catalyst in a manner comprising: the catalyst is mixed with cyclohexylbenzene to form a suspension and oxygen is bubbled in at a rate of 0.2-2mL/min per mL of cyclohexylbenzene.
8. The process of any one of claims 1 to 4, wherein the conditions for contacting cyclohexylbenzene with the oxidant comprise: the reaction temperature is 95-150 ℃, and the reaction time is 3-12 hours.
9. The method as claimed in claim 8, wherein the reaction temperature is 100-110 ℃ and the reaction time is 9-11 hours.
10. The process according to any one of claims 1 to 4, wherein the catalytic manganese dioxide obtained by the solid-liquid separation in step (2) is recycled to be used in step (1).
11. A method for preparing cyclohexanone and phenol by oxidizing and decomposing cyclohexylbenzene comprises the following steps: the process of peroxidation of cyclohexylbenzene to produce cyclohexylbenzene hydroperoxide and decomposing the cyclohexylbenzene hydroperoxide under acidic conditions to produce phenol and cyclohexanone, wherein the process of peroxidation of cyclohexylbenzene to produce cyclohexylbenzene hydroperoxide is as claimed in any one of claims 1 to 10.
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