CN117945860A - Method for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene - Google Patents
Method for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene Download PDFInfo
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- CN117945860A CN117945860A CN202211351501.5A CN202211351501A CN117945860A CN 117945860 A CN117945860 A CN 117945860A CN 202211351501 A CN202211351501 A CN 202211351501A CN 117945860 A CN117945860 A CN 117945860A
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- cyclohexylbenzene
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- hydroxyphthalimide
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- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 title claims abstract description 67
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- QCRRJEABYLEFAE-UHFFFAOYSA-N (1-hydroperoxycyclohexyl)benzene Chemical compound C=1C=CC=CC=1C1(OO)CCCCC1 QCRRJEABYLEFAE-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 16
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical class C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 43
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- -1 N-hydroxyphthalimide compound Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- UTRBHXSKVVPTLY-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-hydroxyisoindole-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(=O)N(O)C2=O UTRBHXSKVVPTLY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- DYQAZJQDLPPHNB-UHFFFAOYSA-N 1-phenyl-2-hexanone Chemical compound CCCCC(=O)CC1=CC=CC=C1 DYQAZJQDLPPHNB-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XXYNZSATHOXXBJ-UHFFFAOYSA-N 4-hydroxyisoindole-1,3-dione Chemical compound OC1=CC=CC2=C1C(=O)NC2=O XXYNZSATHOXXBJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 150000001216 Samarium Chemical class 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000019877 cocoa butter equivalent Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OECMNLAWCROQEE-UHFFFAOYSA-N cyclohexylbenzene;hydrogen peroxide Chemical compound OO.C1CCCCC1C1=CC=CC=C1 OECMNLAWCROQEE-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The present disclosure relates to a process for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene, the process comprising: contacting cyclohexylbenzene and oxygen-containing gas with a supported catalyst and performing catalytic oxidation reaction to obtain a first product containing 1-phenylcyclohexyl hydroperoxide; subjecting the first product to a decomposition reaction under acidic conditions; wherein the supported catalyst comprises a carrier and N-hydroxyphthalimide compounds supported on the carrier; the carrier is a porous inorganic carbon material containing nitrogen element. The method solves the problem that the homogeneous catalyst is difficult to recycle, and simultaneously maintains the higher selectivity of the N-hydroxyphthalimide and the derivatives thereof for preparing the 1-phenylcyclohexyl hydroperoxide by catalyzing and oxidizing the cyclohexylbenzene.
Description
Technical Field
The present disclosure relates to the technical field of organic synthesis applications, and in particular, to a method for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene.
Background
Phenol and cyclohexanone are important organic chemical raw materials, and have wide application range and larger demand. But all of them have disadvantages of varying degrees in industrial production. For example, the industrial production of phenol mainly adopts a cumene oxidation method, and the phenol is produced with the co-production of equimolar amount of acetone, and the low value and the excessive productivity of the acetone affect the economic benefit of the whole process. Industrial production of cyclohexanone mainly includes phenol hydrogenation, cyclohexane oxidation and cyclohexene hydration. The phenol hydrogenation method has poor economy due to the relatively high price of raw materials; the conversion rate of the cyclohexane oxidation method is only 4%, the selectivity of the alcohol ketone is only 75-80%, the atom utilization rate is low, and the environmental pollution is serious; the cyclohexene hydration method also has the problems of low equilibrium conversion rate, difficult separation of benzene, cyclohexane and cyclohexene, high energy consumption and the like.
The technical route for preparing phenol and cyclohexanone by oxidation-decomposition of cyclohexylbenzene simultaneously produces high-value phenol and cyclohexanone with atomic utilization close to 100%, and is therefore of great interest. However, the cyclohexylbenzene has larger steric hindrance and more activatable positions, so that the reaction byproducts are more and the selectivity is poorer.
British patent GB681613 discloses a method for preparing phenol and cyclohexanone by contact oxidation of cyclohexylbenzene with oxygen in the absence of a catalyst, wherein the cyclohexylbenzene and the oxygen are subjected to induction reaction for 3 hours at 105-110 ℃, the conversion rate of the cyclohexylbenzene is 28% after the reaction is continued for 50 hours, and the selectivity of the phenol and the cyclohexanone is 65% and 50%, respectively. The preparation of phenol and cyclohexanone by oxidation of cyclohexylbenzene in the absence of a catalyst has been explored in U.S. Pat. No. 3,218 and U.S. Pat. No. 5,62, but the disadvantages of slow reaction rate and low selectivity are always present. Subsequently, U.S. patent No. 4450303 reports that the use of metal samarium salts, chinese patent No. CN108329243 discloses the use of metalloporphyrins, guo Xin, etc. (fine chemical engineering, 2010,27 (3): 244-247) discloses the use of metal oxides to catalyze the oxidation of cyclohexylbenzene to produce phenol and cyclohexanone, but the selectivity is around 80%. Sun Tingting et al (petroleum processing), 2020,36 (2): 244-251.) carried N-hydroxyphthalimide on polystyrene microspheres, examined the catalytic oxidation performance of cyclohexylbenzene, but the conversion and selectivity were severely affected when the supported catalyst catalyzes the oxidation of cyclohexylbenzene.
Disclosure of Invention
It is an object of the present disclosure to increase the selectivity of cyclohexylbenzene hydroperoxide decomposition to cyclohexanone and phenol.
To achieve the above object, the present disclosure provides a method for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene, the method comprising: contacting cyclohexylbenzene and oxygen-containing gas with a supported catalyst and performing catalytic oxidation reaction to obtain a first product containing 1-phenylcyclohexyl hydroperoxide; subjecting the first product to a decomposition reaction under acidic conditions;
Wherein the supported catalyst comprises a carrier and N-hydroxyphthalimide compounds supported on the carrier; the carrier is a porous inorganic carbon material containing nitrogen element.
Optionally, the temperature of the catalytic oxidation reaction is 80-120 ℃, preferably 95-110 ℃; the reaction pressure is 0.1-3MPa, preferably 0.8-1.2MPa; the reaction time is 3 to 15 hours, preferably 6 to 10 hours.
Alternatively, the loading of the N-hydroxyphthalimide compound is 0.1-50 wt.%, preferably 1-30 wt.%, based on the total weight of the supported catalyst.
Optionally, the nitrogen element content is 0.5-60 wt%, preferably 1.1-43 wt%, based on the total weight of the porous inorganic carbon material; optionally, the porous inorganic carbon material has a specific surface area of 1-800m 2/g, preferably 2-300m 2/g; the pore size of the accessible pores is in the range of 2-30nm, preferably in the range of 5-20 nm; the pore volume is 0.01-0.7mL/g, preferably 0.06-0.5mL/g.
Alternatively, the mass fraction of the supported catalyst is 0.01 to 30%, preferably 0.1 to 15%, based on the total mass of cyclohexylbenzene and the supported catalyst.
Optionally, the supported catalyst is prepared according to the following steps:
S1, dissolving an N-hydroxyphthalimide compound in an organic solvent to obtain a first mixed solution;
s2, impregnating the carrier by using the first mixed solution, stirring and standing to obtain a first mixture;
s3, drying the first mixture.
Optionally, the organic solvent is selected from at least one of acetonitrile, ethanol and tetrahydrofuran; the conditions of the impregnation include: the temperature is 20-40 ℃ and the time is 1-6h; the conditions of the drying treatment include: the temperature is 80-130 ℃ and the time is 4-6h.
Optionally, the volume fraction of oxygen in the oxygen-containing gas is 5-100% based on the total volume of the oxygen-containing gas; preferably, the volume fraction of oxygen in the oxygen-containing gas is 21-100%.
Alternatively, the oxygen-containing gas is introduced at a rate of 0.1 to 5mL/min, preferably 0.5 to 1.5mL/min, in terms of oxygen, relative to 1mL of cyclohexylbenzene.
Optionally, the decomposition reaction comprises decomposing the first product under catalysis of an acidic substance selected from solid and/or liquid acids, preferably liquid acids, more preferably sulfuric acid; the decomposition temperature is 20-50 ℃, and the decomposition time is 0.3-2h.
According to the technical scheme, the porous carbon material containing nitrogen is used as a carrier, the N-hydroxyphthalimide compound is loaded, the heterogeneous catalyst which is easy to separate is prepared, the catalyst can be used for preparing phenol and cyclohexanone through catalytic oxidation of cyclohexylbenzene, the problem that the homogeneous catalyst is difficult to recycle is solved, and meanwhile, the higher selectivity of the N-hydroxyphthalimide and derivatives thereof for preparing 1-phenylcyclohexyl hydroperoxide through catalytic oxidation of cyclohexylbenzene is maintained.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a method for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene, the method comprising: contacting cyclohexylbenzene and oxygen-containing gas with a supported catalyst and performing catalytic oxidation reaction to obtain a first product containing 1-phenylcyclohexyl hydroperoxide; subjecting the first product to a decomposition reaction under acidic conditions;
Wherein the supported catalyst comprises a carrier and N-hydroxyphthalimide compounds supported on the carrier; the carrier is a porous inorganic carbon material containing nitrogen element.
The inventor of the present disclosure found that the separation and reuse of the catalyst and the reaction material can be easily achieved by catalytic oxidation of cyclohexylbenzene using a supported catalyst in which a porous carbon material containing nitrogen is used as a carrier and an N-hydroxyphthalimide compound is used as an active material. Compared with the traditional heterogeneous catalyst for catalyzing and oxidizing the cyclohexylbenzene, the porous carbon containing nitrogen is used as a carrier, oxygen molecules can be activated under the reaction condition, and the porous carbon is combined with the N-hydroxyphthalimide compound, so that the catalyst has better cyclohexylbenzene conversion rate and 1-phenylcyclohexyl hydroperoxide selectivity.
According to the present disclosure, the catalytic oxidation reaction may have a temperature of 80 to 120 ℃, a reaction pressure of 0.1 to 3MPa, and a reaction time of 3 to 15 hours, and as a preferred embodiment of the present disclosure, the catalytic oxidation reaction has a temperature of 95 to 110 ℃, a reaction pressure of 0.8 to 1.2MPa, and a reaction time of 6 to 10 hours.
According to the present disclosure, the loading amount of the N-hydroxyphthalimide compound may be 0.1 to 50 wt%, preferably 1 to 30 wt%, based on the total weight of the supported catalyst. The N-hydroxyphthalimide compound is at least one selected from N-hydroxyphthalimide and 3,4,5, 6-tetrachloro-N-hydroxyphthalimide.
According to the present disclosure, the nitrogen element content may be 0.5 to 60 wt%, preferably 1.1 to 43 wt%, based on the total weight of the porous inorganic carbon material; alternatively, the porous inorganic carbon material may have a specific surface area of 1-800m 2/g, preferably 2-300m 2/g; the pore size of the cocoa butter equivalent may be in the range of 2-30nm, preferably in the range of 5-20 nm; the pore volume may be 0.01-0.7mL/g, preferably 0.06-0.5mL/g.
According to the present disclosure, the mass fraction of the supported catalyst may be 0.01 to 30%, preferably 0.1 to 15%, based on the total mass of cyclohexylbenzene and the supported catalyst.
The supported catalysts in the present disclosure may be prepared by methods conventional in the art, such as physical impregnation and chemical grafting. As a preferred embodiment of the present disclosure, the supported catalyst is prepared according to the following steps:
S1, dissolving an N-hydroxyphthalimide compound in an organic solvent to obtain a first mixed solution;
s2, impregnating the carrier by using the first mixed solution, stirring and standing to obtain a first mixture;
s3, drying the first mixture.
According to the present disclosure, the organic solvent may be selected from at least one of acetonitrile, ethanol, and tetrahydrofuran; the conditions of the impregnation may include: the temperature is 20-40 ℃ and the time is 1-6h; the conditions of the drying process may include: the temperature is 80-130 ℃ and the time is 4-6h.
According to the present disclosure, the volume fraction of oxygen in the oxygen-containing gas may be 5-100% based on the total volume of the oxygen-containing gas; preferably, the volume fraction of oxygen in the oxygen-containing gas is 21-100%.
According to the present disclosure, the oxygen-containing gas may be introduced at a rate of 0.1 to 5mL/min, preferably 0.5 to 1.5mL/min, in terms of oxygen, relative to 1mL of cyclohexylbenzene.
According to the present disclosure, 1-phenylcyclohexyl hydroperoxide is decomposed under the catalysis of an acidic substance to produce phenol and cyclohexanone; the decomposition reaction may comprise subjecting the first product to decomposition under catalysis of an acidic substance, which may be selected from solid and/or liquid acids, preferably liquid acids, more preferably inorganic liquid acids, most preferably sulfuric acid; the decomposition temperature may be 20-50 ℃, and the decomposition time may be 0.3-2h.
In the present disclosure, a conventional solid-liquid separation method is used to separate the heterogeneous catalyst from the decomposed product, and the separated heterogeneous catalyst is reused for the catalytic oxidation reaction of cyclohexylbenzene.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby. Unless otherwise indicated, the reagents used in the examples and comparative examples were all analytically pure.
Cyclohexylbenzene used in examples and comparative examples was purchased from aladine.
The preparation methods of the supported catalysts used in examples and comparative examples were: 3g N-hydroxyphthalimide is dissolved in 100g of acetonitrile, after the 3-hydroxyphthalimide is completely dissolved, 47g of porous carbon material A is immersed, the specific surface of the carbon material A is 23m 2/g, the mixture is uniformly stirred, the acetonitrile is naturally volatilized, after the acetonitrile is volatilized, the mixture is put into a drying oven for drying at 80 ℃ for 3 hours, and the heterogeneous catalyst with the N-hydroxyphthalimide load of 6% is obtained. Wherein the porous carbon material a is from commercial purchase.
The cyclohexylbenzene conversion and 1-phenylcyclohexyl hydroperoxide selectivity were determined and calculated as follows:
Titration of the 1-phenylcyclohexyl hydroperoxide content of the obtained reaction product by using an iodometry method comprises the following specific steps: (a) Taking 450 ml of deionized water, and introducing nitrogen for 10 minutes to prepare deoxidized water; taking 30ml of deoxidized water, placing the deoxidized water into a brown bottle, and adding potassium iodide to prepare a potassium iodide saturated solution; taking 20ml of glacial acetic acid, adding the glacial acetic acid into a 250 ml iodine measuring flask, and introducing nitrogen to replace for 2 minutes; (b) Taking a cyclohexyl benzene oxidation product with the mass of m 1, placing the cyclohexyl benzene oxidation product into an iodometric bottle, and adding 5 milliliters of fresh saturated potassium iodide solution into the iodometric bottle; (c) The iodine flask is placed in a water bath kettle with the temperature of 60 ℃ to react for 35 to 60 minutes in a dark place. Taking out and cooling to room temperature in dark; (d) 60 ml of deoxygenated water was added to an iodometric flask, titrated to a pale yellow color using a standard solution of c 1 (0.1 mol/L) sodium thiosulfate, and 1-2 ml of starch indicator was added. Titration to colorless was done as endpoint and the volume of sodium thiosulfate solution was recorded as V. Repeated 2 times. The average value of 3 times is taken as the content of 1-phenylcyclohexyl hydroperoxide in the cyclohexyl benzene oxidation product.
Then based on the titration result of the iodometry, using the reaction product with known 1-phenylcyclohexyl hydroperoxide content to prepare standard solutions with different concentrations, using chromatographic pure acetonitrile as solvent, using high performance liquid chromatography, using acetonitrile: water (volume ratio 2:1) was the mobile phase, flow rate 1ml per minute, standard curve was established, 258 nm wavelength was used for the detector, and the established standard curve was used to analyze the concentration of 1-phenylcyclohexyl hydroperoxide in the reaction product. Meanwhile, cyclohexylbenzene is used for preparing standard solutions of cyclohexylbenzene with different concentrations, chromatographic pure acetonitrile is used as a solvent, a standard curve of cyclohexylbenzene is established, m 2 g of reaction products are taken and added into a volumetric flask, m 3 g of chromatographic pure acetonitrile is used as a diluent, the concentration of the reaction products is diluted, and the contents of cyclohexylbenzene and 1-phenylcyclohexyl hydroperoxide in the reaction products are subjected to high performance liquid phase analysis, so that the conversion rate of cyclohexylbenzene, the yield of 1-phenylcyclohexyl hydroperoxide and the selectivity of 1-phenylcyclohexyl hydroperoxide in the reaction are calculated.
In the examples and comparative examples, phenol and cyclohexanone were analyzed by gas chromatography normalization, and triphenylphosphine was added in time to the reaction products of different acidolysis times to derive the undecomposed 1-phenylcyclohexyl hydroperoxide into phenylcyclohexanol, to obtain a product system containing phenol, cyclohexanone, cyclohexylbenzene, phenylcyclohexanol and phenylhexanone, and the normalization analysis was performed using gas chromatography (sample inlet temperature 315 ℃, initial column temperature 60 ℃,3 minutes, temperature rise to 315 ℃ at a rate of 5 ℃/min, carrier gas flow rate of 5 ml/min). The amounts of cyclohexanone, phenol, cyclohexylbenzene, phenylcyclohexanol, and phenylhexanone species were each obtained as n 1,n2,n3,n4,n5 per g of liquid.
The amount of 1-phenylcyclohexyl hydroperoxide material per g of liquid mixture was determined by iodometry:
n1- Phenyl cyclohexyl hydroperoxide ＝c1×V×0.5/(m1×1000)
Cyclohexylbenzene quantitative standard curve:
w Cyclohexylbenzene (g/g)＝0.0022×A Cyclohexylbenzene +0.0027
1-phenylcyclohexyl hydroperoxide quantitative standard curve:
w1- Phenyl cyclohexyl hydroperoxide (g/g)＝0.0042×A1- Phenyl cyclohexyl hydroperoxide –0.0013
Wherein w Cyclohexylbenzene is the content of cyclohexylbenzene in the diluted reaction product, and A Cyclohexylbenzene is the peak area of cyclohexylbenzene in the high performance liquid chromatography; w 1- Phenyl cyclohexyl hydroperoxide is the 1-phenylcyclohexyl hydroperoxide content of the diluted reaction product, A 1- Phenyl cyclohexyl hydroperoxide is the 1-phenylcyclohexyl hydroperoxide peak area in high performance liquid chromatography.
Yield (%) = (m) of 1-phenylcyclohexyl hydroperoxide 2+m3)×w1- Phenyl cyclohexyl hydroperoxide /m2
Cyclohexylbenzene conversion (%) =w 0-(m2+m3)×w Cyclohexylbenzene /m2, where w 0 is the mass fraction of cyclohexylbenzene in the starting material.
Selectivity (%) of 1-phenylcyclohexyl hydroperoxide=yield (%) of 1-phenylcyclohexyl hydroperoxide ×160
Wherein n 0 is the amount of 1-phenylcyclohexyl hydroperoxide material in the feed before acidolysis begins.
Example 1
150G of cyclohexylbenzene and a supported catalyst, wherein the mass ratio of the supported catalyst to the cyclohexylbenzene is 0.02:1, are added into a 500 ml reaction kettle, are stirred at a stirring rate of 500 revolutions per minute, are heated to a preset temperature of 105 ℃ by using an electric heating furnace, are introduced with air at 500 ml/minute under a pressure of 1MPa, and react for 8 hours. After the reaction, the obtained mixture was filtered to obtain a liquid mixture containing 1-phenylcyclohexyl hydroperoxide. The liquid mixture was analyzed to determine the conversion of cyclohexylbenzene and the selectivity to 1-phenylcyclohexyl hydroperoxide, and the results are shown in Table 1.
Example 2
The process of this example is the same as that of example 1, except that the temperature of this example is heated to 115℃and the cyclohexylbenzene conversion and 1-phenylcyclohexyl hydroperoxide selectivity of this example are shown in Table 1.
TABLE 1
| Examples numbering | Example 1 | Example 2 |
| Reaction temperature/. Degree.C | 105 | 115 |
| Cyclohexylbenzene conversion/% | 21.55 | 58.04 |
| 1-Phenylcyclohexyl hydroperoxide selectivity/% | 86.80 | 52.09 |
From the results in table 1, it can be seen that: the method disclosed by the disclosure has good selectivity of the 1-phenylcyclohexyl hydroperoxide at the reaction temperature of 80-120 ℃, particularly, when the reaction temperature is 95-110 ℃, the oxidation side reaction in a reaction system is obviously reduced, and the selectivity of the 1-phenylcyclohexyl hydroperoxide is obviously increased.
Examples 3 to 6
The procedure of examples 3-6 was the same as in example 1, except that the reaction pressures of examples 3-6 were as shown in Table 2, and the conversion of cyclohexylbenzene and the selectivity to 1-phenylcyclohexyl hydroperoxide in examples were as shown in Table 2.
TABLE 2
From the results in table 2, it can be seen that: the method disclosed by the invention has good selectivity of the 1-phenylcyclohexyl hydroperoxide under the proper reaction pressure; in particular, 1-phenylcyclohexyl hydroperoxide selectivity is significantly increased at reaction pressures of 0.8 to 1.2 MPa.
Examples 7 to 9
The procedure of examples 7-9 is as in example 2, except that the reaction times of examples 7-9 are shown in Table 3, and the cyclohexylbenzene conversion and 1-phenylcyclohexyl hydroperoxide selectivity of this example are shown in Table 3.
TABLE 3 Table 3
| Examples numbering | Example 2 | Example 7 | Example 8 | Example 9 |
| Reaction time/h | 8 | 6 | 10 | 12 |
| Cyclohexylbenzene conversion/% | 21.55 | 12.05 | 29.03 | 40.51 |
| 1-Phenylcyclohexyl hydroperoxide selectivity/% | 86.80 | 91.66 | 83.41 | 68.94 |
From the results in table 3, it can be seen that: the method disclosed by the invention has good selectivity of the 1-phenylcyclohexyl hydroperoxide in a proper reaction time; in particular, 1-phenylcyclohexyl hydroperoxide selectivity was significantly increased over a reaction time of 6-10 hours.
Comparative example 1
The procedure of this comparative example was the same as in example 7 except that the catalyst used in this comparative example was commercially available copper oxide, and the conversion of cyclohexylbenzene and the selectivity to 1-phenylcyclohexyl hydroperoxide in this comparative example are shown in Table 4.
Comparative example 2
The procedure of this comparative example was the same as in example 10 except that the catalyst used in this comparative example was a catalyst B prepared by supporting N-hydroxyphthalimide on polystyrene microspheres, wherein the polystyrene microspheres were purchased from a national reagent, and the N-hydroxyphthalimide supported in the catalyst B was 0.06 wt.%, and the conversion of cyclohexylbenzene and the selectivity to 1-phenylcyclohexyl hydroperoxide in this comparative example were as shown in Table 4.
Comparative example 3
The procedure of this comparative example was the same as in example 10 except that the catalyst C used in this comparative example was a porous carbon material B containing no nitrogen element, wherein the porous carbon material B was purchased from a national reagent, and the conversion of cyclohexylbenzene and the selectivity of 1-phenylcyclohexyl hydroperoxide in this comparative example are shown in Table 4.
TABLE 4 Table 4
From the results in table 4, it can be seen that: the supported catalyst prepared by taking the porous carbon material containing nitrogen as a carrier has higher selectivity when the conversion rate is higher.
Examples 10 to 11
50G of cyclohexylbenzene catalytic oxidation product is added into a 100mL beaker, magnetons are added, stirring is carried out at the speed of 300 revolutions per minute, acidic substances are added, 1-phenylcyclohexyl hydroperoxide is catalytically decomposed to prepare phenol and cyclohexanone, the reaction is finished, and the selectivity of the phenol and the cyclohexanone is sampled and analyzed. The phenol and cyclohexanone selectivities are shown in table 5.
TABLE 5
| Examples numbering | Example 10 | Example 11 |
| Acidic substance | 98% Concentrated sulfuric acid | Sulfonic acid resin |
| Reaction temperature/. Degree.C | 20 | 50 |
| Acid (mass fraction/%) | 0.06 | 1 |
| Acidolysis time/h | 0.5 | 3 |
| 1-Phenylcyclohexyl hydroperoxide conversion/% | 100 | 70 |
| Phenol selectivity/% | 97.8 | 74.07 |
| Cyclohexanone selectivity/% | 93.4 | 70.67 |
From the results in table 5, it can be seen that: the method disclosed by the invention is used for decomposing under the catalysis of acidic substances, and has good 1-phenylcyclohexyl hydroperoxide conversion rate, high phenol selectivity and high cyclohexanone selectivity. In particular, when the acidic substance is concentrated sulfuric acid, the 1-phenylcyclohexyl hydroperoxide conversion is significantly increased.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (10)
1. A process for preparing phenol and cyclohexanone by catalytic oxidation of cyclohexylbenzene, the process comprising: contacting cyclohexylbenzene and oxygen-containing gas with a supported catalyst and performing catalytic oxidation reaction to obtain a first product containing 1-phenylcyclohexyl hydroperoxide; subjecting the first product to a decomposition reaction under acidic conditions;
Wherein the supported catalyst comprises a carrier and N-hydroxyphthalimide compounds supported on the carrier; the carrier is a porous inorganic carbon material containing nitrogen element.
2. The method according to claim 1, wherein the catalytic oxidation reaction is carried out at a temperature of 80-120 ℃, preferably 95-110 ℃; the reaction pressure is 0.1-3MPa, preferably 0.8-1.2MPa; the reaction time is 3 to 15 hours, preferably 6 to 10 hours.
3. The process according to claim 1, wherein the loading of N-hydroxyphthalimide compounds is 0.1-50 wt%, preferably 1-30 wt%, based on the total weight of the supported catalyst;
Optionally, the N-hydroxyphthalimide compound is selected from at least one of N-hydroxyphthalimide and 3,4,5, 6-tetrachloro-N-hydroxyphthalimide.
4. The method according to claim 1, wherein the nitrogen element content is 0.5-60 wt%, preferably 1.1-43 wt%, based on the total weight of the porous inorganic carbon material;
Optionally, the porous inorganic carbon material has a specific surface area of 1-800m 2/g, preferably 2-300m 2/g; the pore size of the accessible pores is in the range of 2-30nm, preferably in the range of 5-20 nm; the pore volume is 0.01-0.7mL/g, preferably 0.06-0.5mL/g.
5. The process according to claim 1, wherein the mass fraction of the supported catalyst is 0.01-30%, preferably 0.1-15% based on the total mass of cyclohexylbenzene and the supported catalyst.
6. The method of any of claims 1-5, wherein the supported catalyst is prepared by:
S1, dissolving an N-hydroxyphthalimide compound in an organic solvent to obtain a first mixed solution;
s2, impregnating the carrier by using the first mixed solution, stirring and standing to obtain a first mixture;
s3, drying the first mixture.
7. The method according to claim 6, wherein the organic solvent is selected from at least one of acetonitrile, ethanol, and tetrahydrofuran; the conditions of the impregnation include: the temperature is 20-40 ℃ and the time is 1-6h; the conditions of the drying treatment include: the temperature is 80-130 ℃ and the time is 4-6h.
8. The method of claim 1, wherein the volume fraction of oxygen in the oxygen-containing gas is from 5 to 100% based on the total volume of the oxygen-containing gas; preferably, the volume fraction of oxygen in the oxygen-containing gas is 21-100%.
9. The process according to claim 1 or 8, wherein the oxygen-containing gas is introduced at a rate of 0.1-5mL/min, preferably 0.5-1.5mL/min, in terms of oxygen, relative to 1mL of cyclohexylbenzene.
10. A process according to claim 1, wherein the decomposition reaction comprises decomposing the first product under catalysis of an acidic substance selected from solid and/or liquid acids, preferably liquid acids, more preferably sulfuric acid; the decomposition temperature is 20-50 ℃, and the decomposition time is 0.3-2h.
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