Hexafluoropropylene trimer modified bimetallic porous silicon, and preparation method and application thereof

Abstract

The application discloses a kind of hexafluoropropylene trimer modified bimetallic porous silicon and its preparation method and application, the preparation method of hexafluoropropylene trimer modified bimetallic porous silicon is as follows: the silane containing hexafluoropropylene trimer functional group, bimetallic porous silicon is dispersed in alcohol solvent with deionized water, under N2 atmosphere, 20~120 ℃ stirring reaction 6.0 h~96.0 h.The reaction mixture is extracted by filtration under reduced pressure, washed with ethanol, washed with water, vacuum dried, and hexafluoropropylene trimer modified bimetallic porous silicon is obtained.The application also provides a kind of hexafluoropropylene trimer modified bimetallic porous silicon in O2 catalytic oxidation naphthenic hydrocarbon application.The naphthenic hydrocarbon oxidation method provided by the application has high selectivity of partial oxidation products (naphthenyl alcohol and naphthenyl ketone), low content of explosive peroxide and deep oxidation product aliphatic diacid, and is a safe, effective and low-energy-consumption naphthenic hydrocarbon oxidation method.

Description

TECHNICAL FIELD

[0001] The present application relates to a hexafluoropropylene trimer modified bimetallic porous silicon and a preparation method thereof and application of the bimetallic porous silicon as a catalyst in partial oxidation of naphthenes, and belongs to the field of organic catalysis and fine organic synthesis. BACKGROUND

[0002] Catalytic oxidation of naphthene can convert hydrocarbons widely existing in fossil resources into high-value-added alcohol and ketone compounds, which have wide applications in chemical industry (ZL 202111006432.X; ZL 202010884408.5; ZL 201911161924.9). However, due to the higher chemical activity of the generated partial oxidation products (naphthene alcohol and naphthene ketone) than the substrate naphthene, the partial oxidation products are prone to deep oxidation to generate aliphatic diacid and its derivatives, which not only reduces the selectivity of the partial oxidation products, increases the energy consumption and equipment requirements of separation and purification, but also the generated aliphatic diacid and its derivatives are easy to crystallize, causing pipeline blockage and great difficulty for industrial production. In industry, in order to ensure better selectivity of the partial oxidation products (naphthene alcohol and naphthene ketone), the conversion rate of cyclohexane is usually controlled at about 5% to achieve a selectivity of about 85% of the partial oxidation products (Chemical Engineering Journal, 2022, 443: 136126; Chemical Engineering Science, 2022, 260: 117825; Molecular Catalysis, 2023, 535: 112853). Further increasing the substrate conversion rate will significantly reduce the selectivity of the partial oxidation products (cyclohexanol and cyclohexanone), and it is impossible to simultaneously improve the substrate conversion rate and the selectivity of the partial oxidation products. In addition to the higher reactivity of the oxidation products (naphthene alcohol and naphthene ketone), another important reason for the above problems is the frequent contact of the partial oxidation products with the catalytically active center. In the current chemical industry, the catalysts used for catalytic oxidation of naphthene are mainly cobalt (II) and manganese (II) salts, complexes and their derivatives. The above catalysts can not only catalyze O2 to oxidize the C-H bond of naphthene to partial oxidation products such as alcohol and ketone, but also can catalyze O2 to oxidize alcohol and ketone compounds to deep oxidation products. Therefore, effectively avoiding the frequent contact of the partial oxidation products (naphthene alcohol and naphthene ketone) with the catalytically active center will be beneficial to avoid the deep oxidation of alcohol and ketone compounds during the partial oxidation of naphthene, and realize the efficient and selective oxidation of O2 to the partial oxidation products naphthene alcohol and naphthene ketone. By realizing the high-selectivity preparation of naphthene alcohol and naphthene ketone, it is not only beneficial to reduce the difficulty and equipment requirements of separation and purification of the partial oxidation products of naphthene in industry, reduce the separation energy consumption, but also can effectively prevent safety accidents caused by pipeline blockage, which has important significance for the safe, energy-saving and emission-reducing production of naphthene in industry.

[0003] The fluorine-containing compound has strong hydrophobicity and strong repulsion to some oil compounds, especially to some organic compounds with strong polarity, due to its low polarity (CN115926069A; WO 2022059620A1). The partial oxidation of naphthenes to naphthenic alcohols and naphthenic ketones is a process of increasing polarity, and the partial oxidation of naphthenes with low polarity to naphthenic alcohols and naphthenic ketones with increased polarity. Therefore, the present application modifies the catalytic material for the partial oxidation of naphthenes with a low-polarity fluorocarbon chain, which is beneficial to the separation of naphthenic alcohols and naphthenic ketones with strong polarity from the catalytically active center and avoids the contact of the disordered diffusion process with the catalytically active center, preventing deep oxidation. In the above process, due to the low polarity of naphthenes, the introduction of a fluorocarbon chain has little effect on the contact of naphthenes with the catalytically active center, which can make the substrate naphthene contact the catalytically active center smoothly and be partially oxidized to naphthenic alcohol and naphthenic ketone. Therefore, the modification of the naphthene partial oxidation catalyst with a fluorocarbon chain is beneficial to the efficient and selective catalytic oxidation of naphthenes to naphthenic alcohols and naphthenic ketones, which has important significance for the safe, energy-saving and emission-reducing production of naphthenes in industry. SUMMARY

[0004] In view of the above technical problems existing in the prior art, the purpose of the present application is to provide a hexafluoropropene trimer modified bimetallic porous silicon and its preparation method and its application as a catalyst in the partial oxidation of naphthenes. The catalyst of the present application uses hexafluoropropene trimer as a modification group, which makes the partial oxidation products naphthenic alcohol and naphthenic ketone separate from the catalytically active center in time, prevents the contact of the partial oxidation products with the catalytically active center, prevents deep oxidation, and improves the selectivity of the partial oxidation products; the bimetallic center relay catalysis effectively regulates the catalytic conversion of naphthenic peroxide, an intermediate product in oxidation, further improves the selectivity of naphthenic alcohol and naphthenic ketone, and prevents accidents that may be caused by peroxide accumulation. The naphthene partial oxidation method of the present application not only has high selectivity of naphthenic alcohol and naphthenic ketone, but also has low content of naphthenic hydroperoxide and high safety factor, which is an efficient, feasible and safe method for the partial catalytic oxidation of naphthenes to synthesize naphthenic alcohol and naphthenic ketone.

[0005] The technical scheme adopted by the present application is as follows:

[0006] A hexafluoropropene trimer modified bimetallic porous silicon contains a fluorine-containing functional functional group as shown in formula (I):

[0007]

[0008] The bimetallic center of the bimetallic porous silicon is any one of Co(II)-Cu(II), Co(II)-Zn(II), Co(II)-Ni(II), Co(II)-Fe(II), Mn(II)-Cu(II), Mn(II)-Zn(II), Mn(II)-Ni(II), Mn(II)-Fe(II).

[0009] The preparation method of the bimetallic porous silicon modified by the hexafluoropropene trimer comprises the following steps: dispersing a silane containing a hexafluoropropene trimer functional group, bimetallic porous silicon and deionized water in an alcohol solvent, stirring and reacting at a temperature of 20-200 ℃ under N2 atmosphere for 6.0-96.0 h; the reaction mixture is filtered under reduced pressure, washed with ethanol and water, and vacuum dried to obtain the bimetallic porous silicon modified by the hexafluoropropene trimer; the mass ratio of the silane containing the hexafluoropropene trimer functional group to the bimetallic porous silicon is 1:20-200, preferably 1:60-100; the mass ratio of the deionized water to the bimetallic porous silicon is 1:20-200, preferably 1:20-60. The reaction temperature is preferably 60-90 ℃.

[0010] The preparation method of the bimetallic porous silicon comprises the following steps: dissolving MeIM, a first metal salt and a second metal salt in water, stirring for 1-4 hours, then adding TEOS dropwise into the solution, stirring vigorously at room temperature for 5-20 hours, washing with ethanol and water in sequence, then re-dispersing the product with water, and then transferring to a polytetrafluoroethylene-lined autoclave, reacting in an oven at 60-80 ℃ for 6-10 h, and further reacting at 110-130 ℃ for 10-15 h; collecting the product by suction filtration, washing with water and ethanol in sequence, drying, and calcining at 550-650 ℃ in air for 10-30 hours to complete the preparation;

[0011] The first metal salt is a Co salt or a Mn salt, and the molar ratio of the first metal salt to MeIM is 1:5-100, preferably 1:50;

[0012] The second metal salt is a Cu, Zn, Ni or Fe salt, and the molar ratio of the second metal salt to the first metal salt is 1:5-100, preferably 1:50;

[0013] The molar ratio of TEOS to MeIM is 0.8-1.2:1, preferably 1:1.

[0014] Further, the silane containing a hexafluoropropene trimer functional group has a branched structure as shown in formula (II) or formula (III):

[0015]

[0016] Further, the alcohol solvent is any one of methanol, ethanol, isopropanol, n-propanol or any mixture thereof, preferably any one of methanol, ethanol, isopropanol or any mixture thereof.

[0017] Further, the mass ratio of the branched hexafluoropropene trimer modified bimetallic porous silicon to the cycloalkane is 1:5-1000, preferably 1:100-300, the unit of mass is mg, and the unit of amount of substance is mmol. The cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclododecane. The partial oxidation product includes cycloalkyl alcohol and cycloalkyl ketone.

[0018] The technical concept of the present application is that the branched hexafluoropropene trimer modified bimetallic porous silicon is used as a catalyst to catalyze the partial oxidation of cycloalkane by O2 to prepare partial oxidation products cycloalkyl alcohol and cycloalkyl ketone. The branched hexafluoropropene trimer is used as a modification group to make the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone timely separate from the catalytically active center, prevent the contact between the partial oxidation products and the catalytically active center, prevent the deep oxidation of the partial oxidation products, and improve the selectivity of the partial oxidation products. The bimetallic center is used to relay catalyze and effectively control the catalytic conversion of the oxidation intermediate cycloalkyl hydroperoxide, further improve the selectivity of cycloalkyl alcohol and cycloalkyl ketone, and prevent the accidents caused by the accumulation of peroxide. Therefore, the cycloalkane partial oxidation method of the present application not only has high selectivity of cycloalkyl alcohol and cycloalkyl ketone, but also has low cycloalkyl hydroperoxide content and high safety factor, and has the potential to solve the problem that the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone are easy to be deeply oxidized to generate aliphatic diacid and other by-products in the process of industrial catalytic oxidation of cycloalkane, and to realize the efficient synthesis of partial oxidation products. Not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity of other catalytic oxidation systems.

[0019] The beneficial effects of the present application mainly include that the branched hexafluoropropene trimer modified bimetallic porous silicon is used as a catalyst, which is ingenious in design, novel in structure, and widely applicable. In the partial oxidation reaction of cycloalkane, the selectivity of cycloalkyl alcohol and cycloalkyl ketone is high, which effectively inhibits the deep oxidation of the partial oxidation products and the generation of aliphatic diacid and its derivatives. The low selectivity of aliphatic diacid and its derivatives is also beneficial to the continuous process of cycloalkane partial oxidation and the low-energy consumption separation of products. The present application has the potential to solve the problem that the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone are easy to be deeply oxidized to generate aliphatic diacid and other by-products in the process of industrial catalytic oxidation of cycloalkane, and to realize the efficient synthesis of partial oxidation products. Not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity of other catalytic oxidation systems. The present application is a new method for selective catalytic oxidation of cycloalkane with high efficiency and feasibility. DETAILED DESCRIPTION

[0020] The application will be further described in connection with specific examples, but the scope of the application is not limited thereto.

[0021] Examples 1-4 are the synthesis of the bimetallic porous silicon precursor;

[0022] Examples 5-6 are the synthesis of the hexafluoropropene trimer precursor;

[0023] Examples 7-28 are the synthesis of the hexafluoropropene trimer modified bimetallic porous silicon catalyst;

[0024] Examples 29-50 are comparative experiments of the application of the hexafluoropropene trimer modified bimetallic porous silicon catalyst in naphthene partial oxidation reaction;

[0025] Examples 51-54 are comparative experiments of the application of the hexafluoropropene trimer modified bimetallic porous silicon catalyst in naphthene partial oxidation reaction with the precursor;

[0026] Examples 55-58 are the application of the hexafluoropropene trimer modified bimetallic porous silicon catalyst in different naphthene partial oxidation reactions;

[0027] Example 59 is a scale-up experiment of the application of the hexafluoropropene trimer modified bimetallic porous silicon catalyst in naphthene partial oxidation reaction.

[0028] The bimetallic porous silicon Si@M1@M2 used in the application is synthesized by reference to the preparation method of monometallic porous silicon in Inorganic Chemistry 2020, 59: 767-776. The silanes (II) and (III) containing hexafluoropropene trimer functional groups used are self-made in the laboratory (Chemical Engineering of Chinese Universities, 2009, 23(4): 679-683; Pesticides, 2007, 46(8): 520-522.). Other reagents used are commercially available analytical pure.

[0029] Naming rules for hexafluoropropene trimer modified bimetallic porous silicon. Si@Co@Cu@F(II)-60@75@80@72 indicates that the bimetallic (Co@Cu) porous silicon is modified by the silane (II) containing hexafluoropropene trimer functional groups, the mass ratio of the silane containing hexafluoropropene trimer functional groups to the bimetallic porous silicon in the modification reaction is 1:60, the mass ratio of deionized water to the bimetallic porous silicon is 1:75, the reaction temperature is 80°C, and the reaction time is 72.0h.

[0030]

[0031] Example 1

[0032] MeIM (2.4633 g, 30 mmol), Co(N03)2-6H20 (0.1746 g, 0.60 mmol), Cu(N03)2-3H20 (0.1450 g, 0.60 mmol) were dissolved in H20 (20 ml), stirred for three hours, then TEOS (6.2498 g, 30 mmol) was added dropwise to the solution, further stirred vigorously at room temperature for 12 h, washed with ethanol (3 x 50 mL), washed with water (3 x 50 mL), replenished with deionized water (20 mL), then transferred to a Teflon-lined autoclave, reacted at 70 °C in an oven for 8 h, and further reacted at 120 °C for 12 h. Collected by suction filtration, washed with water (3 x 50 mL), washed with ethanol (3 x 50 mL), and dried in a vacuum oven at 75 °C overnight. The resulting solid sample was subsequently calcined in air at 600 °C for 20 hours to obtain the bimetallic porous silicon Si@Co@Cu-1 : 1@41.7563 g.

[0033] Example 2

[0034] Example 2 catalyst preparation process repeated Example 1, the only difference is that "Cu(N03)2-3H20 (0.1450 g, 0.60 mmol), replaced by Ni(N03)2-6H20 (0.1745 g, 0.60 mmol)", the rest of the conditions repeated Example 1, finally obtained bimetallic porous silicon Si@Co@Ni-1 : 1@41.8164 g.

[0035] Example 3

[0036] Example 3 catalyst preparation process repeated Example 1, the only difference is that "Cu(N03)2-3H20 (0.1450 g, 0.60 mmol), replaced by Zn(N03)2-6H20 (0.1785 g, 0.60 mmol)", the rest of the conditions repeated Example 1, finally obtained bimetallic porous silicon Si@Co@Zn-1 : 1@41.8265 g.

[0037] Example 4

[0038] Example 4 catalyst preparation process repeated Example 1, the only difference is that "Co(N03)2-6H20 (0.1746 g, 0.60 mmol), replaced by Mn(N03)2-4H20 (0.1506 g, 0.60 mmol)", the rest of the conditions repeated Example 1, finally obtained bimetallic porous silicon Si@Mn@Cu-1 : 1@41.5236 g.

[0039] Example 5

[0040] In a 250 mL three-necked round-bottom flask, trimeric hexafluoropropene (4.5006 g, 10.0 mmol) and 4-hydroxybenzyl chloride (1.4258 g, 10.0 mmol) were stirred and dispersed in pure dichloromethane (150 mL) with a steady N2purge for 1.0 min, N2was turned off, and stirring was continued for 12 h. 3-aminopropyltrimethoxysilane (1.7937 g, 10.0 mmol) and triethylamine (2.0238 g, 20.0 mmol) were added dropwise, and stirring was continued for 12 h. The product was concentrated and purified by column chromatography to obtain silane (II) containing hexafluoropropene trimer functional groups (6.7415 g).

[0041] Example 6

[0042] Example 6 The preparation process of the catalyst of Example 6 was repeated, except that “3-aminopropyltrimethoxysilane (1.7937 g, 10.0 mmol) was replaced by 3-aminopropyltriethoxysilane (2.2137 g, 10.0 mmol)”, and the other conditions were repeated as in Example 5. Finally, silane (III) containing hexafluoropropene trimer functional groups (6.9467 g) was obtained.

[0043] Example 7

[0044] In a 250 mL three-necked round-bottom flask, silane (II) containing hexafluoropropene trimer functional groups (0.2500 g), bimetallic porous silicon Si@Co@Cu (15.00 g), and deionized water (0.2500 g) were stirred and dispersed in analytical pure anhydrous ethanol (150 mL) with a steady N2purge for 1.0 min, and N2was turned off. Under an N2atmosphere, the temperature was increased to 80°C, and the reaction temperature was maintained while stirring for 60.0 h. After the reaction was completed, the temperature was decreased to room temperature while stirring, the reaction mixture was filtered under reduced pressure, the obtained filter cake was washed with ethanol (3 x 50 mL) and water (3 x 50 mL), and vacuum drying was performed at 80°C for 8.0 h to obtain hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@60 14.16 g.

[0045] Example 8

[0046] The preparation process of the catalyst of Example 8 was repeated, except that “silane (II) containing hexafluoropropene trimer functional groups (0.2500 g) was replaced by silane (III) containing hexafluoropropene trimer functional groups (0.2500 g)”, and the other conditions were repeated as in Example 7. Finally, hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(III)-60@60@80@60 14.41 g was obtained.

[0047] Example 9

[0048] The preparation process of the catalyst of Example 9 repeats Example 7, with the only difference being that "bimetallic porous silicon Si@Co@Cu (15.00 g) is replaced by bimetallic porous silicon Si@Co@Ni (15.00 g)", and the rest of the conditions repeat Example 7, finally obtaining hexafluoropropylene trimer modified bimetallic porous silicon Si@Co@Ni@F(II)-60@60@80@60 14.32 g.

[0049] Example 10

[0050] The preparation process of the catalyst of Example 10 repeats Example 7, with the only difference being that "bimetallic porous silicon Si@Co@Cu (15.00 g) is replaced by bimetallic porous silicon Si@Co@Zn (15.00 g)", and the rest of the conditions repeat Example 7, finally obtaining hexafluoropropylene trimer modified bimetallic porous silicon Si@Co@Zn@F(II)-60@60@80@60 14.73 g.

[0051] Example 11

[0052] The preparation process of the catalyst of Example 11 repeats Example 7, with the only difference being that "bimetallic porous silicon Si@Co@Cu (15.00 g) is replaced by bimetallic porous silicon Si@Mn@Cu (15.00 g)", and the rest of the conditions repeat Example 7, finally obtaining hexafluoropropylene trimer modified bimetallic porous silicon Si@Mn@Cu@F(II)-60@60@80@60 14.22 g.

[0053] Example 12

[0054] The preparation process of the catalyst of Example 12 repeats Example 7, with the only difference being that "silane (II) containing hexafluoropropylene trimer functional groups (0.2500 g) is replaced by silane (II) containing hexafluoropropylene trimer functional groups (0.7500 g)", and the rest of the conditions repeat Example 7, finally obtaining hexafluoropropylene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-20@60@80@60 14.30 g.

[0055] Example 13

[0056] The preparation process of the catalyst of Example 13 repeats Example 7, with the only difference being that "silane (II) containing hexafluoropropylene trimer functional groups (0.2500 g) is replaced by silane (II) containing hexafluoropropylene trimer functional groups (0.1500 g)", and the rest of the conditions repeat Example 7, finally obtaining hexafluoropropylene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-100@60@80@60 14.10 g.

[0057] Example 14

[0058] Example 14 The preparation process of catalyst repeats Example 7, the only difference is that “silane (II) containing hexafluoropropene trimer functional group (0.2500 g) is replaced by silane (II) containing hexafluoropropene trimer functional group (0.0750 g)”, the rest repeats Example 7, finally hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-200@60@80@60 14.05 g is obtained.

[0059] Example 15

[0060] Example 15 The preparation process of catalyst repeats Example 7, the only difference is that “stirring with deionized water (0.2500 g) is replaced by stirring with deionized water (0.7500 g)”, the rest repeats Example 7, finally hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@20@80@60 14.28 g is obtained.

[0061] Example 16

[0062] Example 16 The preparation process of catalyst repeats Example 7, the only difference is that “stirring with deionized water (0.2500 g) is replaced by stirring with deionized water (0.3000 g)”, the rest repeats Example 7, finally hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@50@80@60 14.35 g is obtained.

[0063] Example 17

[0064] Example 17 The preparation process of catalyst repeats Example 7, the only difference is that “stirring with deionized water (0.2500 g) is replaced by stirring with deionized water (0.0750 g)”, the rest repeats Example 7, finally hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@200@80@60 13.65 g is obtained.

[0065] Example 18

[0066] Example 18 The preparation process of catalyst repeats Example 7, the only difference is that “dissolved in analytical pure anhydrous ethanol (150 mL) is replaced by dissolved in analytical pure anhydrous methanol (150 mL)”, the rest repeats Example 7, finally hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@60 14.29 g is obtained.

[0067] Example 19

[0068] Example 19 The preparation process of catalyst repeats Example 7, the only difference is that "dissolved in analytical pure anhydrous ethanol (150 mL), replaced by dissolved in analytical pure anhydrous isopropanol (150 mL)", the rest of the conditions repeat Example 7, finally get hexafluoropropene trimer modified double metal porous silicon Si@Co@Cu@F(II)-60@60@80@6014.37 g.

[0069] Example 20

[0070] The preparation process of catalyst repeats Example 7, the only difference is that "dissolved in analytical pure anhydrous ethanol (150 mL), replaced by dissolved in analytical pure anhydrous n-propanol (150 mL)", the rest of the conditions repeat Example 7, finally

[0071] hexafluoropropene trimer modified double metal porous silicon Si@Co@Cu@F(II)-60@60@80@6014.85 g.

[0072] Example 21

[0073] The preparation process of catalyst repeats Example 7, the only difference is that "stirring to 80 ℃, replaced by stirring to 20 ℃", the rest of the conditions repeat Example 7, finally get hexafluoropropene trimer modified double metal porous silicon Si@Co@Cu@F(II)-60@60@20@6012.35 g.

[0074] Example 22

[0075] The preparation process of catalyst repeats Example 7, the only difference is that "stirring to 80 ℃, replaced by stirring to 60 ℃", the rest of the conditions repeat Example 7, finally get hexafluoropropene trimer modified double metal porous silicon Si@Co@Cu@F(II)-60@60@60@6013.67 g.

[0076] Example 23

[0077] The preparation process of catalyst repeats Example 7, the only difference is that "stirring to 80 ℃, replaced by stirring to 90 ℃", the rest of the conditions repeat Example 7, finally get hexafluoropropene trimer modified double metal porous silicon Si@Co@Cu@F(II)-60@60@90@6014.22 g.

[0078] Example 24

[0079] The preparation process of the catalyst of Example 24 was repeated as in Example 7, except that "stirring was raised to 80°C, replaced by stirring was raised to 120°C", and the rest of the conditions were repeated as in Example 7, finally obtaining the hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@120@6013.75 g.

[0080] Example 25

[0081] The preparation process of the catalyst of Example 25 was repeated as in Example 7, except that "the reaction temperature was kept stirring for 60.0 h, replaced by the reaction temperature was kept stirring for 6.0 h", and the rest of the conditions were repeated as in Example 7, finally obtaining the hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@612.99 g.

[0082] Example 26

[0083] The preparation process of the catalyst of Example 26 was repeated as in Example 7, except that "the reaction temperature was kept stirring for 60.0 h, replaced by the reaction temperature was kept stirring for 48.0 h", and the rest of the conditions were repeated as in Example 7, finally obtaining the hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@4813.68 g.

[0084] Example 27

[0085] The preparation process of the catalyst of Example 27 was repeated as in Example 7, except that "the reaction temperature was kept stirring for 60.0 h, replaced by the reaction temperature was kept stirring for 72.0 h", and the rest of the conditions were repeated as in Example 7, finally obtaining the hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@7214.28 g.

[0086] Example 28

[0087] The preparation process of the catalyst of Example 28 was repeated as in Example 7, except that "the reaction temperature was kept stirring for 60.0 h, replaced by the reaction temperature was kept stirring for 96.0 h", and the rest of the conditions were repeated as in Example 7, finally obtaining the hexafluoropropene trimer modified bimetallic porous silicon Si@Co@Cu@F(II)-60@60@80@9614.85 g.

[0088] Example 29

[0089] In a 100 mL stainless steel autoclave with polytetrafluoroethylene liner, the catalyst obtained in Example 7 (1.0 mg) was dispersed in cyclohexane (16.8320 g, 200 mmol), the reaction system was sealed, and the temperature was increased to 125°C with stirring. When the temperature reached the set temperature, oxygen was introduced to 1.00 MPa, and the temperature and oxygen pressure were maintained at the set values, and the reaction was stirred for 8.0 h. After the reaction was completed, the reaction liquid was stirred to room temperature, and a small amount of residual cycloalkyl hydroperoxide was completely decomposed and converted at room temperature for 6.0 h. After the reaction was completed, the residual gas was slowly released, the reaction kettle was opened, and anhydrous methanol was added to 100 mL. 10 mL of the constant volume solution was accurately removed, toluene (0.1843 g, 2.0 mmol) was added as a gas phase analysis internal standard for GC analysis to determine the conversion rate of the substrate cyclohexane, the yield and selectivity of the partial oxidation products cyclohexanol and cyclohexanone; 10 mL of the constant volume solution was accurately removed, benzoic acid (0.1221 g, 1.0 mmol) was added as a liquid phase analysis internal standard for HPLC analysis to determine the yield and selectivity of the deep oxidation products adipic acid and glutaric acid. GC and HPLC analysis showed that the conversion rate of cyclohexane was 12.6%, the selectivity of cyclohexanol was 46%, the selectivity of cyclohexanone was 51%, the selectivity of adipic acid was 3%, and glutaric acid and other by-products were not detected.

[0090] Example 30

[0091] Example 30 The catalytic experiment of Example 29 was repeated, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 8 (1.0 mg)", and the other conditions were repeated according to Example 29. Finally, the conversion rate of cyclohexane was 12.1%, the selectivity of cyclohexanol was 44%, the selectivity of cyclohexanone was 52%, the selectivity of adipic acid was 4%, and glutaric acid and other by-products were not detected.

[0092] Example 31

[0093] Example 31 The catalytic experiment of Example 29 was repeated, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 9 (1.0 mg)", and the other conditions were repeated according to Example 29. Finally, the conversion rate of cyclohexane was 11.7%, the selectivity of cyclohexanol was 46%, the selectivity of cyclohexanone was 52%, the selectivity of adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0094] Example 32

[0095] Example 32 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 10 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 12.0%, the selectivity of cyclohexanol was 42%, the selectivity of cyclohexanone was 56%, the selectivity of adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0096] Example 33

[0097] Example 33 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 11 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 10.7%, the selectivity of cyclohexanol was 39%, the selectivity of cyclohexanone was 60%, the selectivity of adipic acid was 1%, and glutaric acid and other by-products were not detected.

[0098] Example 34

[0099] Example 34 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 12 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 12.3%, the selectivity of cyclohexanol was 47%, the selectivity of cyclohexanone was 51%, the selectivity of adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0100] Example 35

[0101] Example 35 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 13 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 12.4%, the selectivity of cyclohexanol was 46%, the selectivity of cyclohexanone was 52%, the selectivity of adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0102] Example 36

[0103] Example 36 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 14 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 10.8%, the selectivity of cyclohexanol was 40%, the selectivity of cyclohexanone was 57%, the selectivity of adipic acid was 3%, and glutaric acid and other by-products were not detected.

[0104] Example 37

[0105] Example 37 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 15 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 11.8%, the selectivity of cyclohexanol was 36%, the selectivity of cyclohexanone was 60%, the selectivity of adipic acid was 4%, and glutaric acid and other by-products were not detected.

[0106] Example 38

[0107] Example 38 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 16 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 12.0%, the selectivity of cyclohexanol was 40%, the selectivity of cyclohexanone was 57%, the selectivity of adipic acid was 3%, and glutaric acid and other by-products were not detected.

[0108] Example 39

[0109] Example 39 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 17 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 11.5%, the selectivity of cyclohexanol was 41%, the selectivity of cyclohexanone was 56%, the selectivity of adipic acid was 3%, and glutaric acid and other by-products were not detected.

[0110] Example 40

[0111] Example 40 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 18 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 12.0%, the selectivity of cyclohexanol was 44%, the selectivity of cyclohexanone was 52%, the selectivity of adipic acid was 4%, and glutaric acid and other by-products were not detected.

[0112] Example 41

[0113] Example 41 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 19 (1.0 mg)", and the other conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 11.6%, the selectivity of cyclohexanol was 38%, the selectivity of cyclohexanone was 57%, the selectivity of adipic acid was 5%, and glutaric acid and other by-products were not detected.

[0114] Example 42

[0115] Example 42 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 20 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 10.5%, the cyclohexanol selectivity was 45%, the cyclohexanone selectivity was 54%, the adipic acid selectivity was 1%, and glutaric acid and other by-products were not detected.

[0116] Example 43

[0117] Example 43 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 21 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 10.7%, the cyclohexanol selectivity was 40%, the cyclohexanone selectivity was 58%, the adipic acid selectivity was 2%, and glutaric acid and other by-products were not detected.

[0118] Example 44

[0119] Example 44 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 22 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 12.4%, the cyclohexanol selectivity was 37%, the cyclohexanone selectivity was 58%, the adipic acid selectivity was 5%, and glutaric acid and other by-products were not detected.

[0120] Example 45

[0121] Example 45 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 23 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 11.9%, the cyclohexanol selectivity was 41%, the cyclohexanone selectivity was 54%, the adipic acid selectivity was 5%, and glutaric acid and other by-products were not detected.

[0122] Example 46

[0123] Example 46 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 24 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 10.3%, the cyclohexanol selectivity was 48%, the cyclohexanone selectivity was 51%, the adipic acid selectivity was 1%, and glutaric acid and other by-products were not detected.

[0124] Example 47

[0125] Example 47 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 25 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 11.4%, the cyclohexanol selectivity was 41%, the cyclohexanone selectivity was 57%, the adipic acid selectivity was 2%, and glutaric acid and other by-products were not detected.

[0126] Example 48

[0127] Example 48 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 26 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 12.4%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 57%, the adipic acid selectivity was 4%, and glutaric acid and other by-products were not detected.

[0128] Example 49

[0129] Example 49 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 27 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 11.7%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 56%, the adipic acid selectivity was 3%, and glutaric acid and other by-products were not detected.

[0130] Example 50

[0131] Example 50 The catalytic experiment was repeated as in Example 29, except that "the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 28 (1.0 mg)", and the other conditions were repeated as in Example 29. The final cyclohexane conversion was 11.3%, the cyclohexanol selectivity was 39%, the cyclohexanone selectivity was 56%, the adipic acid selectivity was 3%, and glutaric acid and other by-products were not detected.

[0132] Example 51

[0133] Example 51 The catalytic experiment was repeated as in Example 29, except that "dispersion in cyclohexane (16.8320, 200 mmol) was replaced by dispersion in cyclopentane (14.0280, 200 mmol)", and the other conditions were repeated as in Example 29. The final cyclopentane conversion was 11.4%, the cyclopentanol selectivity was 20%, the cyclopentanone selectivity was 65%, the glutaric acid selectivity was 15%, and succinic acid and other by-products were not detected.

[0134] Example 52

[0135] Example 52 The catalytic experiment was repeated as in Example 29, except that "dispersed in cyclohexane (16.8 g, 200 mmol) was replaced by dispersed in cycloheptane (19.6 g, 200 mmol)", and the rest of the conditions were repeated as in Example 29. The final conversion of cycloheptane was 24.5%, the selectivity to cycloheptanol was 26%, the selectivity to cycloheptanone was 61%, the selectivity to heptanedioic acid was 3%, and no adipic acid or other byproducts were detected.

[0136] Example 53

[0137] Example 53 The catalytic experiment was repeated as in Example 29, except that "dispersed in cyclohexane (16.8 g, 200 mmol) was replaced by dispersed in cyclooctane (22.4 g, 200 mmol)", and the rest of the conditions were repeated as in Example 29. The final conversion of cyclooctane was 30.1%, the selectivity to cyclooctanol was 46%, the selectivity to cyclooctanone was 51%, the selectivity to octanedioic acid was 3%, and no heptanedioic acid or other byproducts were detected.

[0138] Example 54

[0139] Example 54 The catalytic experiment was repeated as in Example 29, except that "dispersed in cyclohexane (16.8 g, 200 mmol) was replaced by cyclododecane (33.6 g, 200 mmol)", and the rest of the conditions were repeated as in Example 29. The final conversion of cyclododecane was 38.6%, the selectivity to cyclododecanol was 46%, the selectivity to cyclododecanone was 54%, and no cyclododecanedioic acid, cycloundecanedioic acid, or other byproducts were detected.

[0140] Example 55

[0141] Example 55 The catalytic experiment was repeated as in Example 29, except that "the catalyst from Example 7 (1.0 mg) was replaced by the catalyst from Example 1 (1.0 mg)", and the rest of the conditions were repeated as in Example 29. The final conversion of cyclohexane was 7.5%, the selectivity to cyclohexanol was 34%, the selectivity to cyclohexanone was 51%, the selectivity to adipic acid was 11%, the selectivity to glutaric acid was 4%, and no other byproducts were detected.

[0142] Example 56

[0143] Example 65 The catalytic experiment was repeated as in Example 29, except that "the catalyst from Example 7 (1.0 mg) was replaced by the catalyst from Example 2 (1.0 mg)", and the rest of the conditions were repeated as in Example 29. The final conversion of cyclohexane was 6.9%, the selectivity to cyclohexanol was 40%, the selectivity to cyclohexanone was 46%, the selectivity to adipic acid was 10%, the selectivity to glutaric acid was 4%, and no other byproducts were detected.

[0144] Example 57

[0145] Example 57 The catalytic experiment was repeated as in Example 29, except that the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 3 (1.0 mg), and the rest of the conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 6.7%, the selectivity of cyclohexanol was 41%, the selectivity of cyclohexanone was 44%, the selectivity of adipic acid was 13%, the selectivity of glutaric acid was 2%, and no other by-products were detected.

[0146] Example 58

[0147] The catalytic experiment was repeated as in Example 29, except that the catalyst obtained in Example 7 (1.0 mg) was replaced by the catalyst obtained in Example 4 (1.0 mg), and the rest of the conditions were repeated as in Example 29. Finally, the conversion of cyclohexane was 6.6%, the selectivity of cyclohexanol was 47%, the selectivity of cyclohexanone was 41%, the selectivity of adipic acid was 9%, the selectivity of glutaric acid was 3%, and no other by-products were detected.

[0148] By comparing the catalysts and the comparative experiments, it can be clearly seen that the catalyst prepared in the present application can improve the conversion of cycloalkane and greatly improve the selectivity of partial oxidation products (cycloalkanol and cycloalkanone) during the catalytic oxidation of cycloalkane by O2, and effectively inhibit the deep oxidation.

[0149] Example 59

[0150] In a 1 L stainless steel autoclave with a polytetrafluoroethylene liner, the hexafluoropropylene trimer modified bimetallic porous silicon catalyst Si@Co@Cu@F(II)-60@60@80@60 (10.0 mg) was dispersed in cyclohexane (168.32 g, 2 mol). The reaction system was sealed, and the temperature was increased to 125°C under stirring. When the temperature reached the set temperature, oxygen was introduced to 1.00 MPa. The temperature and oxygen pressure were kept constant, and the stirring reaction was carried out for 8.0 h. After the reaction was completed, the reaction liquid was cooled to room temperature under stirring, and the stirring reaction was carried out at room temperature for 6.0 h to completely decompose and convert a small amount of residual cycloalkyl hydroperoxide.

[0151] The experiment was repeated three times, and the reaction mixtures were combined. Cyclohexane was separated by atmospheric distillation. Cyclohexanone was obtained by vacuum rectification at 156°C, and cyclohexanol was obtained by vacuum rectification at 162°C. The remaining mixture was recrystallized from isopropyl alcohol / cyclohexane (1:1) to obtain 12.15 g of white crystals. According to the calculation, the conversion of cyclohexane was 15.4%, the selectivity of cyclohexanol was 41%, the selectivity of cyclohexanone was 50%, and the selectivity of adipic acid was 9%.

[0152] The content described in the specification is merely a list of forms of the inventive concept, and the protection scope of the present application should not be regarded as being limited to the specific forms stated in the embodiments.

Claims

1. A hexafluoropropene trimer-modified bimetallic porous silicon, characterized by, It contains a functional functional group containing fluorine as shown in formula (I): The bimetallic center of the bimetallic porous silicon is any one of Co(II)-Cu(II), Co(II)-Zn(II), Co(II)-Ni(II), Co(II)-Fe(II), Mn(II)-Cu(II), Mn(II)-Zn(II), Mn(II)-Ni(II), Mn(II)-Fe(II); The preparation method of the hexafluoropropylene trimer modified bimetallic porous silicon comprises the following steps: dispersing a silane containing a hexafluoropropylene trimer functional group, bimetallic porous silicon and deionized water in an alcohol solvent, stirring and reacting under N2 atmosphere at a temperature of 20-200℃ for 6.0h-96.0h; the reaction mixture is filtered under reduced pressure, washed with ethanol and water, and vacuum dried to obtain the hexafluoropropylene trimer modified bimetallic porous silicon; The silane containing a hexafluoropropylene trimer functional group has a branched structure as shown in formula (II) or formula (III): The preparation method of the bimetallic porous silicon is: dissolving MeIM, a first metal salt and a second metal salt in water, stirring for 1-4 hours, then adding TEOS dropwise into the solution, stirring vigorously at room temperature for 5-20 hours, then re-dispersing the product in water, and then transferring it into a polytetrafluoroethylene-lined autoclave, reacting in an oven at 60-80℃ for 6-10h, and further reacting at 110-130℃ for 10-15h; collecting the product by filtration, washing with water and ethanol in sequence, drying, and calcining at 550-650℃ in air atmosphere for 10-30h to complete the preparation.

2. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 1, wherein, The mass ratio of the silane containing a hexafluoropropylene trimer functional group to the bimetallic porous silicon is 1:20-200; the mass ratio of deionized water to the bimetallic porous silicon is 1:20-200; and the reaction temperature of the preparation method of the hexafluoropropylene trimer modified bimetallic porous silicon is 60-90℃.

3. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 2, wherein, The mass ratio of the silane containing a hexafluoropropylene trimer functional group to the bimetallic porous silicon is 1:60-100; and the mass ratio of deionized water to the bimetallic porous silicon is 1:20-60.

4. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 2, wherein, The alcohol solvent is any one or any mixture of methanol, ethanol, isopropanol and n-propanol.

5. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 4, wherein, The alcohol solvent is any one or any mixture of methanol, ethanol, isopropanol and n-propanol.

6. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 1, wherein, The first metal salt is a Co salt or a Mn salt, and the molar ratio of the first metal salt to MeIM is 1:5-100; The second metal salt is a Cu, Zn, Ni or Fe salt, and the molar ratio of the second metal salt to the first metal salt is 1:5-100; The molar ratio of TEOS to MeIM is 0.8-1.2:

1.

7. A hexafluoropropene trimer modified bimetallic porous silicon according to claim 6, wherein, The first metal salt is a Co salt or a Mn salt, and the molar ratio of the first metal salt to MeIM is 1:50; The second metal salt is a Cu, Zn, Ni or Fe salt, and the molar ratio of the second metal salt to the first metal salt is 1:50; The molar ratio of TEOS to MeIM is 1:

1.

8. Use of the hexafluoropropylene terpolymer modified bimetallic porous silicon according to claim 1 in catalyzing the partial oxidation of cycloalkanes.

9. Use according to claim 8, wherein The application method is as follows: the hexafluoropropylene terpolymer modified bimetallic porous silicon is dispersed in cycloalkanes, the reaction system is sealed, the temperature is raised to 100-150℃ under stirring, oxygen is introduced to 0.40 MPa-2.0 MPa, the set temperature and oxygen pressure are maintained, and the stirring reaction is carried out for 3.0 h-15.0 h; then the reaction liquid is stirred and cooled to room temperature, and the stirring reaction is carried out at room temperature for 3.0 h-12.0 h, to obtain a reaction mixture containing the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone.

10. The use according to claim 9, wherein The mass ratio of the hexafluoropropylene terpolymer modified bimetallic porous silicon to the cycloalkane is 1:5-1000, the unit of mass is mg, and the unit of amount of substance is mmol.

11. Use according to claim 9, wherein The cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclododecane.

12. The use according to claim 11, wherein The cycloalkane is at least one of cyclohexane, cycloheptane, cyclooctane and cyclododecane.

13. The use according to claim 9, wherein The partial oxidation products include cycloalkyl alcohol and cycloalkyl ketone.

Images