Phenazine vanadium compound and method for synthesizing naphthenic alcohol and naphthenic ketone from phenazine vanadium compound through selective catalytic oxidation of naphthenic hydrocarbon

Abstract

The invention discloses a phenazine vanadium compound and a method for preparing naphthenic alcohol and naphthenic ketone through selective oxidation of naphthenic hydrocarbon by using the phenazine vanadium compound. The preparation method comprises the following steps: reacting 1-hydroxyphenazine with vanadyl acetylacetonate in a hydrocarbon solvent or a halogenated hydrocarbon solvent, and standing and filtering after the reaction is finished to obtain a phenazine vanadium compound; and by taking cycloalkane as a reaction raw material and the phenazine vanadium compound as a homogeneous catalyst, adding an oxidizing agent, carrying out catalytic oxidation reaction, and after the reaction is finished, carrying out post-treatment on the reaction liquid to obtain a mixture of naphthenic alcohol and naphthenic ketone. As a catalyst, the phenazine vanadium compound can be used for a catalytic oxidation process of cycloalkane oxidation. Meanwhile, the method disclosed by the invention has the advantages of high selectivity of naphthenic alcohol and naphthenic ketone, low reaction temperature, few byproducts, small environmental influence, high safety coefficient and the like.

Description

Technical Field

[0001] The invention belongs to the field of fine chemicals and relates to a production process for cycloalkane oxidation, and specifically relates to a phenazine vanadium compound and a method for using the compound in the selective catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohols and cycloalkyl ketones. Background Art

[0002] At present, one of the main industrial preparation methods of cycloalkyl alcohols and cycloalkyl ketones is the cycloalkane oxidation method. Cycloalkane oxidation reaction mainly produces cycloalkyl ketones and cycloalkyl alcohols. The non-catalytic oxidation process is commonly used in industry, which has the disadvantages of low selectivity for the production of cycloalkane hydroperoxides, and the organic acid produced by over-oxidation has an adverse effect on the catalyst activity of the subsequent decomposition reaction, resulting in unsatisfactory molecular yields of cycloalkyl alcohols and cycloalkyl ketones produced by the decomposition reaction of cycloalkane hydroperoxides, low ketone-alcohol ratio, and increased production costs.

[0003] Among them, cycloalkanes represented by cyclohexane are the most widely used cycloalkanes. This mixture produced by the oxidation of cyclohexane is usually called KA oil (ketone / alcohol oil), which is an important chemical raw material. Most KA oils are used to produce nylon 66 and nylon 6 precursors, and can also be used to prepare intermediates for chemicals such as dyes, coatings, and medicines. It can also be used to prepare rubber antioxidants, spices, and fruit mildew inhibitors. KA oil mixtures are easily oxidized to produce adipic acid, which is an important reactant for the preparation of certain condensation polymers, including polyamides and nylon 66.

[0004] The traditional process of cyclohexane oxidation to obtain KA oil (i.e., a mixture of cyclohexanone and cyclohexanol) is carried out in two steps. First, cyclohexane is oxidized to prepare an oxidation liquid containing cyclohexyl hydroperoxide (CyOOH). In the second step, chromium ions or cobalt ions are used as homogeneous catalysts to catalyze the decomposition of CyOOH to obtain KA oil. With the restrictions of regulations in various countries around the world, the demand for replacement of environmentally unfavorable catalysts such as chromium and cobalt is becoming more and more urgent. Most technologies have begun to focus on the use of different types of homogeneous catalysts to catalyze hydrogen peroxide to oxidize cyclohexane to prepare KA oil. At present, most efforts are focused on the use of molecular sieves, polymers, and transition metal complexes supported by silica. Although some of these materials show relatively good activity and selectivity for K / A oil, most of them will undergo deactivation and / or metal leaching, which hinders their industrial application.

[0005] For example, CN103007978A discloses a supported gold catalyst for cyclohexane oxidation reaction, which is composed of an active component Au and a carrier cobalt oxide, with the mass percentage of Au being 1-5% and the mass percentage of cobalt oxide being 95-99%. The reaction is carried out under an oxygen pressure of 1.5 MPa and a temperature of 150°C for 3 hours, and the cyclohexane conversion rate reaches 8.5%, and the total selectivity is 91.4%.

[0006] CN111943808A discloses a method for the synergistic catalytic oxidation of cycloalkanes by MOFs PCN-224(Mn) / Zn(II) salts. PCN-224(Mn) (0.001% to 5%, g / mol) and Zn(II) salts (0.01% to 10%, mol / mol) are dispersed in cycloalkanes, the reaction system is sealed, the temperature is raised to 120°C with stirring, oxygen is introduced to 1.0 MPa, the reaction is stirred for 8.0 hours, the cyclohexane conversion rate is 7.00%, the cyclohexanol selectivity is 75.58%, and the cyclohexanone selectivity is 17.49%.

[0007] Although heterogeneous noble metal catalysts have good cyclohexane oxidation activity, the cost of this type of catalyst is relatively high, which greatly limits its industrial application prospects.

[0008] Therefore, researchers have also prepared a variety of homogeneous catalysts, among which vanadium compounds can be used as a good catalyst.

[0009] CN109251126A discloses a method for preparing KA oil by oxidation of cyclohexane, wherein the vanadium phosphorus oxide catalyst is used for catalytic reaction, and the vanadium phosphorus oxide is prepared by the following method: V205, phosphoric acid and distilled water are reacted at 100-120°C for 16-24 hours, and the obtained solid product is added to an isobutyl alcohol solvent, and reacted at 90-130°C for 16-24 hours to obtain a catalyst precursor, which is activated to obtain the catalyst. The conversion rate of cyclohexane catalyzed by the vanadium phosphorus oxide catalyst reaches 7-8%, and the selectivity of KA oil can reach about 50%.

[0010] CN109248699A discloses a method for preparing KA oil by oxidation of cyclohexane, wherein a vanadium phosphorus oxygen catalyst is used for catalytic reaction, and the catalyst is added to an isobutanol solvent together with a bismuth salt, and reacted at 90 to 130°C for 16 to 24 hours to obtain a catalyst precursor, which is activated to obtain the catalyst. The invention uses a vanadium phosphorus oxygen catalyst for the preparation of KA oil by oxidation of cyclohexane, and provides a new method for preparing KA oil by oxidation of cyclohexane. The prepared vanadium phosphorus oxygen catalyst has a catalytic conversion rate of about 10% for cyclohexane, and the selectivity of KA oil can reach more than 90%. The addition of the active component bismuth changes the V in the vanadium phosphorus oxygen catalyst system. 5+ (VOPO4) and V 4+ The ratio of ((VO)2P2O7) makes it have better synergistic effect in catalyzing the conversion of cyclohexane, while increasing the transfer rate of lattice oxygen in the catalyst, thereby improving activity.

[0011] CN109251125A discloses a method for preparing cyclohexanol by oxidation of cyclohexane, wherein the reaction is catalyzed by a vanadium phosphorus oxide catalyst, and the catalyst is prepared by the following method: V205 and phosphoric acid are reacted in an aqueous solution environment, the obtained powder product is added to isobutanol, and the reaction is carried out at 30-90°C for 4-8 hours under normal pressure, the solvent is evaporated, and the solid is dried to obtain a catalyst powder; or the catalyst is made into a supported type.

[0012] This indicates that vanadium substances can be used to catalyze the oxidation of cycloalkanes. However, the selectivity of this type of vanadium phosphorus oxygen catalyst is still low, and the activity of the catalyst needs to be further improved. Summary of the invention

[0013] Purpose of the invention: The purpose of the present invention is to provide a phenazine vanadium compound and a method for using the phenazine vanadium compound and the ...

[0014] Technical solution: The purpose of the present invention is achieved through the following technical solution:

[0015] The present invention provides a phenazine vanadium compound, the structural formula of which is as follows:

[0016]

[0017] The present invention also provides a method for preparing the phenazine vanadium compound, comprising the following steps: reacting 1-hydroxyphenazine with acetylacetonatovanadium in a hydrocarbon solvent or a halogenated hydrocarbon solvent, and standing and filtering after the reaction to obtain the phenazine vanadium compound.

[0018] Preferably, the hydrocarbon solvent is selected from one of benzene, toluene, xylene, cyclohexane, cyclopentane, n-hexane or n-pentane; and the halogenated hydrocarbon solvent is selected from one of dichloromethane, dichloroethane or chloroform.

[0019] Toluene, cyclohexane or n-hexane is further preferred.

[0020] Preferably, the reaction temperature is -10 to 100°C. More preferably, the reaction temperature is 30 to 80°C.

[0021] Preferably, the molar ratio of 1-hydroxyphenazine to vanadyl acetylacetonate is 1.9:1 to 2.1:1. Further preferably, the molar ratio of 1-hydroxyphenazine to vanadyl acetylacetonate is 2:1.

[0022] In the present invention, the reaction time can be selected according to the reaction conditions, and generally can be selected to be 1 to 1800 min; preferably 30 to 600 min.

[0023] The temperature for static filtration after the reaction is completed can be selected according to the reactants and products, and can generally be -10 to 50°C; preferably 0 to 35°C.

[0024] The time for standing and filtering after the reaction is completed can be determined according to the reactants and products, and can generally be selected to be 1 to 1200 minutes, preferably 10 to 600 minutes.

[0025] The phenazine vanadium compound can be dried by volatilizing the solvent under natural conditions, or can be dried in an oven.

[0026] The invention also provides the use of the phenazine vanadium compound in the selective catalytic oxidation of cycloalkanes to synthesize cycloalkyl alcohols and cycloalkyl ketones.

[0027] The present invention also provides a method for synthesizing cycloalkyl alcohols and cycloalkyl ketones by selectively catalytically oxidizing cycloalkane using the phenazine vanadium compound, wherein cycloalkane is used as a reaction raw material, the phenazine vanadium compound is used as a homogeneous catalyst, an oxidant is added, and a catalytic oxidation reaction is carried out. After the reaction is completed, the reaction liquid is post-treated to obtain a mixture of cycloalkyl alcohols and cycloalkyl ketones.

[0028] The present invention oxidizes cycloalkanes in a homogeneous phase by adding the phenazine vanadium compound for catalytic oxidation, wherein the phenazine vanadium compound is dispersed in a liquid phase reaction system. The conversion rate of cycloalkanes in the present invention is not less than 40%.

[0029] Preferably, the cycloalkane is a cycloalkane containing three or more carbon atoms, or a cycloalkane containing an alkyl substituent.

[0030] Further preferably, the cycloalkane is one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane or cyclododecane.

[0031] In the present invention, the oxidant is not particularly limited, and for example, sulfoxides such as hydrogen peroxide, air, oxygen, dimethyl sulfoxide, dibutyl sulfoxide, diphenyl sulfoxide, and tetramethylene sulfoxide can be used. Two or more of these oxidants can be mixed. From the perspective of productivity and ease of operation, it is preferred to use hydrogen peroxide, air, oxygen, dimethyl sulfoxide, tetramethylene sulfoxide, or a mixture of these oxidants.

[0032] In the present invention, the preferred oxidant is hydrogen peroxide, oxygen, air or any mixture thereof.

[0033] In the present invention, when oxygen is used as an oxidant, oxygen may be mixed with other gases, for example, oxygen may be mixed with air or an inert gas.

[0034] In the present invention, when air or oxygen is used as an oxidant, there is no particular limitation on the method of supplying air or oxygen. For example, the following methods can be used: a method of replacing the gas phase in contact with the reaction solution with air or oxygen, a method of allowing the gas phase in contact with the reaction solution to flow in air or oxygen, a method of blowing air or oxygen into the reaction solution, etc.

[0035] Preferably, the amount of the catalyst is 0.01-1% of the total weight of the reaction mixture.

[0036] Preferably, the reaction pressure is 0.10-10 MPa; further preferably, the reaction pressure is 0.10-1.5 MPa.

[0037] In the present invention, the reaction temperature can be determined according to the reactants, and the reaction temperature is usually 0 to 200°C; preferably, the reaction temperature is 100 to 180°C.

[0038] In the present invention, the reaction time can be determined according to the reactants, and the reaction time is usually 1 to 600 minutes.

[0039] In the present invention, the catalytic oxidation reaction is carried out under stirring, and the stirring rate is 200-1500 rpm; preferably, the stirring rate is 500-1000 rpm.

[0040] Beneficial effects:

[0041] The present invention develops a new phenazine vanadium compound, which is a new technology containing vanadium-based catalytic oxidation, and can be used in the catalytic oxidation process of cycloalkane oxidation. The method of the present invention has the advantages of high selectivity for cycloalkyl alcohols and cycloalkyl ketones, low reaction temperature, few by-products, low environmental impact, high safety factor, etc. The present invention provides an efficient, feasible and safe method for synthesizing cycloalkyl alcohols and cycloalkyl ketones by selective catalytic oxidation of cycloalkane. DETAILED DESCRIPTION

[0042] The technical solution of the present invention is described in detail below through specific embodiments, but the protection scope of the present invention is not limited to the embodiments.

[0043] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased through regular channels.

[0044] The experimental methods in the following examples are conventional methods unless otherwise specified. The experimental materials used in the following examples are commercially available products unless otherwise specified.

[0045] Example 1

[0046] Catalyst synthesis method 1:

[0047] In a 100mL flask, add 3.92g (0.02mol) 1-hydroxyphenazine and 2.6g (0.01mol) acetylacetonatovanadium, add 50mL cyclohexane, and heat the obtained dark green mixture to 50℃ for 4 hours to obtain a dark solution. After cooling to 25℃ and standing for 2 hours, filter out the solid to obtain a dark product, wash with a small amount of cyclohexane, and dry the product to obtain 3.4g of dark solid. LC-MS (ESI) m / z: 457.1.

[0048] Example 2

[0049] Catalyst synthesis method 2:

[0050] In a 100mL flask, add 1.96g (0.01mol) 1-hydroxyphenazine and 1.3g (0.005mol) acetylacetonatovanadium, add 35mL dichloromethane, and react at 40°C for 3.5 hours to obtain a dark solution. Cool to 25°C, stand for 1.5 hours, filter out the solid, obtain a dark product, wash with n-hexane, and dry to obtain 1.6g of dark solid. LC-MS (ESI) m / z: 457.1.

[0051] Example 3

[0052] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0053] In a 100mL polytetrafluoroethylene-lined autoclave, 35g (0.5mol) of cyclopentane and 0.22g of the solid catalyst prepared in Example 1 were added, the temperature was raised to 130°C with stirring, oxygen (1.0MPa) was introduced, and the reaction was stirred at 600rpm for 1 hour. After the reaction was completed, 20g of triphenylphosphine was added to the reaction mixture, stirred at 25°C for 1 hour, and a sample was taken for gas chromatography analysis. The cyclopentane conversion rate was 62%, and the cyclopentanol / ketone selectivity was 94%.

[0054] Example 4

[0055] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0056] In a 100mL polytetrafluoroethylene-lined autoclave, 42g (0.5mol) of cyclohexane and 0.04g of the solid catalyst prepared in Example 1 were added, the temperature was raised to 140°C with stirring, oxygen (1.0MPa) was introduced, and the reaction was stirred at 800rpm for 2 hours. After the reaction was completed, 20g of triphenylphosphine was added to the reaction mixture, stirred at 25°C for 1 hour, and a sample was taken for gas chromatography analysis. The cyclohexane conversion was 74%, and the cyclohexanol / ketone selectivity was 92%.

[0057] Example 5

[0058] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0059] In a 100mL polytetrafluoroethylene-lined autoclave, 42g (0.5mol) of cyclohexane and 0.08g of the solid catalyst prepared in Example 1 were added, and 30mL of 30% hydrogen peroxide was added, and the mixture was heated to 120°C with stirring, and stirred at 600rpm for 1 hour. After the reaction was completed, 20g of triphenylphosphine was added to the reaction mixture, and the mixture was stirred at 25°C for 1 hour, and a sample was taken for gas chromatography analysis. The cyclohexane conversion was 76%, and the cyclohexanol / ketone selectivity was 97%.

[0060] Example 6

[0061] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0062] In a 100 mL polytetrafluoroethylene-lined autoclave, 20 g of cyclohexane and 0.02 g of the solid catalyst prepared in Example 2 were added, and 30 mL of hydrogen peroxide was added. The mixture was heated to 140° C. with stirring and reacted at 600 rpm for 1 hour. After the reaction was completed, 10 g of triphenylphosphine was added to the reaction mixture, and the mixture was stirred at 25° C. for 1 hour. The mixture was sampled for gas chromatography analysis. The cyclohexane conversion was 85%, and the cyclohexanol / ketone selectivity was 93%.

[0063] Example 7

[0064] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0065] In a 100mL polytetrafluoroethylene-lined autoclave, 22.4g of cyclooctane and 0.015g of the solid catalyst prepared in Example 2 were added, the temperature was raised to 160°C with stirring, oxygen (1.2MPa) was introduced, and the reaction was stirred at 600rpm for 2 hours. After the reaction was completed, 15g of triphenylphosphine was added to the reaction mixture, stirred at 25°C for 1 hour, and a sample was taken for gas chromatography analysis. The cyclooctane conversion was 64%, and the cyclooctanol / ketone selectivity was 83%.

[0066] Example 8

[0067] Synthesis of cycloalkyl alcohols and cycloalkyl ketones:

[0068] In a 100mL polytetrafluoroethylene-lined autoclave, 20g of cyclododecane and 0.08g of the solid catalyst prepared in Example 2 were added, and 50mL of hydrogen peroxide was added, and the mixture was heated to 100°C with stirring, and stirred at 400rpm for 1 hour. After the reaction was completed, 10g of triphenylphosphine was added to the reaction mixture, and the mixture was stirred at 25°C for 1 hour, and a sample was taken for gas chromatography analysis. The conversion rate of cyclododecane was 47%, and the selectivity of cyclododecyl alcohol / ketone was 81%.

[0069] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes in form and details may be made without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A phenazine vanadium compound, characterized in that: Its structural formula is as follows:

2. The method for preparing a phenazine vanadium compound according to claim 1, characterized in that: The method comprises the following steps: reacting 1-hydroxyphenazine with vanadium acetylacetonate in a hydrocarbon solvent or a halogenated hydrocarbon solvent, and after the reaction is completed, standing and filtering to obtain a phenazine vanadium compound.

3. The preparation method according to claim 2, characterized in that: The hydrocarbon solvent is selected from one of benzene, toluene, xylene, cyclohexane, cyclopentane, n-hexane or n-pentane; the halogenated hydrocarbon solvent is selected from one of dichloromethane, dichloroethane or chloroform.

4. The preparation method according to claim 2, characterized in that: The reaction temperature is -10 to 100°C.

5. The preparation method according to claim 2, characterized in that: The molar ratio of the 1-hydroxyphenazine to the vanadyl acetylacetonate is 1.9:1 to 2.1:

1.

6. Use of the phenazine vanadium compound according to claim 1 in the selective catalytic oxidation of cycloalkanes to synthesize cycloalkyl alcohols and cycloalkyl ketones.

7. A method for synthesizing cycloalkyl alcohols and cycloalkyl ketones by selective catalytic oxidation of cycloalkanes using the phenazine vanadium compound according to claim 1, characterized in that: Cycloalkane is used as a reaction raw material, the phenazine vanadium compound is used as a homogeneous catalyst, an oxidant is added, and a catalytic oxidation reaction is carried out. After the reaction is completed, the reaction liquid is post-treated to obtain a mixture of cycloalkyl alcohol and cycloalkyl ketone.

8. The method according to claim 7, characterized in that The cycloalkane is a cycloalkane containing three or more carbon atoms, or a cycloalkane containing an alkyl substituent; preferably one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane or cyclododecane; The oxidant is hydrogen peroxide, oxygen, air or any mixture thereof.

9. The method according to claim 7, characterized in that: The amount of the catalyst used accounts for 0.01-1% of the total weight of the reaction mixture.

10. The method according to claim 7, characterized in that The reaction pressure is 0.10-10 MPa, the reaction temperature is 0-200° C., and the reaction time is 1-600 min.

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