Method for preparing 9, 10-anthraquinone through oxidation of 9, 10-dihydroanthracene

Abstract

The invention belongs to the technical field of fine chemical engineering, and discloses a method for preparing 9, 10-anthraquinone through oxidation of 9, 10-dihydroanthracene, 9, 10-dihydroanthracene is taken as a raw material, tert-butyl hydroperoxide is taken as an oxidant, in a water phase reaction system, RuOx-Ce0. 7Zr0. 3O2 is taken as a catalyst, 9, 10-dihydroanthracene is subjected to selective oxidation under the mild conditions of 40 DEG C and normal pressure, the conversion rate of dihydroanthracene is 100%, and 9, 10-anthraquinone is prepared through oxidation of 9, 10-dihydroanthracene. And the selectivity of the 2, 10-anthraquinone is 90%. According to the present invention, the environmentally-friendly dihydroanthracene is adopted as the raw material to construct the green and efficient anthraquinone catalytic synthesis system, the traditional anthraquinone production process is replaced, the emission of the strong acid wastewater and the heavy metal wastewater is avoided, the reaction condition is mild, the conversion rate of the 9, 10-dihydroanthracene and the selectivity of the 9, 10-anthraquinone are high, and the good industrial application prospect is provided.

Description

Technical Field

[0001] This invention belongs to the field of fine chemical technology and relates to a method for preparing anthraquinone, specifically a method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene. Background Technology

[0002] Anthraquinones are quinone compounds with 10 isomers, but only 1,2-anthraquinone, 1,4-anthraquinone, and 9,10-anthraquinone are structurally stable. Currently, the anthraquinone extracted is usually 9,10-anthraquinone. Anthraquinones are insoluble in water (their solubility is 6 mg / L at 50 °C), but they have good solubility in 1,4-dioxane and concentrated sulfuric acid.

[0003] Anthraquinones are crucial raw materials and organic intermediates in chemical production, widely used in industrial dyes, papermaking, textiles, pharmaceuticals, agronomy, and catalysts. Anthraquinone dyes are the most numerous and widely used dyes besides azo dyes, comprising over 430 varieties, with both production and demand increasing annually. Anthraquinones are also used as catalysts for pulp delignification in the papermaking industry; as degumming agents in the textile industry; and in the production of hydrogen peroxide and coal gas desulfurization. Anthraquinone derivatives also possess immunomodulatory and antitumor effects. The widespread application of anthraquinone compounds and their derivatives in various fields has led to a severe shortage in both domestic and international markets. Therefore, improving anthraquinone industrial production technology to increase yield and reduce production costs is of great significance for promoting the development of the entire chemical industry.

[0004] With the continuous development of anthraquinone applications, its demand is also increasing. However, its production is relatively scarce in both domestic and international markets. With increasingly stringent environmental policies, traditional synthetic anthraquinone processes are being phased out, making the efficient, safe, and green production of anthraquinone a major challenge for anthraquinone production.

[0005] Currently, the industrial production methods for anthraquinone both domestically and internationally generally include the anthraquinone oxidation method, the naphthoquinone method, the styrene method, and the phthalic anhydride synthesis method. The anthraquinone oxidation method uses refined anthraquinone as raw material and oxidizes it to anthraquinone under the action of a catalyst. The purity of the refined anthraquinone has a significant impact on the purity and yield of anthraquinone. To obtain high-purity anthraquinone, high-purity refined anthraquinone is usually used. In his article "Selective oxidation of anthraquinone in acetic acid with air in presence of nitric acid", Francisco Rodrfoguze mentioned the use of nitric acid as an oxidant for liquid-phase oxidation of anthraquinone. Although the purity requirement for anthraquinone is relatively low, it is easy to cause serious environmental pollution [Francisco Rodrfoguze, Adrodos LF, et al. Selective oxidation of anthracene to anthraquinone in acetic acid with air in presence of nitric acid [J]. Tetrahedron Letters, 1989, 30 (18): 2417-20.]. Bordoloi used mesoporous silicates supported on molybdovanadophosphoric acids as catalysts to generate anthraquinones through the oxidation reaction of anthraquinones with O2 in the air. O2 in this process is readily available and inexpensive. However, this technical route requires high purity of anthraquinones, the equipment for preparing anthraquinones is complex, the reaction temperature and pressure are high, and the production cost is high, which limits industrialization [Bordoli A, Lefebvre F, Halligudi S. Selective oxidation of anthracene using inorganic-organic hybrid materials based on molybdovanadophosphoric acids[J]. journal of catalysis2007, 247, 167-175].

[0006] The naphthoquinone process uses naphthalene and butadiene as raw materials, which have a wider range of sources compared to refined anthracene and generate less waste during production. However, the one-step synthesis of naphthoquinone from naphthalene is usually accompanied by the formation of phthalic anhydride and deep oxides, which reduces the yield of naphthoquinone [Tesser R, Di Serio M, Ambrosio M, et al. Heterogeneous catalysts for the production of anthraquinone from 2-benzoylbenzoic acid [J]. Chemical Engineering Journal, 2002, 90 (1): 195-201.]. From an economic perspective, improving the conversion rate of naphthalene and the selectivity of naphthoquinone is the key to whether the anthraquinone production process using the naphthoquinone process can be industrialized.

[0007] The phthalic anhydride synthesis method uses phthalic anhydride and benzene as raw materials, with benzene acting as both a raw material and a solvent in the reaction. Given my country's national conditions, with the development of the petroleum industry, there is an overcapacity of phthalic anhydride and benzene, resulting in low prices. This method has become one of the important methods for producing anthraquinones in my country. The phthalic anhydride method for synthesizing anthraquinones (Chinese patents CN1231278A and CN111410602A) is currently the most widely used anthraquinone production process, requiring relatively low equipment requirements, easily scalable for industrial production, and offering good economic benefits. However, this production process requires a huge amount of aluminum trichloride and is not environmentally friendly. 1 mol of phthalic anhydride not only needs to undergo a complexation reaction with 1 mol of aluminum trichloride, but also needs to form an intermediate, o-benzoylbenzoic acid, to form a salt at the same time. In addition, to obtain a relatively pure o-benzoylbenzoic acid (BBA) salt at the end of the reaction, the complex needs to be hydrolyzed. Hydrolysis produces three times the amount of hydrochloric acid compared to aluminum trichloride. Moreover, the catalyst in the reaction process cannot be recovered. The amount of concentrated sulfuric acid used in the second step is generally 3 to 4 times that of BBA, and the concentrated sulfuric acid needs to be diluted to precipitate anthraquinone crystals, which can easily cause equipment corrosion and generate a large amount of acidic wastewater. The environmental problems are prominent. With increasingly stringent environmental policies, traditional production processes are facing challenges, and manufacturers using traditional production processes to produce anthraquinone face the risk of closure. To solve the serious pollution problems of "three wastes" and equipment corrosion problems in the production process, it is necessary to develop a green and clean production process. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a method for preparing 9,10-anthraquinone from 9,10-dihydroanthracene, using RuO as the catalyst. x -Ce 1-y Zr y O2 has the characteristics of simple process, high catalytic efficiency, environmental friendliness and mild conditions.

[0009] The technical solution of the present invention:

[0010] A method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene, comprising the following steps:

[0011] 1) Preparation of Ce using the citric acid sol-gel method 1-y Zr y O2, and then the third metal element Ru is introduced to Ce using a wet impregnation method. 1-y Zr y O2 was modified to obtain RuO x -Ce 1-y Zr y O2 catalyst;

[0012] 2) Take the RuO obtained in step 1) x -Ce 1-y Zr y In a reaction solution, O2 catalyst and 9,10-dihydroanthracene are reacted with an oxidant to produce 9,10-anthraquinone.

[0013] Ce 1-y Zr y In O2, y represents the amount of Zr incorporated, and y can be 0, 0.1, 0.3, 0.5, 0.7, 0.9, or 1; preferably 0.3.

[0014] RuO x -Ce 1-y Zr y The loading of the noble metal Ru in the O2 catalyst is 2.5%;

[0015] In step 2), RuO x -Ce 1-y Zr y The mass ratio of O2 catalyst to dihydroanthracene is 1:4, and the reaction solution is water;

[0016] The oxidant is tert-butyl hydroperoxide, and the amount used is 8-20 equivalents of dihydroanthracene; preferably 10-16 equivalents.

[0017] In step 2), the reaction temperature is 30-60 ℃, preferably 40 ℃; the reaction time is 1-8 h, preferably 8 h.

[0018] The beneficial effects of this invention are:

[0019] (1) The present invention uses 9,10-dihydroanthracene as raw material, which avoids the discharge of strong acids such as concentrated sulfuric acid and concentrated nitric acid compared with the liquid phase oxidation method of pure anthracene;

[0020] (2) The present invention uses 9,10-dihydroanthracene as raw material for oxidation process, which is green and environmentally friendly. Compared with traditional anthracene liquid phase oxidation, it avoids the discharge of heavy metal wastewater.

[0021] (3) The present invention uses 9,10-dihydroanthracene as raw material. Compared with the traditional method for preparing anthraquinone, it can be achieved under mild reaction conditions, and the selectivity and yield of anthraquinone are improved, making it suitable for industrial production. Attached Figure Description

[0022] Figure 1 The graph shows the effect of t-BHP dosage on the oxidation of anthraquinone by 9,10-dihydroanthracene. Detailed Implementation

[0023] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings and technical solutions.

[0024] Example 1:

[0025] 10 mmol Ce(NO3)3·6H2O was dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol of citric acid was added, and the mixture was stirred at 60 °C for 1 h. The mixture was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The syrup was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain the CeO2 support. 0.4 g of the CeO2 support was weighed into 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until completely impregnated. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x -CeO2 catalyst.

[0026] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -CeO2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 42.67%, and the selectivity for anthraquinone was 49.31%.

[0027] Example 2:

[0028] 9 mmol Ce(NO3)3·6H2O and 1 mmol Zr(NO3)4·5H2O were dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The liquid was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain Ce. 0.9 Zr 0.1 O2 carrier. Weigh 0.4 g Ce 0.9 Zr 0.1 The O2 support was placed in 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until complete impregnation. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x -Ce 0.9 Zr 0.1 O2 catalyst.

[0029] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.9 Zr 0.1 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 43.42%, and the selectivity for anthraquinone was 58.31%.

[0030] Example 3:

[0031] 7 mmol Ce(NO3)3·6H2O and 3 mmol Zr(NO3)4·5H2O were dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The solution was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain Ce. 0.7 Zr 0.3 O2 carrier. Weigh 0.4 g Ce 0.7 Zr 0.3The O2 support was placed in 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until complete impregnation. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x - Ce 0.7 Zr 0.3 O2 catalyst.

[0032] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 67.99% and the selectivity for anthraquinone was 60.85%.

[0033] Example 4:

[0034] 5 mmol Ce(NO3)3·6H2O and 5 mmol Zr(NO3)4·5H2O were dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The liquid was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain Ce. 0.5 Zr 0.5 O2 carrier. Weigh 0.4 g Ce 0.5 Zr 0.5 The O2 support was placed in 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until complete impregnation. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x - Ce 0.5 Zr 0.5 O2 catalyst.

[0035] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.5 Zr 0.5 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 45.50%, and the selectivity for anthraquinone was 59.49%.

[0036] Example 5:

[0037] 3 mmol Ce(NO3)3·6H2O and 7 mmol Zr(NO3)4·5H2O were dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The solution was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain Ce. 0.3 Zr 0.7 O2 carrier. Weigh 0.4 g Ce 0.3 Zr 0.7 The O2 support was placed in 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until complete impregnation. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x - Ce 0.3 Zr 0.7 O2 catalyst.

[0038] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.3 Zr 0.7 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 42.35%, and the selectivity for anthraquinone was 62.12%.

[0039] Example 6:

[0040] 1 mmol Ce(NO3)3·6H2O and 9 mmol Zr(NO3)4·5H2O were dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The solution was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain Ce. 0.1 Zr 0.9 O2 carrier. Weigh 0.4 g Ce 0.1 Zr 0.9 The O2 support was placed in 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until complete impregnation. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x - Ce 0.7 Zr 0.3 O2 catalyst.

[0041] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.1 Zr 0.9 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 41.37%, and the selectivity for anthraquinone was 61.99%.

[0042] Example 7:

[0043] 10 mmol Zr(NO3)4·5H2O was dissolved in 20 mL of deionized water. After stirring for ten minutes, 1.5 mmol citric acid was added, and the mixture was stirred at 60 °C for 1 h. The solution was then rotary evaporated at 80 °C to obtain a syrupy liquid, which was dried overnight at 80 °C. The solution was transferred to a muffle furnace and calcined at 300 °C for 1 h to remove citric acid, followed by calcination at 450 °C for 3 h to obtain a ZrO2 support. 0.4 g of the ZrO2 support was weighed into 20 mL of anhydrous ethanol, and 1.5 mL of a 6.683 g / L RuCl3 ethanol solution was added. The mixture was stirred at room temperature for 8 hours until completely impregnated. The ethanol in the suspension was removed in a rotary evaporator at 35 °C, and the resulting residue was dried overnight in an oven at 80 °C. The resulting solid was placed in a tube furnace and heated at 450 °C in an O2 / Ar (20 / 40 mL min) atmosphere. -1 Calcination was carried out under a certain atmosphere for 3 h at a heating rate of 5 °C / min to finally obtain RuO. x - ZrO2 catalyst.

[0044] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x - Ce 0.5 Zr 0.5 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 30 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 19.00%, and the selectivity for anthraquinone was 51.41%.

[0045]

[0046] Example 8:

[0047] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 1 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 73.23% and the selectivity for anthraquinone was 65.64%.

[0048] Example 9:

[0049] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 50 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 77.08%, and the selectivity for anthraquinone was 61.04%.

[0050] Example 10:

[0051] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 60 °C for 1 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 86.31%, and the selectivity for anthraquinone was 56.55%.

[0052] Examples 3 and Examples 8-10 are listed in the table below:

[0053]

[0054] Example 11:

[0055] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 2 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 77.23%, and the selectivity for anthraquinone was 68.89%.

[0056] Example 12:

[0057] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 4 h. After the reaction was completed, the gas chromatography analysis was performed, and the conversion rate of dihydroanthracene was calculated to be 82.47%, and the selectivity for anthraquinone was 66.43%.

[0058] Example 13:

[0059] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr0.3 O2 catalyst was added to 4 mL of water, followed by 8 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 93.31% and the selectivity for anthraquinone was 63.05%.

[0060] Examples 3 and Examples 11-13 are listed in the table below:

[0061]

[0062] Example 14:

[0063] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 10 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 92.38% and the selectivity for anthraquinone was 76.83%.

[0064] Example 15:

[0065] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 12 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 93.72% and the selectivity for anthraquinone was 81.31%.

[0066] Example 16:

[0067] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 14 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 100.00% and the selectivity for anthraquinone was 89.78%.

[0068] Example 17:

[0069] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 16 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 97.49% and the selectivity for anthraquinone was 91.13%.

[0070] Example 18:

[0071] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 18 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 100.00% and the selectivity for anthraquinone was 90.12%.

[0072] Example 19:

[0073] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 20 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the gas chromatography analysis showed that the conversion rate of dihydroanthracene was 100.00% and the selectivity for anthraquinone was 91.59%.

[0074] Examples 13-19 are listed in the table below:

[0075]

[0076] Example 20:

[0077] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 14 equivalents of t-BHP (70 wt.% aqueous solution). The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the reaction was analyzed by gas chromatography. Dihydroanthracene did not react.

[0078] Example 21:

[0079] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of RuO x -Ce 0.7 Zr 0.3O2 catalyst was added to 4 mL of water, followed by 14 equivalents of H2O2. The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the reaction was analyzed by gas chromatography. Dihydroanthracene did not react.

[0080] Example 22:

[0081] 0.4 mmol of 9,10-dihydroanthracene was mixed with 18 mg of -Ce 0.7 Zr 0.3 O2 catalyst was added to 4 mL of water, followed by 14 equivalents of H2O2. The reaction was carried out at 40 °C for 8 h. After the reaction was completed, the reaction was analyzed by gas chromatography. Dihydroanthracene did not react.

[0082]

[0083] The above description of the embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene, characterized in that, The steps are as follows: 1) Preparation of Ce using the citric acid sol-gel method 1-y Zr y O2, and then the third metal element Ru is introduced to Ce using a wet impregnation method. 1-y Zr y O2 was modified to obtain RuO x -Ce 1-y Zr y O2 catalyst; 2) Take the RuO obtained in step 1) x -Ce 1-y Zr y In a reaction solution, O2 catalyst and 9,10-dihydroanthracene are reacted with an oxidant to produce 9,10-anthraquinone.

2. The method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene according to claim 1, characterized in that, The RuO x -Ce 1-y Zr y The loading of the noble metal Ru in the O2 catalyst is 2.5%.

3. The method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene according to claim 1, characterized in that, The Ce 1-y Zr y In O2, y represents the amount of Zr incorporated, where y is between 0 and 1, and the preferred amount of Zr incorporated is 0.

3.

4. The method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene according to claim 1, characterized in that, In step 2), RuO x -Ce 1-y Zr y The mass ratio of O2 catalyst to dihydroanthracene is 1:4, and the reaction solution is water.

5. The method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene according to claim 1, characterized in that, The oxidant is tert-butyl hydroperoxide, and the amount used is 8-20 equivalents of dihydroanthracene, preferably 10-16 equivalents of tert-butyl hydroperoxide.

6. The method for preparing 9,10-anthraquinone by oxidation of 9,10-dihydroanthracene according to claim 1, characterized in that, In step 2), the reaction temperature is 30-60 ℃, preferably 40 ℃, and the reaction time is 1-8 h, preferably 8 h.

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