Preparation method of novel uranium-based UO4. 2H2O and application of novel uranium-based UO4. 2H2O in catalytic synthesis of nitrosobenzene or derivatives thereof

Abstract

Uranium as an indispensable strategic resource in the nuclear energy field of China has self-evident importance. However, along with continuous expansion and deepening of the nuclear energy application field, how to safely and efficiently treat a large amount of depleted uranium (especially 238U which does not cause direct radiation harm to human bodies but still has toxicity similar to that of common heavy metals) generated in the nuclear concentration process has become an urgent subject to be solved in the strategy of environmental protection and sustainable development. The invention aims to explore a new mode for utilizing depleted uranium (238U, which has no radiation injury to human bodies), and particularly, U3O8 prepared by depleting UF6 is used as a raw material, and UO4. 2H2O is prepared by a simple dissolution and reprecipitation method. UO4. 2H2O is used as a catalyst, an organic solvent is used as a reaction solvent, hydrogen peroxide is used as an environment-friendly oxidizing agent, and aniline or derivatives thereof can be catalyzed to be selectively oxidized to generate nitrosobenzene or derivatives thereof. According to the implementation of the method, breakthrough progress is achieved in the field of nuclear waste management, on one hand, the problem of reutilization of the depleted uranium waste is innovatively solved, and a novel and efficient method is provided for resource utilization of the nuclear waste. And on the other hand, by ingeniously converting aniline and derivatives thereof into nitrosobenzene or derivatives thereof with higher economic value, the idea of resource recycling is practiced, gorgeous transformation from wastes to high-added-value products is realized, and the comprehensive utilization rate of resources is greatly improved.

Description

Technical Field

[0001] The present invention relates to a novel technology for utilizing depleted uranium, in particular to using depleted UF6 as a raw material to prepare UO4·2H2O for selective catalytic oxidation of aniline or its derivatives to prepare nitrosobenzene or its derivatives. Technical Background

[0002] The scientific and efficient use of nuclear energy has immeasurable strategic value for the steady improvement of my country's national defense strength and the sustainable transformation of its energy structure. However, with the continuous expansion and deepening of the application of nuclear energy, how to properly and safely deal with the huge amount of depleted uranium waste generated during nuclear reactions and explore feasible ways to reuse it has quietly become a major issue in the field of environmental protection and pollution control that needs to be solved urgently and without delay. This challenge is not only related to the maintenance of ecological balance, but also directly affects the long-term interests of public health and national security. Therefore, we must increase investment in the research and development of depleted uranium treatment technology, innovate management mechanisms, and ensure that the nuclear energy industry can achieve harmonious coexistence with environmental protection while promoting social and economic development.

[0003] Naturally occurring uranium is a mixture of three isotopes: 238 U. 235 U and 234 U. Isotope 238 U accounts for 99.28% of the mixture (see Journal of Nuclear Materials, 1986, Vol. 8, 140-143.). Uranium is mainly used in the nuclear industry, where it is isotopically enriched 235 U (3-4%) (see Journal of Nuclear Materials, 2002, Vol. 18, 167-170.) The enriched byproduct is called depleted uranium. Isotopes 235 U and 234The main part of U is recovered in the enrichment stage. The radioactivity of depleted uranium is two times lower than that of natural uranium, but it still has similar toxicity to ordinary heavy metals. Because the actinide uranium (U) has a large ionic radius and contributes its 5f orbital to generate coordination numbers and unique coordination structures in bond formation, it exhibits electronic flexibility in multiple oxidation states from +II to +VI in solution and solid state. Its oxidation ability is higher than that of common lanthanide catalysts, including lanthanum oxide and cerium oxide-based catalysts; in addition, due to the participation of electrons in the f orbital, uranium oxide is easy to form oxygen vacancies, which is conducive to enhancing catalytic oxidation ability. H. Idriss et al. used uranium dioxide to synthesize 4-methyl-1,3-pentadiene through the aldol condensation of acetone molecule dimers (see "Surface Science", 2007, Vol. 601, 5690-5700.). H.Madhavaram et al. used UO2 to synthesize crotonaldehyde from two molecules of acetaldehyde, and synthesized furan by cyclization of acetaldehyde using α-UO3 and β-UO3 (see Journal of Catalysis, 2004, Vol. 224, No. 2, 358-369). Taylor et al. used uranium oxide to destroy short-chain alkanes and achieve the treatment of volatile organic compounds (VOCs) (see Applied Catalysis B-Environmental, 2000, Vol. 25, 137-149).

[0004] Nitrosobenzene and its derivatives are a class of vital fine chemicals. They occupy a pivotal position in the chemical industry and are widely used as key raw materials for synthetic polymers, pharmaceuticals, dyes, perfumes and other diversified products. Studies have found that Pt / TiO2 can also catalyze the oxidation of aniline to synthesize nitrosobenzene or its derivatives under light conditions (see "Acs Catalysis", 2014, Vol. 4, No. 8, 2418-2425.). In addition, the research work reported on the use of hydrogen peroxide as an oxidant includes: a phosphotungstate complex catalyst, using hydrogen peroxide as an oxidant, catalyzing the oxidation of aniline to synthesize nitrosobenzene or its derivatives (see "Journal of Catalysis", 2015, Vol. 331, 110-117.). It can be seen that the current optimal synthesis method of nitrosobenzene and its derivatives is direct oxidation synthesis using aniline or its derivatives as raw materials and H2O2 as an oxidant.

[0005] Given the inherent ability of uranium oxide to easily form oxygen vacancies, which significantly enhances its catalytic oxidation ability, and the fact that the current nuclear industry is facing the key challenge of depleted uranium storage and application, it is necessary to explore and develop the remaining 238The application of U resources is particularly urgent and important. To this end, we consider designing a uranium-based catalyst prepared with depleted uranium waste as raw material. This catalyst is designed to catalyze the oxidation reaction of aniline and its derivatives, and promote the synthesis of high-value nitrosobenzene and its derivatives through its unique catalytic properties.

[0006] In summary, we have developed a new uranium-based heterogeneous catalyst UO4·2H2O and pioneered its first introduction into the field of thermal catalysis, achieving a leap in the efficiency of fine chemical synthesis. The preparation process of this catalyst is simple and convenient. It uses U3O8 obtained from depleted UF6 as raw material and can be prepared by a simple precipitation method. What is more worth mentioning is that the method of directly catalyzing aniline to synthesize nitrosobenzene and its derivatives using UO4·2H2O has not been reported so far.

[0007] We innovatively proposed a solution using UO4·2H2O as a catalyst. The preparation process of this catalyst is simple and convenient. It uses U3O8 obtained from depleted UF6 as raw material and can be prepared by a simple precipitation method. What is more worth mentioning is that the method of directly catalyzing aniline to synthesize nitrosobenzene and its derivatives using UO4·2H2O has not been reported so far. This breakthrough innovation not only solves the problem that has long plagued the industry, but also solves the problem that has long plagued the industry. 238 It has opened up a new solution to the problem of difficult-to-handle U residue, and successfully achieved the goal of synthesizing high-value-added fine chemicals at low cost and high efficiency, fully demonstrating its unprecedented application potential and huge commercial value. Summary of the invention

[0008] The present invention finds that the UO4·2H2O catalyst prepared by using U3O8 obtained from depleted UF6 as raw material can catalytically oxidize aniline or its derivatives to form nitrosobenzene or its derivatives. Therefore, the present invention not only provides a new method for utilizing depleted uranium, but also proposes a low-cost, green and efficient method for preparing nitrosobenzene or its derivatives. The method is simple, low-cost, and highly safe, and is more in line with the concept of green and friendly chemistry. Specifically, it includes the following contents:

[0009] In a first aspect, the present invention provides a method for preparing a UO4·2H2O catalyst by using U3O8 obtained from depleted UF6 as a raw material through simple dissolution and reprecipitation.

[0010] Preferably, the catalyst preparation method comprises the following steps:

[0011] (1) Preparation of UO4·2H2O: Weigh a specific mass of U3O8 prepared from depleted UF6, place it in a container, add an appropriate amount of concentrated nitric acid or concentrated hydrochloric acid while heating and stirring, and add an appropriate amount of deionized water to completely dissolve the U3O8 to form a transparent uranyl salt solution, then add an appropriate amount of hydrogen peroxide, continue stirring for several hours, separate the solid product, wash and dry it to obtain UO4·2H2O. Its XRD crystal structure is shown in the attached figure. Figure 1 The transmission electron microscope image is shown in the attached Figure 2 The scanning electron microscope image is shown in the attached Figure 3 The full spectrum of its X-ray photoelectron spectrum is shown in the attached Figure 4 shown.

[0012] Preferably, the structural formula of the aniline or its derivative is as shown in the following formula (I), and the structural formula of the nitrosobenzene or its derivative is as shown in the following formula (II):

[0013]

[0014] Among them, R1-R5 are independently selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid, nitro, substituted or unsubstituted straight or branched alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino, and cyano.

[0015] Preferably, R1-R5 are independently selected from hydrogen, methyl, chlorine, bromine, and methoxy.

[0016] Preferably, the aniline or its derivatives include: aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-chloroaniline, p-bromoaniline and p-methoxyaniline.

[0017] In a second aspect, the present invention provides a method for preparing nitrosobenzene or its derivatives, the method comprising: using aniline or its derivatives shown in the following formula (I) as a raw material, an organic solvent as a reaction solvent, UO4·2H2O as a catalyst, and hydrogen peroxide as an oxidant, and catalytically oxidizing to synthesize nitrosobenzene shown in the following formula (II), wherein the organic solvent comprises one or a combination of isopentane, n-pentane, n-octane, n-heptane, cyclohexane, n-hexane, and cyclopentane;

[0018]

[0019] Among them, R1-R5 are independently selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid, nitro, substituted or unsubstituted straight or branched alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino, and cyano.

[0020] Preferably, R1-R5 are independently selected from hydrogen, methyl, chlorine, bromine, and methoxy.

[0021] Preferably, the aniline or its derivatives include: aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-chloroaniline, p-bromoaniline and p-methoxyaniline.

[0022] Preferably, the catalyst is UO4·2H2O.

[0023] Preferably, the ratio of the catalyst to aniline or its derivatives is 1-50 mg:1 mmol.

[0024] Preferably, the ratio of the catalyst to aniline or its derivatives is 5-45 mg:1 mmol.

[0025] Preferably, the ratio of the catalyst to aniline or its derivatives is 20-40 mg:1 mmol.

[0026] Preferably, the ratio of the catalyst to aniline or its derivatives is 25-35 mg:1 mmol.

[0027] Preferably, the ratio of the catalyst to aniline or its derivatives is 30 mg:1 mmol.

[0028] Preferably, the oxidant is hydrogen peroxide.

[0029] Preferably, the molar ratio of hydrogen peroxide to aniline or its derivatives is 1-10:1.

[0030] Preferably, the molar ratio of hydrogen peroxide to aniline or its derivatives is 2-5:1.

[0031] Preferably, the molar ratio of hydrogen peroxide to aniline or its derivatives is 3:1.

[0032] Preferably, the reaction solvent is n-pentane.

[0033] Preferably, the mass ratio of the reaction solvent to aniline or its derivatives is 1-50:1.

[0034] Preferably, the mass ratio of the reaction solvent to aniline or its derivatives is 2-30:1.

[0035] Preferably, the mass ratio of the reaction solvent to aniline or its derivatives is 3-20:1.

[0036] Preferably, the mass ratio of the reaction solvent to aniline or its derivatives is 5-10:1.

[0037] Preferably, the mass ratio of the reaction solvent to aniline or its derivatives is 6:1.

[0038] Preferably, the method comprises: adding aniline or its derivatives, UO4·2H2O and hydrogen peroxide into a reaction solvent, reacting at 10-60°C for 1-15h; filtering, distilling and recrystallizing to obtain nitrosobenzene or its derivatives.

[0039] Preferably, the reaction temperature is 10-60°C.

[0040] Preferably, the reaction temperature is 15-50°C.

[0041] Preferably, the reaction temperature is 25-35°C.

[0042] Preferably, the reaction temperature is 30°C.

[0043] Preferably, the reaction time is 1-16h.

[0044] Preferably, the reaction time is 5-14 hours.

[0045] Preferably, the reaction time is 8-13 hours.

[0046] Preferably, the reaction time is 12 h.

[0047] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0048] (1) The present invention uses depleted uranium waste as raw material to prepare the catalyst, which effectively solves the problem of safe disposal and reuse of depleted uranium in my country's nuclear energy utilization;

[0049] (2) Aniline or its derivatives used in the present invention are basic raw materials commonly used in industry and are cheap and readily available;

[0050] (3) The present invention uses cheap and readily available hydrogen peroxide as an oxidant, and the reaction temperature is low. Compared with the traditional method using oxidants such as peracetic acid and perbenzoic acid, the cost of the oxidant is greatly reduced, and the problem of toxic substance emissions generated by the use of oxidants is solved;

[0051] (4) The method of the present invention can catalytically oxidize aniline or its derivatives to the corresponding nitrosobenzene or its derivatives with good specificity and a high yield of the target product.

[0052] The present invention will be further described in detail with reference to specific embodiments, but the protection scope of the present invention is not limited thereto. The raw materials used in the following embodiments are all commercially available unless otherwise specified. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 X-ray diffraction crystal structure of the prepared UO4·2H2O catalyst;

[0054] Figure 2Transmission electron microscopy image of the prepared UO4·2H2O catalyst;

[0055] Figure 3 Scanning electron microscopy image of the prepared UO4·2H2O catalyst;

[0056] Figure 4 The full spectrum of X-ray photoelectron spectrum of the prepared UO4·2H2O catalyst;

[0057] Figure 5 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 1;

[0058] Figure 6 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 2;

[0059] Figure 7 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 3;

[0060] Figure 8 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 4;

[0061] Fig. 9 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 5;

[0062] Fig.10 Mass spectrum of the product nitrosobenzene synthesized by the method described in Example 6;

[0063] Fig.11 Mass spectrum of o-methylnitrosobenzene, the product synthesized by the method described in Example 7;

[0064] Fig.12 Mass spectrum of the product m-nitrosomethylbenzene synthesized by the method described in Example 7;

[0065] Fig.13 Mass spectrum of the product p-nitrosomethylbenzene synthesized by the method described in Example 7;

[0066] Fig.14 Mass spectrum of the product p-chloronitrosobenzene synthesized by the method described in Example 7;

[0067] Fig.15 Mass spectrum of the product p-bromonitrosobenzene synthesized by the method described in Example 7;

[0068] Fig.16 Mass spectrum of the product p-methoxynitrosobenzene synthesized by the method described in Example 7.

[0069] Example 1 Synthesis of nitrosobenzene using different reaction solvents

[0070] 1. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 2.049 g of n-octane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% aqueous hydrogen peroxide solution) dropwise at 30°C while stirring, react for 12 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0071] 2. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.878 g of isopentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0072] 3. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 2.109 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0073] 4. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-heptane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0074] 5. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 2.340 g of cyclohexane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0075] 6. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.977 g of n-hexane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0076] 7. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.950 g of cyclopentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0077] The product yield of nitrosobenzene obtained by the preparation method described in 1-7 above was calculated, and the results are shown in Table 1 below:

[0078] Table 1 Process parameters of the preparation method described in Example 1 and the yield of the product nitrosobenzene

[0079]

[0080] The mass spectrum of the product synthesized by the above reaction is as follows Figure 5 As shown (the mass spectra of the main products of the above 7 reactions are the same, so only one mass spectrum is provided). The above results show that aniline can be catalyzed to synthesize nitrosobenzene using organic solvents (isopentane, n-pentane, n-octane, n-heptane, cyclohexane, n-hexane, cyclopentane, etc.) as reaction solvents, hydrogen peroxide as oxidant, and UO4·2H2O as catalyst; among them, the yield of synthesizing nitrosobenzene using n-pentane as reaction solvent is as high as 98%.

[0081] Example 2 Synthesis of nitrosobenzene with different amounts of reaction solvent

[0082] 1. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 0.620 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% aqueous hydrogen peroxide solution) dropwise at 30°C while stirring, react for 12 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0083] 2. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.240 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 30°C. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0084] 3. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0085] 4. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 2.480 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 ml of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0086] 5. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 3.10 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 30°C. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0087] 6. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 3.72 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0088] The product yield of nitrosobenzene obtained by the preparation method described in 1-6 above was calculated, and the results are shown in Table 2 below:

[0089] Table 2 Process parameters of the preparation method described in Example 2 and the yield of the product nitrosobenzene

[0090]

[0091] The mass spectrum of the main product obtained from the above reaction is as follows Figure 6As shown (the mass spectra of the main products of the above 6 reactions are the same, so only one mass spectrum is provided). The above results show that aniline can be catalyzed to synthesize nitrosobenzene using n-pentane as the reaction solvent (the mass ratio of n-pentane to aniline is 1-50:1), hydrogen peroxide as the oxidant, and UO4·2H2O as the catalyst; at the same time, when the mass ratio of n-pentane to aniline is 5-35:1, the yield of nitrosobenzene obtained by the reaction is more than 80%, and when the mass ratio of n-pentane to aniline is 15-30:1, the yield of nitrosobenzene obtained by the reaction is as high as more than 90%, and can reach up to 99% at the highest.

[0092] Example 3 Synthesis of nitrosobenzene at different reaction temperatures

[0093] 1. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 10°C while stirring, react for 12 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0094] 2. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 15°C. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0095] 3. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 20°C. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0096] 4. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 25°C. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0097] 5. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0098] 6. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 35°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0099] 7. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 40°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0100] 8. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 45°C while stirring, react for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0101] 9. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 50°C while stirring, react for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0102] 10. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 55°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0103] 11. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 60°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0104] The product yield of nitrosobenzene obtained by the preparation method described in 1-11 above was calculated, and the results are shown in Table 3 below:

[0105] Table 3 Process parameters of the preparation method described in Example 3 and the yield of the product nitrosobenzene

[0106]

[0107] The mass spectrum of the main product obtained from the above reaction is as follows Figure 7 As shown (the mass spectra of the main products of the above 11 reactions are the same, so only one mass spectrum is provided). The above results show that when the reaction temperature is 10-60°C, hydrogen peroxide is used as an oxidant, n-pentane is used as a reaction solvent, and UO4·2H2O is used as a catalyst, aniline can be catalyzed to synthesize nitrosobenzene; when the reaction temperature is 15-35°C, the yield of nitrosobenzene obtained by the reaction is more than 80%; and when the reaction temperature is 20-35°C, the yield of nitrosobenzene obtained by the reaction can reach more than 90%.

[0108] Example 4 Synthesis of nitrosobenzene with different reaction times

[0109] 1. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 1 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0110] 2. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 2 h, then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0111] 3. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 4 hours, then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0112] 4. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 6 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0113] 5. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 8 hours, then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0114] 6. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 30°C. React for 10 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0115] 7. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0116] 8. Add 30.0 mg of UO4·2H2O catalyst into a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 14 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0117] 9. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 16 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0118] The product yield of nitrosobenzene obtained by the preparation method described in 1-9 above was calculated, and the results are shown in Table 4 below:

[0119] Table 4 Process parameters of the preparation method described in Example 4 and the yield of the product nitrosobenzene

[0120]

[0121]

[0122] The mass spectrum of the main product obtained from the above reaction is as follows Figure 8 As shown (the mass spectra of the main products of the above 9 reactions are the same, so only one mass spectrum is provided). The above results show that when the reaction time is 1-16h, hydrogen peroxide is used as an oxidant, n-pentane is used as a reaction solvent, and UO4·2H2O is used as a catalyst, aniline can be catalyzed to synthesize nitrosobenzene; when the reaction time is 5-16h, the yield of nitrosobenzene obtained by the reaction is more than 80%; and when the reaction time is 10-16h, the yield of nitrosobenzene obtained by the reaction can reach more than 99%.

[0123] Example 5 Synthesis of nitrosobenzene with different amounts of hydrogen peroxide added

[0124] 1. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 1 mmol of hydrogen peroxide (i.e., 0.1 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0125] 2. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 2 mmol of hydrogen peroxide (i.e., 0.2 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 30°C. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0126] 3. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0127] 4. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 4 mmol of hydrogen peroxide (i.e., 0.4 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0128] 5. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 5 mmol of hydrogen peroxide (i.e., 0.5 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0129] 6. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 6 mmol of hydrogen peroxide (i.e., 0.6 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0130] The product yield of nitrosobenzene obtained by the preparation method described in 1-6 above was calculated, and the results are shown in Table 5 below:

[0131] Table 5 Process parameters of the preparation method described in Example 5 and the yield of the product nitrosobenzene

[0132]

[0133] The mass spectrum of the main product obtained from the above reaction is as follows Fig. 9As shown (the mass spectra of the main products of the above 6 reactions are the same, so only one mass spectrum is provided). The above results show that when the molar ratio of the oxidant hydrogen peroxide to aniline is 1-6:1, n-pentane is used as the reaction solvent, and UO4·2H2O is used as the catalyst, aniline can be catalyzed to synthesize nitrosobenzene; when the molar ratio of the oxidant hydrogen peroxide to aniline is 2-5:1, the yield of nitrosobenzene obtained by the reaction is more than 80%; and when the molar ratio of the oxidant hydrogen peroxide to aniline is 3-4:1, the yield of nitrosobenzene obtained by the reaction is as high as more than 92%.

[0134] Example 6 Synthesis of nitrosobenzene with different catalyst addition amounts

[0135] 1. Add 1.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0136] 2. Add 5.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise while stirring at 30°C. React for 12 hours, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0137] 3. Add 10.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0138] 4. Add 15.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0139] 5. Add 20.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0140] 6. Add 25.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill, and recrystallize to obtain the product nitrosobenzene.

[0141] 7. Add 30.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0142] 8. Add 35.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0143] 9. Add 40.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0144] 10. Add 45.0 mg of UO4·2H2O catalyst to a reaction tube with a volume of 25 mL, then add 0.093 g of aniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0145] 11. Add 50.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.093 g of aniline and 1.860 g of n-pentane, add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of a 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 12 h, and then filter, distill and recrystallize to obtain the product nitrosobenzene.

[0146] The product yield of nitrosobenzene obtained by the preparation method described in 1-11 above was calculated, and the results are shown in Table 6 below:

[0147] Table 6 Process parameters of the preparation method described in Example 6 and the yield of the product nitrosobenzene

[0148]

[0149]

[0150] The mass spectrum of the main product obtained from the above reaction is as follows Fig.10 As shown (the mass spectra of the main products of the above 11 reactions are the same, so only one mass spectrum is provided). The above results show that when hydrogen peroxide is used as an oxidant, n-pentane is used as a reaction solvent, UO4·2H2O is used as a catalyst, and the ratio of the catalyst to aniline or its derivatives is 1-50 mg:1 mmol, aniline can be catalyzed to synthesize nitrosobenzene; and when the ratio of the catalyst to aniline or its derivatives is 20-50 mg:1 mmol, the yield of nitrosobenzene obtained in the reaction is higher than 80%; at the same time, when the ratio of the catalyst to aniline or its derivatives is 25-45 mg:1 mmol, the yield of nitrosobenzene obtained in the reaction is as high as more than 90%.

[0151] Example 7 Synthesis of Nitrosobenzene Derivatives Using Different Aniline Derivatives

[0152] 1. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.107 g of o-methylaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, then filter, distill, and recrystallize to obtain the product o-methylnitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.11 As shown, the structural formula is shown in Formula 2.

[0153]

[0154] 2. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.107 g of m-methylaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, then filter, distill, and recrystallize to obtain the product m-methylnitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.12 As shown, the structural formula is shown in Formula 3.

[0155]

[0156] 3. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.107 g of p-methylaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, then filter, distill, and recrystallize to obtain the product p-methylnitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.13 As shown, the structural formula is shown in Formula 4.

[0157]

[0158] 4. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.127 g of p-chloroaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 12 hours, and then filter, distill, and recrystallize to obtain the product p-chloronitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.14 As shown, the structural formula is shown in Formula 5.

[0159]

[0160] 5. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.172 g of p-bromoaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring, react for 12 hours, and then filter, distill, and recrystallize to obtain the product p-bromonitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.15 As shown, the structural formula is shown in Formula 6.

[0161]

[0162] 6. Add 30.0 mg of UO4·2H2O catalyst to a 25 mL reaction tube, then add 0.123 g of p-chloroaniline and 1.860 g of n-pentane, and add 3 mmol of hydrogen peroxide (i.e., 0.3 mL of 30% hydrogen peroxide aqueous solution) dropwise at 30°C while stirring. React for 12 hours, then filter, distill, and recrystallize to obtain the product p-methoxynitrosobenzene. The mass spectrum of the product is shown in the figure below. Fig.16 As shown, the structural formula is shown in Formula 7.

[0163]

[0164] The product yield of the nitrosobenzene derivative obtained by the preparation method described in 1-6 above was calculated, and the results are shown in Table 7 below:

[0165] Table 7 Process parameters and product yields of the preparation method described in Example 7

[0166]

[0167] The mass spectra of the main products in the above reactions 1-6 are as follows: Figure 11-16 As shown. The above results show that, with n-pentane as the reaction solvent, hydrogen peroxide as the oxidant, and UO4·2H2O as the catalyst, o-methylaniline can be catalyzed to synthesize o-methylnitrosobenzene with a yield of 91%; m-methylaniline can be catalyzed to synthesize m-methylnitrosobenzene with a yield of 93%; p-methylaniline can be catalyzed to synthesize p-methylnitrosobenzene with a yield of 94%; p-chloroaniline can be catalyzed to synthesize p-chloronitrosobenzene with a yield of 86%; p-bromoaniline can be catalyzed to synthesize p-bromonitrosobenzene with a yield of 82%; and p-methoxyaniline can be catalyzed to synthesize p-methoxynitrosobenzene with a yield of 96%. Therefore, the method of the present invention can catalyze aniline or its derivatives to synthesize nitrosobenzene or its derivatives, and the yield of the target product obtained is relatively high.

[0168] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.

Claims

1. Preparation method of depleted uranium-based UO4·2H2O and its application in catalytic synthesis of nitrosobenzene or its derivatives.

2. As claimed in claim 1, a method for preparing a UO4·2H2O heterogeneous catalyst, characterized in that: U3O8 made from depleted UF6 is used as the starting material, concentrated acid is used as the solvent, a specific oxidant is added, and deionized water is used as the diluent. The specific operation steps are as follows: Preparation of UO4·2H2O: Weigh a specific mass of U3O8 prepared with depleted UF6 as raw material, place it in a container, add an appropriate amount of concentrated acid while heating and stirring, so that U3O8 is completely dissolved, then add an appropriate amount of deionized water to form a transparent uranyl salt solution, and then add an appropriate amount of oxidant. After continuous stirring for several hours, separate the solid product, wash and dry it to obtain UO4·2H2O.

3. A method for preparing UO4·2H2O according to claims 1 and 2, characterized in that: The concentrated acid described in claim 2 is concentrated nitric acid with a mass fraction greater than 65% or concentrated hydrochloric acid with a mass fraction greater than 37%, the oxidant is hydrogen peroxide with a mass fraction greater than 25%, the uranyl salt is uranyl nitrate or uranyl chloride, and the stirring time is 2-25h.

4. A method for preparing UO4·2H2O according to claims 1 and 2, characterized in that: The drying temperature described in claim 2 is 60-240° C. and the drying time is 2-8 hours.

5. The use of catalytic synthesis of nitrosobenzene or its derivatives as claimed in claim 1, characterized in that: The structural formula of the nitrosobenzene or its derivatives is shown in the following formula (II). The raw material for synthesizing nitrosobenzene or its derivatives is aniline or its derivatives, and its structural formula is shown in the following formula (I): Among them, R1-R5 are independently selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid, nitro, substituted or unsubstituted straight or branched alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino, and cyano.

6. A method for preparing nitrosobenzene or a derivative thereof as claimed in claims 1 and 5, comprising: Aniline or its derivatives shown in the following formula (I) are used as raw materials, an organic solvent is used as a reaction solvent, UO4·2H2O is used as a catalyst, and hydrogen peroxide is used as an oxidant to synthesize nitrosobenzene or its derivatives shown in the following formula (II) through a catalytic oxidation reaction, wherein the organic solvent comprises one or a combination of isopentane, n-pentane, n-octane, n-heptane, cyclohexane, n-hexane, and cyclopentane; Among them, R1-R5 are independently selected from any one of hydrogen, halogen, hydroxyl, sulfonic acid, nitro, substituted or unsubstituted straight or branched alkyl, alkoxy, carbonyl, alkenyl, alkynyl, substituted or unsubstituted aryl, acylamino, and cyano.

7. The synthesis method according to claims 1, 5 and 6, characterized in that: The amount ratio of the catalyst to aniline or its derivative is 1-50 mg:1 mmol. The molar ratio of hydrogen peroxide to aniline or its derivative is 1-10:

1. The mass ratio of the reaction solvent to aniline or its derivative is 1-50:

1. The reaction temperature is 10-60°C and the reaction time is 1-16 hours.

8. The synthesis method according to claims 5-7, characterized in that: The R1-R5 are selected from hydrogen, methyl, chlorine, bromine, and methoxy. The aniline or its derivatives include: aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-chloroaniline, p-bromoaniline, and p-methoxyaniline.

9. The synthesis method according to any one of claims 5 to 8, characterized in that: Aniline or its derivatives, UO4·2H2O (the amount ratio of UO4·2H2O to aniline or its derivatives is 30 mg:1 mmol), and hydrogen peroxide (the molar ratio of UO4·2H2O to aniline or its derivatives is 3:1) are added to n-pentane (the mass ratio of UO4·2H2O to aniline or its derivatives is 6:1), and the mixture is reacted at 30° C. for 12 hours; nitrosobenzene or its derivatives are obtained by filtration, distillation, and recrystallization.

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