Method for chemically synthesizing decenacarbonyl dirhenium
Through the heating decomposition of ammonium perrhenate and the heating and pressurization reaction in the autoclave, high-purity decacarbonyl dirhenium was successfully prepared, which solved the problems of high reaction temperature and equipment corrosion in the prior art, and achieved low-temperature decomposition and high-purity products are available for fine chemistry and aviation.
Patent Information
- Application Number
- CN202411290116.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-14
- Publication Date
- 2024-12-17
AI Technical Summary
In the prior art, the chloride decomposition reaction of rhenium leads to high reaction temperature and serious corrosion of equipment, and lacks an effective preparation process for decacarbonyl dirhenium.
Ammonium perrhenate is heated and decomposed in a tube furnace to form an intermediate rhenium compound, and heated and pressurized reaction with the carbon compound in an autoclave. The decacarbonyl dirhenium with a purity of more than 99% is obtained by filtration and drying of the reactant. .
Low-temperature decomposition and plating of rhenium is achieved, reducing equipment corrosion, and obtaining high-purity decacarbonyl dirhenium. It is suitable for fine chemistry and aviation fields. It has simple process, high economic value, and is feasible for industrialization.
Smart Images
Figure CN119143185A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of compound preparation, in particular to a method for chemically synthesizing dirhenium decacarbonyl. Technical Background
[0002] Dirhenium decacarbonyl (Re2(CO) 10 ) is an important organic synthesis catalyst with unique structure and catalytic properties, and plays a key role in the field of fine chemical synthesis. Decacarbonyldirhenium is widely used in hydrogenation reactions, oxidation reactions and carbonylation reactions due to its high activity and selectivity. In addition, rhenium is favored in the aviation field due to its high temperature resistance specificity. The current method used for chemical vapor deposition rhenium plating is mainly achieved through the decomposition reaction of rhenium chloride, which has problems such as high reaction temperature and severe equipment corrosion. Decacarbonyldirhenium as a precursor material can achieve low-temperature decomposition rhenium plating, and the degree of equipment corrosion is lighter. At present, there are few literature reports on the process of preparing decacarbonyldirhenium. Summary of the invention
[0003] In order to solve the above problems, the object of the present invention is to provide a method for chemically synthesizing dirhenium decacarbonyl.
[0004] The technical solution adopted by the present invention to solve the technical problem is:
[0005] Ammonium perrhenate is placed in a tubular furnace and heated and decomposed in a specific atmosphere to generate an intermediate rhenium compound; the obtained rhenium compound is placed in a high-pressure reactor, a carbon compound is added, heated and pressurized to react, and crude decacarbonyl dirhenium is synthesized; the crude decacarbonyl dirhenium is leached with a reactant, filtered and dried to obtain decacarbonyl dirhenium with a purity greater than 99%.
[0006] In the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the ammonium perrhenate is commercially available with a purity of 4N;
[0007] Furthermore, in the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the specific atmosphere is argon, helium or hydrogen;
[0008] Furthermore, in the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the carbon compound is carbon monoxide.
[0009] Furthermore, in the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the thermal decomposition of ammonium perrhenate is carried out at 320°C-450°C.
[0010] In the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the carbon compound heating and pressurizing reaction is carried out under the conditions of 28MPa-32MPa and 400℃-460℃.
[0011] In the above-mentioned method for chemically synthesizing dirhenium decacarbonyl, the purification reactant may be nitric acid or hydrogen peroxide.
[0012] The beneficial effects of the present invention are as follows: the present invention uses commercially available 4N purity ammonium perrhenate to synthesize decacarbonyl dirhenium through a series of reactions, which can be widely used in the fields of fine chemistry, aerospace, etc. The process reagents are common and easily available, the experimental operation is simple, no expensive equipment investment and strict operating requirements are required, and the product is a new material product with high added value, high economic value, and strong industrial feasibility. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 This is the XRD pattern of the dirhenium decacarbonyl product. DETAILED DESCRIPTION
[0014] Example 1
[0015] Commercially available 4N pure ammonium perrhenate was placed in a tube furnace and a gas flow rate of 0.5 m 3 / h of helium was heated and decomposed at 320℃ for 2h, and then the solid product powder was evenly placed in an autoclave, and carbon monoxide gas was introduced. The reaction was carried out for 48h under the conditions of 400℃ and 28MPa in the autoclave. After the reaction was completed, the temperature in the autoclave was cooled to room temperature and the reactant was taken out. Hydrogen peroxide and the solid product were mixed at a liquid-solid ratio of 2:1 and stirred at room temperature for 2h. After the reaction, it was filtered and dried to obtain dirhenium decacarbonyl with a purity of 99%, and the overall reaction conversion rate was 43.43%.
[0016] Example 2
[0017] Commercially available 4N pure ammonium perrhenate was placed in a tube furnace and a gas flow rate of 0.8 m 3 / h of argon gas was heated and decomposed at 420℃ for 2h, and the obtained solid product powder was evenly placed in an autoclave, and carbon monoxide gas was introduced. The reaction was carried out for 48h under the conditions of the temperature in the reactor being 420℃ and the reaction pressure being 30MPa. After the reaction was completed, the temperature in the reactor was cooled to room temperature and the reactant was taken out. Hydrogen peroxide and the obtained solid product were mixed at a liquid-solid ratio of 3:1 and stirred at room temperature for 2h. After the reaction, it was filtered and dried to obtain dirhenium decacarbonyl with a purity of 99%, and the overall reaction conversion rate was 60.51%.
[0018] Example 3
[0019] Commercially available 4N pure ammonium perrhenate was placed in a tube furnace and a gas flow rate of 0.05 m 3 / h of hydrogen was heated and decomposed at 450℃ for 2h, and the obtained solid product powder was evenly placed in an autoclave, and carbon monoxide gas was introduced. The reaction was carried out for 48h under the conditions of the temperature in the reactor being 460℃ and the reaction pressure being 32MPa. After the reaction was completed, the temperature in the reactor was cooled to room temperature and the reactant was taken out. 10% nitric acid was mixed with the obtained solid product at a liquid-solid ratio of 3:1 and stirred at room temperature for 2h. After the reaction, it was filtered and dried to obtain dirhenium decacarbonyl with a purity of 99%, and the overall reaction conversion rate was 38.34%.
[0020] Depend on Figure 1 The X-ray diffraction (XRD) characterization diagram shows that the diffraction peaks of the experimental results show good consistency with the standard card in terms of 2θ values, indicating that the crystal structure of the sample is consistent with expectations and is dirhenium decacarbonyl.
Claims
1. A method for chemically synthesizing dirhenium decacarbonyl, It is characterized in that Ammonium perrhenate is heated and decomposed under a specific atmosphere to prepare a rhenium compound; the obtained rhenium compound is then placed in a high-pressure reactor, and a carbon compound is introduced to react under heating and pressure to synthesize a crude product of decacarbonyl dirhenium; thereafter, the compound is leached with a reactant, filtered and dried to obtain decacarbonyl dirhenium with a purity greater than 99%.
2. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The ammonium perrhenate is commercially available with a purity of 4N.
3. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The specific atmosphere is helium, argon or hydrogen.
4. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The carbon compound is carbon monoxide.
5. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The ammonium perrhenate thermal decomposition is heated at 320°C-450°C.
6. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The heating and pressurizing reaction of the carbon compound is carried out under the conditions of 28MPa-32MPa and 400℃-460℃.
7. A method for chemically synthesizing dirhenium decacarbonyl according to claim 1, Features: The reactant for the decacarbonyl dirhenium purification reaction can be nitric acid or hydrogen peroxide.