A method and device for synthesizing metal precursor organic carbonyl cobalt compounds

Abstract

The invention discloses a method and device for synthesizing a metal precursor organic carbonyl cobalt compound, which is particularly suitable for the synthesis and preparation of dicarbonyl cyclopentadienyl cobalt and (3,3-dimethyl-1-butyne) hexacarbonyl dicobalt. Specifically related to the technical field of compound synthesis, comprising the following steps: S01-S07, raw materials are weighed to include the following components: 120 parts of activated carbon, 250 parts of water, 3-9.1 parts of gold chloride, 118.9-129.8 parts of cobalt salt, 40%-80% hydrazine hydrate aqueous solution, 30% sodium hydroxide aqueous solution, 500 parts of dichloromethane, 69.4 parts of cyclopentadiene monomer; activated carbon, gold chloride, cobalt salt and water are added to the reactor, stirring is started, and the temperature is controlled at 10-15°C, 40% hydrazine hydrate aqueous solution is added dropwise, and the temperature is slowly heated to 50-55°C after the addition is completed; the reaction solution is filtered, and the filtered solid is dried and then put into the reactor. The invention uses cobalt salts, which are widely available and inexpensive, as raw materials to synthesize carbonyl cobalt compounds, without the need to use expensive dicobalt octacarbonyl or the like as a carbonyl cobalt source for reaction with corresponding organic matter for synthesis.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, and in particular to a method and device for synthesizing a metal precursor organic carbonyl cobalt compound. Background Art

[0002] Carbonyl cobalt compound is a metal complex. With the development of emerging companies in 5G communications, artificial intelligence and the Internet of Things, carbonyl cobalt compounds are widely used in chip manufacturing, electronic components, magnetic materials and other fields.

[0003] According to patent number CN202311079368.7, publication (announcement) date: 2023-11-28, a method for preparing dicarbonyl cyclopentadienyl cobalt is disclosed, comprising the following steps: adding raw material octacarbonyl dicobalt and tetrahydrofuran solvent to a reaction bottle under the protection of an inert gas, setting up a normal pressure reflux device, and starting stirring; adding a tetrahydrofuran solution of cyclopentadienyl sodium dropwise to the reaction bottle, and after the addition is completed, maintaining 70-80°C for stirring and reacting for 6-10 hours; after the stirring and reflux is completed, first perform atmospheric distillation to evaporate the solvent tetrahydrofuran; then change to a vacuum distillation device, and perform vacuum distillation to obtain a crude dicarbonyl cyclopentadienyl cobalt product; the obtained crude dicarbonyl cyclopentadienyl cobalt product is subjected to vacuum distillation to obtain a finished dicarbonyl cyclopentadienyl cobalt product; all of the above steps are carried out under an inert gas environment. The preparation method has a simple synthesis route, readily available raw materials, short reaction time, high synthesis efficiency, high product yield, little raw material residue, high product purity, can be used for industrial production, and can meet the growing market demand.

[0004] In the prior art including the above-mentioned patents, when producing cobalt carbonyl compounds such as dicarbonyl cyclopentadienyl cobalt and (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, octacarbonyl dicobalt and the like are basically used as carbonyl cobalt sources for reaction with corresponding organic substances for synthesis, wherein octacarbonyl dicobalt is mainly prepared by reacting cobalt salts with synthesis gas (CO, H2) in an inert solvent under high temperature and high pressure conditions, resulting in problems such as high operating conditions, complex production processes and safety risks in the synthesis process, thereby increasing the cost of cobalt carbonyl compounds synthesized by reaction of organic substances with octacarbonyl dicobalt and the like as carbonyl cobalt sources. Summary of the invention

[0005] The purpose of the present invention is to provide a method and device for synthesizing metal precursor organic carbonyl cobalt compounds, aiming to solve the above problems.

[0006] In order to achieve the above object, the present invention provides the following technical solution: a method for synthesizing a metal precursor organic carbonyl cobalt compound, specifically comprising the following steps:

[0007] S01, the raw materials are weighed in parts by weight, including the following components: 120 parts of activated carbon, 250 parts of water, 3-9.1 parts of gold chloride, 118.9-129.8 parts of cobalt salt, 40%-80% mass concentration of hydrazine hydrate aqueous solution, 30% mass concentration of sodium hydroxide aqueous solution, 500 parts of dichloromethane, and 69.4 parts of cyclopentadiene monomer;

[0008] S02, add activated carbon, gold chloride, cobalt salt and water into the reactor, start stirring, control the temperature at 10-15°C, add 40% hydrazine hydrate aqueous solution dropwise, and slowly heat to 50-55°C after the addition is complete;

[0009] S03, add 30% sodium hydroxide aqueous solution to the reactor to control the pH of the reaction solution to be maintained between 7.5 and 8, and stir the reaction at controlled temperature for 5 to 6 hours;

[0010] S04, filtering to obtain the solid in the reaction kettle, eluting the solid with deionized water, and drying it at 120-125° C. under absolute pressure for 10 h to obtain a black solid powder;

[0011] S05. Add the black solid powder into the reactor under the protection of inert gas, then add dichloromethane and cyclopentadiene monomer, control the temperature at 25-30° C., introduce carbon monoxide gas into the reactor until the gas phase pressure reaches 0.3-0.4 MPa, and continue stirring;

[0012] S06, the gas phase pressure in the reactor is stable, the reaction is completed, the filtrate in the reactor is collected, and the filtered solid is eluted with dichloromethane and combined with the filtrate for collection;

[0013] S07. Most of the solvent in the filtrate is distilled off under normal pressure, and then distilled under absolute pressure to obtain dicarbonylcyclopentadienylcobalt liquid.

[0014] Preferably, the cobalt salt is cobalt carbonate or cobalt chloride.

[0015] Preferably, the filter solid obtained in step S05 and aqua regia are added into a reactor, the temperature is controlled at 25-30°C and stirred for 3-4 hours, and then filtered to obtain the filter solid. After being washed with clean water, the filter solid can replace the gold chloride and activated carbon in step S01 as a catalyst and its carrier.

[0016] Preferably, the cyclopentadiene monomer in step S05 is replaced by 3,3-dimethyl-1-butyne to obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl liquid in step S06.

[0017] A synthesis device for metal precursor organic carbonyl cobalt compounds, which is used to realize the above-mentioned synthesis method of metal precursor organic carbonyl cobalt compounds, comprises a reaction kettle on which a collecting and distributing mechanism is arranged, the collecting and distributing mechanism comprises a rotating shaft and a collecting and distributing paddle movably arranged at the first end of the rotating shaft, the collecting and distributing paddle is driven to rotate forward to collect filtered solids and reverse to diffuse the filtered solids in the collecting and distributing paddle.

[0018] Preferably, a filter plate is provided at the first end of the collecting and distributing blade, a distributing opening is provided at one side of the collecting and distributing blade, and the collecting and distributing blade is driven to rotate forward to collect filtered solids on the filter plate through the distributing opening.

[0019] Preferably, an arc surface is provided on the other side of the collecting and distributing blade, and a guide angle is provided at the first end of the collecting and distributing blade. The collecting and distributing blade is driven to reverse to guide the liquid to flow along the guide angle and flow rapidly along both ends of the distributing opening to form a fast flow zone.

[0020] Preferably, the reactor is provided with a dripping mechanism, which includes a dripping head, a hollow cavity is provided on the rotating shaft, an annular groove is provided on the hollow cavity, and the dripping head alternately sprays a fast and a slow droplet, and the two droplets collide in the annular groove to diffuse the droplets to the fast flow area.

[0021] Preferably, the collecting and distributing paddles are slidably connected to the first end of the rotating shaft, and the two collecting and distributing paddles fit together and maintain an inclined state as the rotating shaft is lifted, and the two collecting and distributing paddles fit together and maintain a horizontal state as the rotating shaft is lowered.

[0022] Preferably, a rotation slot is provided on the rotating shaft, and a flip connection plate arranged on the collecting and distributing blade is slidably connected in the rotation slot.

[0023] In the above technical scheme, the present invention provides a method and device for synthesizing a metal precursor organic carbonyl cobalt compound, which has the following beneficial effects: using a widely available and low-priced cobalt salt as a raw material, reducing it with a catalyst in water through a reducing agent, and co-crystallizing it into an active cobalt-containing complex that is deposited on a carrier. The complex shows high activity to traditional carbonylation reagents and can be efficiently converted into an active carbonyl cobalt species under mild conditions to react with an organic source to generate an organic carbonyl cobalt compound, without the need to use expensive octacarbonyl dicobalt or the like as a carbonyl cobalt source to react with the corresponding organic matter for synthesis. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0025] Figure 1 A schematic diagram of a process flow provided by an embodiment of the present invention;

[0026] Figure 2 The hydrogen nuclear magnetic spectrum of dicarbonylcyclopentadienylcobalt provided in the embodiment of the present invention;

[0027] Figure 3 The nuclear magnetic carbon spectrum of dicarbonylcyclopentadienylcobalt provided in the embodiment of the present invention;

[0028] Figure 4 The nuclear magnetic hydrogen spectrum of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl provided in the embodiment of the present invention;

[0029] Figure 5 The nuclear magnetic carbon spectrum of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl provided in the embodiment of the present invention;

[0030] Figure 6 A schematic diagram of a reaction kettle provided in an embodiment of the present invention;

[0031] Figure 7 A schematic diagram of a reactor explosion provided in an embodiment of the present invention;

[0032] Figure 8 for Figure 7 The enlarged schematic diagram at A in the middle;

[0033] Fig. 9 An exploded schematic diagram of a collecting and distributing mechanism provided by an embodiment of the present invention;

[0034] Fig.10 for Fig. 9 The enlarged schematic diagram of point B in the middle;

[0035] Fig.11 A cross-sectional schematic diagram of a liquid dripping mechanism provided by an embodiment of the present invention;

[0036] Fig.12 A schematic cross-sectional view of a liquid dripping mechanism and a reaction kettle provided in an embodiment of the present invention;

[0037] Fig.13 A schematic diagram of a clockwise operation of a collecting and distributing mechanism provided by an embodiment of the present invention;

[0038] Fig.14 A schematic diagram of the counterclockwise operation of the collecting and distributing mechanism provided in an embodiment of the present invention.

[0039] Description of reference numerals:

[0040] 1. Reactor; 11. Pressure-resistant upper cover; 2. Collecting and distributing mechanism; 21. Rotating shaft; 210. Flip connecting plate; 211. Annular groove; 212. Turning slide; 213. Retention contact; 214. Extrusion strip; 22. Collecting and distributing blade; 221. Guide angle; 2211. Cover plate; 2212. Filter plate; 222. Arc surface; 223. Dispersing opening; 3. Dripping mechanism; 30. Liquid storage tank; 31. Dripping head; 32. First extrusion capsule; 321. Second extrusion capsule; 33. Air guide tube; 331. Liquid outlet pipe; 332. Spiral protrusion; 34. Barrier strip. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical solution and advantages of the embodiments of the present disclosure clearer, the technical solution of the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings of the embodiments of the present disclosure. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of the embodiments. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure. Embodiment 1

[0042] 129.8 g of cobalt chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly raised to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0043] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C. Carbon monoxide gas was introduced into the reactor to a gas phase pressure of 0.3-0.4MPa, and a small amount of heat was released during the ventilation process. Carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3-0.4MPa, and the temperature was controlled and stirred for 36-38h. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then distilled at absolute pressure to obtain 22.5g of dark red liquid, and the molar yield calculated as cobalt chloride was 12.5%. The sample was tested by NMR, and the obtained product was identified as the target product by comparing with the NMR spectrum of the standard product: dicarbonyl cyclopentadienyl cobalt; 1HNMR (C6D6, 500MHZ): δ = 4.40 (s, 5H); 13CNMR (C6D6, 500MHZ): δ = 84.23. The inorganic purity detected by ICP-MS was > 6N; the organic purity detected by NMR was > 99%. Embodiment 2

[0044] 129.8 g of cobalt chloride, 3 g of gold chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly heated to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0045] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C to pass carbon monoxide gas into the reactor until the gas phase pressure was 0.3-0.4MPa, and a small amount of heat was released during the ventilation process. Carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3-0.4MPa, and the temperature was controlled and stirred for 12-14h, and the gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, and a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then distilled at absolute pressure to obtain 163.5g of dark red liquid, and the molar yield calculated as cobalt chloride was 90.8%. ICP-MS detected inorganic purity>6N; Au content <1ppm; NMR detected organic purity>99%. Embodiment 3

[0046] 118.9 g of cobalt carbonate, 3 g of gold chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly heated to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0047] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C to pass carbon monoxide gas into the reactor until the gas phase pressure was 0.3-0.4MPa, and a small amount of heat was released during the ventilation process. By continuously replenishing carbon monoxide, the gas phase pressure in the reactor was controlled to be maintained between 0.3-0.4MPa, and the temperature was controlled and stirred for 12-14h, and the gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then 161.3g of dark red liquid was obtained by absolute pressure distillation, and the molar yield calculated as cobalt carbonate was 89.6%. ICP-MS detected inorganic purity>6N; Au content <1ppm; NMR detected organic purity>99%. Embodiment 4

[0048] 129.8 g of cobalt chloride, 6.1 g of gold chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly heated to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0049] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C. Carbon monoxide gas was introduced into the reactor until the gas phase pressure was 0.3-0.4MPa. A small amount of heat was released during the ventilation process, and carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3-0.4MPa. The temperature was controlled and stirred for 6-8h, and the gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, and a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then 165.3g of dark red liquid was obtained by absolute pressure distillation, and the molar yield calculated as cobalt chloride was 91.8%. ICP-MS detected inorganic purity>6N; Au content <1ppm; NMR detected organic purity>99%. Embodiment 5

[0050] 129.8 g of cobalt chloride, 9.1 g of gold chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly raised to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0051] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and then 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450~500r / min, and the temperature was controlled at 25~30℃. Carbon monoxide gas was introduced into the reactor until the gas phase pressure was 0.3~0.4MPa. During the ventilation process, heat was released slightly, and carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3~0.4MPa. The temperature was controlled and stirred for 6~8h, and the gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented, and the inert gas was replaced 3 times. The reaction solution was transferred out for suction filtration, and a small amount of dichloromethane was used to wash the filter solid. The filtrate was combined and collected, and most of the solvent in the filtrate was distilled off at normal pressure, and then distilled at absolute pressure to obtain 169.6g of dark red liquid, and the molar yield calculated by cobalt chloride was 94.2%. ICP-MS detected inorganic purity>6N; Au content <1ppm; NMR detected organic purity>99%.

[0052] In summary, the dicarbonylcyclopentadienyl cobalt liquids prepared in Examples 1 to 5 were respectively placed in a nuclear magnetic resonance detector for nuclear magnetic resonance detection, and the data were: 1HNMR (C6D6, 500MHZ): δ=4.41 (s, 5H); 13CNMR (C6D6, 500MHZ): δ=84.23.

[0053] The detailed data of the comparative ingredients are as follows:

[0054]

[0055] In summary, based on the above table, it can be seen that by adding more than 3g of catalyst gold chloride, corresponding to 119~130g of cobalt salt, the molar yield is as high as 89%, avoiding the addition of octacarbonyl dicobalt, and when it is 129.8g of cobalt chloride and 9.1g of gold chloride, the crude product yield reaches 94.2%, which is the best ratio.

[0056] In the process of the present invention, the molar ratio of the cobalt salt, gold chloride, hydrazine hydrate, activated carbon and water is 1:0-0.03:0.6-1:10:25.

[0057] In the preparation process of the present invention, the key factors affecting the reaction activity are: reaction temperature, pH value of the reaction solution and stirring rate.

[0058] According to existing experience, the reaction temperature is preferably 50-55°C, the reaction solution pH is preferably 7.5-8, and the stirring rate is preferably 450-500 r / min. This process parameter is specific to the embodiment of the present invention, and other implementations can be optimized and adjusted accordingly according to the type of reducing agent, the size of the reactor, and the stirring form. Embodiment 6

[0059] 129.8 g of cobalt chloride, 3 g of gold chloride, 120 g of activated carbon and 250 g of water were added to the reactor, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C. 75.1 g of 40% hydrazine hydrate aqueous solution was slowly added to the reaction solution, and a small amount of heat was released during the addition. After the addition was completed, the temperature was slowly heated to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0060] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 90.4g of 3,3-dimethyl-1-butyne were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C to introduce carbon monoxide gas into the reactor until the gas phase pressure was 0.3-0.4MPa, and a small amount of heat was released during the ventilation process. Carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3-0.4MPa, and the temperature was controlled and stirred for 8-10h. The gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, and a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then distilled at absolute pressure to obtain 159.4g of dark red liquid, with a molar yield of 86.6% calculated as cobalt chloride.

[0061] The sample was tested by NMR, and the obtained product was identified as the target product by comparison with the NMR spectrum of the standard product: (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl; 1HNMR (C6D6, 500MHZ): δ=1.05 (s, 9H); 5.43 (s, 1H); 13CNMR (C6D6, 500MHZ): δ=32.89; 35.64; 72.30; 110.90; 200.16. The inorganic purity detected by ICP-MS was> 6N; the Au content was <1ppm; the organic purity detected by NMR was> 99%.

[0062] Based on Example 6, it can be seen that by adding 90.4 grams of 3,3-dimethyl-1-butyne instead of 69.4 grams of cyclopentadiene monomer (prepared by thermal decomposition of dicyclopentadiene), and also using 3 grams of gold chloride as a catalyst, (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl can be obtained, and the molar yield calculated as cobalt chloride is 86.6%, indicating that the cobalt salt derivatization activation and carbonylation strategy provided by the present invention has a certain universality for many organic sources and is a relatively general method for synthesizing organic carbonyl cobalt compounds. Embodiment 7

[0063] Au / activated carbon composite regeneration and recovery: The solid obtained by filtering the dicarbonyl cyclopentadienyl cobalt reaction solution in Example 2 was transferred to a reactor, and 150 g of aqua regia (prepared by one volume of 66% nitric acid and three volumes of 37% hydrochloric acid) was added. The temperature was controlled at 25-30°C and the stirring speed was 300-350 r / min. The mixture was stirred for 3-4 hours. The solid was filtered and washed with a small amount of clean water to obtain a black solid powder.

[0064] The above-mentioned black solid powder, 129.8 grams of cobalt chloride and 250 grams of water were added to the reactor successively, the stirring speed was controlled at 450-500 r / min, and the temperature was controlled at 10-15 °C to slowly add 75.1 grams of 40% hydrazine hydrate aqueous solution to the reaction solution. After the addition was completed, the temperature was slowly raised to 50-55 °C. During the reaction, the pH of the reaction solution was controlled to be maintained between 7.5 and 8 by adding 30% sodium hydroxide aqueous solution. The temperature was controlled and stirred for 5-6 hours. Filter by suction, and rinse the filtered solid with a small amount of deionized water. The obtained solid was placed at 120-125 °C and dried at absolute pressure for 10 hours to obtain a black solid powder.

[0065] Under the protection of inert gas, the black solid powder prepared above was transferred to a pressure-resistant reactor, and 500g of dichloromethane and 69.4g of cyclopentadiene monomer (prepared by pyrolysis of dicyclopentadiene) were added. The stirring speed was controlled at 450-500r / min, and the temperature was controlled at 25-30°C to pass carbon monoxide gas into the reactor until the gas phase pressure was 0.3-0.4MPa, and a small amount of heat was released during the ventilation process. Carbon monoxide was continuously replenished to control the gas phase pressure in the reactor to be maintained between 0.3-0.4MPa, and the temperature was controlled and stirred for 12-18h. The gas phase pressure in the reactor was basically stable. After the reaction was completed, the gas in the reactor was slowly vented and replaced with inert gas 3 times. The reaction solution was transferred out for suction filtration, and a small amount of dichloromethane was used to rinse the solid, and the filtrate was collected and combined. Most of the solvent in the filtrate was evaporated at normal pressure, and then 158.1g of dark red liquid was obtained by absolute pressure distillation, and the molar yield calculated as cobalt chloride was 87.8%. ICP-MS detected inorganic purity>6N; Au content <1ppm; NMR detected organic purity>99%.

[0066] Based on Example 7, it can be known that the excess filtered solid obtained at the end can be used instead of the catalyst after being treated with aqua regia, and the molar yield calculated with cobalt chloride is 87.8%. The catalyst has the ability to be recovered and reused. Embodiment 8

[0067] like Figure 6-14 As shown, a synthesis device of metal precursor organic carbonyl cobalt compounds includes a reaction kettle 1, on which a collecting and distributing mechanism 2 is arranged, the collecting and distributing mechanism 2 includes a rotating shaft 21 and a collecting and distributing blade 22 movably arranged at the first end of the rotating shaft 21, the collecting and distributing blade 22 is driven to rotate forward to collect filtered solids and reverse to diffuse the filtered solids in the collecting and distributing blade 22.

[0068] Specifically, the rotating shaft 21 is arranged at the output end of the motor to rotate along the reactor 1. The first end of the rotating shaft 21 (with Figure 7 For reference, the first end is the lower end) symmetrically provided with collecting and distributing blades 22. Before stirring, the solid material is placed on the collecting and distributing blades 22, and then the liquid is added for rotation stirring. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse (with Fig.13 For reference, positive rotation means clockwise rotation), at this time, the collecting and dispersing blade 22 disperses the solid material inside to diffuse it into the reactor 1 for reaction. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward to collect the solids in the reactor 1 into the collecting and dispersing blade 22 to facilitate the collection of the solids.

[0069] Furthermore, the reactor 1 is provided with a pressure-resistant upper cover 11 for sealing.

[0070] As an embodiment provided by the present invention, a filter plate 2212 is provided at the first end of the collecting and distributing blade 22, and a uniform distribution opening 223 is opened on one side of the collecting and distributing blade 22. The collecting and distributing blade 22 is driven to rotate forward to collect the filtered solids on the filter plate 2212 through the uniform distribution opening 223.

[0071] Specifically, the first end of the collecting and distributing blade 22 (with Fig. 9 For reference, the first end is the right end) and a filter plate 2212 is provided. A covering plate 2211 is also provided at the first end of the collecting and distributing blade 22. The covering plate 2211 is used to cooperate with the filter plate 2212 to intercept solids and allow liquids to pass through. A uniform distribution opening 223 is provided on one side of the collecting and distributing blade 22. The uniform distribution opening 223 faces the rotating shaft 21. When the collecting and distributing blade 22 rotates forward with the rotating shaft 21, the liquid and solid are wrapped into the collecting and distributing blade 22 through the uniform distribution opening 223, and then the liquid is filtered through the filter plate 2212, and the solid is intercepted to achieve solid collection.

[0072] Before stirring, the solid material is placed in the collecting and dispersing blade 22, and then the liquid is added for rotation and stirring. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse. At this time, the collecting and dispersing blade 22 disperses the solid material inside to diffuse it into the reactor 1 for reaction. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward to wrap the liquid and solid into the collecting and dispersing blade 22 through the dispersing opening 223, and then the liquid is filtered through the filter plate 2212, and the solid is intercepted and collected.

[0073] As an embodiment provided by the present invention, an arc surface portion 222 is provided on the other side of the collecting and distributing blade 22, and a guide angle 221 is provided at the first end of the collecting and distributing blade 22. The collecting and distributing blade 22 is driven to reverse to guide the liquid to flow along the guide angle 221, and flow rapidly along the two ends of the uniformly dispersing opening 223 to form a fast flow zone.

[0074] Specifically, when the solid is diffused at the initial stage of mixing, as the collecting and dispersing blade 22 flips, the guide angle 221 will guide the water flow to disperse, one of which flows along the arc surface 222, and the other flows along the uniform dispersion opening 223, and converges with the filter plate 2212 to form a fast flow area. The fast flow area will drive the solid in the collecting and dispersing blade 22 to diffuse, so as to promote the diffusion of the solid and accelerate the reaction. When rotating forward, the liquid and solid entering the uniform dispersion opening 223 will flow along the arc surface 222 to impact the filter plate 2212, so as to avoid the solid blocking the filter plate 2212, thereby keeping the filter plate 2212 unobstructed.

[0075] Before stirring, the solid material is placed in the collecting and dispersing blade 22, and then the liquid is added and the mixture is rotated and stirred. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse. At this time, the guide angle 221 will guide the water flow to disperse, one of which flows along the arc surface 222, and the other flows along the uniform dispersion opening 223, and converges with the filter plate 2212 to form a fast flow area. The fast flow area will drive the solid in the collecting and dispersing blade 22 to diffuse, so as to promote the solid to diffuse into the reactor 1 for reaction. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward, and the liquid and solid are wrapped into the collecting and dispersing blade 22 through the uniform dispersion opening 223. Then the liquid is filtered through the filter plate 2212, and the solid is intercepted and collected.

[0076] As an embodiment provided by the present invention, a dripping mechanism 3 is provided on the reactor 1, and the dripping mechanism 3 includes a dripping head 31. A hollow cavity is provided on the rotating shaft 21, and an annular groove 211 is provided on the hollow cavity. The dripping head 31 alternately sprays a fast and a slow droplet, and the two droplets collide in the annular groove 211 to diffuse the droplets to the fast flow area.

[0077] Specifically, the dripping head 31 is arranged in the hollow cavity, and the two are rotatably connected. The dripping head 31 is fixed on the frame (the frame can be a stainless steel bracket or an aluminum alloy profile), and an annular groove 211 is provided on the hollow cavity. A liquid storage tank 30 is provided in the dripping head 31, and a liquid outlet pipe 331 is provided on the liquid storage tank 30. A spiral protrusion 332 is provided at the outlet of the liquid outlet pipe 331. When in use, the dripping head 31 is driven to alternately spray fast and slow droplets. When the slow droplets enter the annular groove 211, they are impacted by the fast droplets to impact and diffuse in the annular groove 211. The diffused droplets fall into the fast flow area for mixing.

[0078] Furthermore, the mechanism for controlling the droplet head 31 to alternately spray out fast and slow droplets may be an air pump, which controls the air delivery speed and air delivery volume of the air pump into the hollow cavity to control the size and speed of the liquid.

[0079] Before stirring, the solid material is placed in the collecting and dispersing blade 22, and then the liquid is added and the mixture is rotated and stirred. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse. At this time, the guide angle 221 will guide the water flow to disperse, one of which flows along the arc surface 222, and the other flows along the uniform dispersion opening 223, and converges with the filter plate 2212 to form a fast flow area. The fast flow area will drive the solid in the collecting and dispersing blade 22 to diffuse, so as to promote the solid to diffuse into the reactor 1 for reaction. When dripping, the dripping head 31 is driven to alternately spray out a fast and a slow droplet. When the slow droplet enters the annular groove 211, it is hit by the fast droplet to impact and diffuse in the annular groove 211. The diffused droplets fall into the fast flow area for mixing. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward, and the liquid and solid are wrapped into the collecting and dispersing blade 22 through the uniform dispersion opening 223. Then the liquid is filtered through the filter plate 2212, and the solid is intercepted and collected.

[0080] As an embodiment provided by the present invention, an air guide tube 33 is opened on the drip head 31, a first squeezing capsule 32 and a second squeezing capsule 321 are arranged on the drip head 31, and a squeezing bar 214 is arranged on the hollow cavity. The squeezing bar 214 rotates with the rotating shaft 21 to alternately squeeze the first squeezing capsule 32 and the second squeezing capsule 321.

[0081] Specifically, the air guide tube 33 is connected to the outside, the liquid storage tank 30, the first squeezing bag 32 and the second squeezing bag 321 respectively. A one-way valve is provided on the air guide tube 33. When the first squeezing bag 32 or the second squeezing bag 321 is squeezed by the squeezing bar 214, the one-way valve restricts the gas supply to the liquid storage tank 30 so that the squeezed liquid is squeezed out along the liquid outlet tube 331. After the squeezing bar 214 passes, the first squeezing bag 32 or the second squeezing bag 321 rebounds to suck the outside gas, so as to facilitate the subsequent squeezing again. The length and thickness of the first squeezing bag 32 and the second squeezing bag 321 correspond to the slow large droplets and the fast small droplets respectively.

[0082] A barrier strip 34 is provided in the hollow cavity, and an infusion layer is provided on the barrier strip 34 to temporarily intercept slow large droplets and further decelerate them. However, the fast small droplets are narrow and difficult to be intercepted. A retention contact 213 is provided at the bottom of the annular groove 211. When the slow droplets fall too fast, they will drip onto the retention contact 213 and then be impacted by subsequent fast small droplets to splash droplets.

[0083] Before stirring, the solid material is placed in the collecting and dispersing blade 22, and then the liquid is added for rotation and stirring. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse. At this time, the guide angle 221 will guide the water flow to disperse, one of which flows along the arc surface 222, and the other flows along the uniform dispersion opening 223, and converges with the filter plate 2212 to form a fast flow area. The fast flow area will drive the solid in the collecting and dispersing blade 22 to diffuse, so as to promote the solid to diffuse into the reactor 1 for reaction. When dripping, the first extrusion capsule 32 or the second extrusion capsule 32 The pressure bag 321 is squeezed by the squeezing bar 214 to drive the drip head 31 to alternately spray out a fast and a slow droplet. When the slow droplet enters the annular groove 211, it is hit by the fast droplet to impact and diffuse in the annular groove 211. The diffused droplets fall into the fast flow area for mixing. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward, and the liquid and solid are wrapped into the collecting and dispersing blade 22 through the uniform dispersion opening 223. Then the liquid is filtered through the filter plate 2212, and the solid is intercepted and collected.

[0084] As the best embodiment provided by the present invention, the collecting and distributing blades 22 are slidably connected to the first end of the rotating shaft 21, and the two collecting and distributing blades 22 are attached to each other and maintained in an inclined state as the rotating shaft 21 is lifted, and the two collecting and distributing blades 22 are attached to the bottom of the reactor 1 and maintained in a horizontal state as the rotating shaft 21 is lowered;

[0085] A rotation slot 212 is formed on the rotating shaft 21 , and a flip connection plate 210 disposed on the collecting and distributing blades 22 is slidably connected in the rotation slot 212 .

[0086] Specifically, the bottom of the collecting and distributing paddle 22 is arc-shaped, which is convenient for rotation and reduces friction with the bottom of the reactor 1. Before placing the collecting and distributing paddle 22, lift the rotating shaft 21. At this time, the collecting and distributing paddle 22 naturally falls with its weight and slides and fits along the rotating chute 212, maintaining an inclined state. At this time, the arc portion 222 is used to carry solid materials. At the same time, the rotating shaft 21 can be directly lifted after the filtered solid collection is completed. During rotation, the rotating shaft 21 is lowered so that the arc fits the bottom of the inner wall of the bottom reactor 1 to maintain the horizontal state of the collecting and distributing paddle 22, and then rotate.

[0087] Before stirring, lift the rotating shaft 21. At this time, the collecting and distributing blade 22 naturally falls with the weight, slides and fits along the rotating chute 212, and maintains an inclined state. At this time, the arc surface 222 is used to carry the solid material and place the solid material in the collecting and distributing blade 22. Then, after adding liquid, the rotating stirring is carried out. At the initial stage of stirring, the rotating shaft 21 is controlled to reverse. At this time, the guide angle 221 will guide the water flow to disperse, one of which flows along the arc surface 222, and the other flows along the uniform dispersion opening 223, and converges with the filter plate 2212 to form a fast flow area. The fast flow area will drive the solid in the collecting and distributing blade 22 to diffuse, so as to promote the diffusion of the solid. The reaction is carried out in the reactor 1. When dripping, the first squeezing capsule 32 or the second squeezing capsule 321 is squeezed by the squeezing bar 214 to drive the dripping head 31 to alternately spray out a fast droplet and a slow droplet. When the slow droplet enters the annular groove 211, it is hit by the fast droplet to impact and diffuse in the annular groove 211. The diffused droplets fall into the fast flow area for mixing. After the reaction is completed and filtration is required, the rotating shaft 21 is rotated forward, and the liquid and solid are wrapped into the collecting and dispersing blade 22 through the uniform dispersion opening 223. Then the liquid is filtered through the filter plate 2212, and the solid is intercepted and collected.

[0088] The above description is only by way of illustration of certain exemplary embodiments of the present invention. It is undoubted that those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

Claims

1. A method for synthesizing a metal precursor organic carbonyl cobalt compound, characterized in that: The specific steps include: S01, the raw materials are weighed in parts by weight, including the following components: 120 parts of activated carbon, 250 parts of water, 3-9.1 parts of gold chloride, 118.9-129.8 parts of cobalt salt, 75.1 parts of 40%-80% mass concentration hydrazine hydrate aqueous solution, 30% mass concentration sodium hydroxide aqueous solution, 500 parts of dichloromethane, and 69.4 parts of cyclopentadiene monomer; S02, add activated carbon, gold chloride, cobalt salt and water into the reaction kettle, start stirring, control the temperature at 10-15°C, add 40% hydrazine hydrate aqueous solution dropwise, and slowly heat to 50-55°C after the addition is complete; S03, add 30% sodium hydroxide aqueous solution to the reactor to control the pH of the reaction solution to be maintained between 7.5 and 8, and stir and react at controlled temperature for 5 to 6 hours; S04, filtering to obtain the solid in the reaction kettle, eluting the solid with deionized water, and drying it at 120-125° C. under absolute pressure for 10 h to obtain a black solid powder; S05. Add the black solid powder into the reactor under the protection of inert gas, then add dichloromethane and cyclopentadiene monomer, control the temperature at 25-30° C., introduce carbon monoxide gas into the reactor until the gas phase pressure reaches 0.3-0.4 MPa, and continue stirring; S06, the gas phase pressure in the reactor is stable, the reaction is completed, the filtrate in the reactor is collected, and the filtered solid is eluted with dichloromethane and combined with the filtrate for collection; S07. Most of the solvent in the filtrate is distilled off under normal pressure, and then distilled under absolute pressure to obtain dicarbonylcyclopentadienylcobalt liquid.

2. The method for synthesizing a metal precursor organic carbonyl cobalt compound according to claim 1, characterized in that: The cobalt salt is cobalt carbonate or cobalt chloride.

3. The method for synthesizing a metal precursor organic carbonyl cobalt compound according to claim 1, characterized in that: The filtered solid obtained in step S06 and aqua regia are added into the reaction kettle, the temperature is controlled at 25-30°C and stirred for 3-4 hours, and then filtered to obtain the filtered solid. After being washed with clean water, the filtered solid can replace the gold chloride and activated carbon in step S01 as a catalyst and its carrier.

4. The method for synthesizing a metal precursor organic carbonyl cobalt compound according to claim 1, characterized in that: The cyclopentadiene monomer in step S05 is replaced with 3,3-dimethyl-1-butyne to obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl liquid in step S06.

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