Continuous preparation method of metal carbonyl compound

Abstract

The invention relates to the technical field of carbonyl compounds, and provides a continuous preparation method of a metal carbonyl compound. The method comprises the following steps: continuously introducing metal powder and CO into a high-pressure tubular reactor, and carrying out carbonylation reaction to obtain a metal carbonyl compound; and the high-pressure tubular reactor is vertically fixed underground. According to the invention, the high-pressure tubular reactor is vertically fixed underground, so that the problem that the long high-pressure tubular reactor is difficult to fix above the ground is solved, the operation safety is better, the explosion risk is small, the reaction of metal powder and CO is more sufficient, and the reaction rate and the product yield are improved. In conclusion, continuous feeding and continuous discharging can be achieved, the production efficiency is high, the cost is low, the technology is simple, and the method is suitable for large-scale production. Results of the embodiment show that continuous preparation of the metal carbonyl compound can be achieved, and the yield can reach 98.5% or above when the reaction lasts for 20 h.

Description

Technical Field

[0001] The invention relates to the technical field of carbonyl compounds, and in particular to a continuous preparation method of metal carbonyl compounds. Background Art

[0002] Metal carbonyl compounds are a type of complex composed of carbon monoxide as a ligand and a metal element, with the general formula M x (CO) y Metal carbonyl compounds are not only the earliest and most common type of organic complexes, but also have important applications in metal organic synthesis, fine organic synthesis and basic organic synthesis. Metal carbonyl compounds are also an important and efficient catalyst. Due to their high catalytic activity and relatively low price, they have very broad application prospects.

[0003] At present, the preparation methods of metal carbonyl compounds mainly include direct synthesis, reduction-carbonylation and ligand substitution. Among them, the direct synthesis method is to directly react metal powder with carbon monoxide; the reduction-carbonylation method is to generate metal carbonyl compounds by reacting a reducing agent with carbon monoxide; the ligand substitution method is to generate new metal carbonyl compounds by replacing existing ligands. This method is more common in organic synthesis and is suitable for preparing metal carbonyl compounds with specific functions and properties. However, the current synthesis method mainly adopts an intermittent production method, that is, directly adding the reaction raw materials to the autoclave, reacting under high pressure and high temperature, and then carrying out the next batch of reactions after the reaction is completed. The intermittent method can effectively control the key parameters in the reaction process, such as temperature and pressure, so as to achieve precise regulation of the chemical reaction, but the production efficiency is low and it is difficult to achieve large-scale production.

[0004] Since the preparation of metal carbonyl compounds needs to be carried out under high temperature and high pressure conditions and is a gas-solid reaction, it is difficult to achieve continuous production. Currently, there are very few reports on the continuous preparation of metal carbonyl compounds in the art. Summary of the invention

[0005] In view of this, the present invention provides a continuous preparation method of a metal carbonyl compound. The preparation method provided by the present invention can realize the continuous preparation of a metal carbonyl compound, has high production efficiency, low cost, and high product yield.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] A continuous preparation method for a metal carbonyl compound comprises the following steps:

[0008] Metal powder and CO are continuously fed into a high-pressure tubular reactor for carbonylation reaction to obtain a metal carbonyl compound; the temperature of the carbonylation reaction is 50 to 350° C. and the pressure is 5 to 70 MPa; the high-pressure tubular reactor is vertically fixed underground, and the top of the high-pressure tubular reactor is exposed from the ground surface.

[0009] Preferably, the high-pressure tubular reactor is a single-tube reactor; the inner diameter of the reaction tube of the high-pressure tubular reactor is 50 to 1000 mm, and the length is 10 to 1000 m.

[0010] Preferably, a jacket or a heating belt is provided on the outside of the high-pressure tubular reactor.

[0011] Preferably, the length of the high-pressure tubular reactor buried underground is 50% to 99.5% of the total length.

[0012] Preferably, the fixing method comprises: vertically placing the high-pressure tubular reactor into a preset well, and then filling cement in the gap between the well wall and the high-pressure tubular reactor for fixing.

[0013] Preferably, the metal powder is a transition metal powder or a lanthanide metal powder; the particle size of the metal powder is less than 100 μm; the purity of the CO is ≥ 90%;

[0014] The feed rate of the metal powder is 0.1-10 m / s; the feed rate of CO is 0.1-10 m / s; and the molar ratio of the metal powder to CO is 1:0.5-10.

[0015] Preferably, the metal carbonyl compound gas is obtained after the carbonylation reaction, and the process further comprises cooling the metal carbonyl compound gas to obtain a metal carbonyl compound liquid or solid; the cooling temperature is 20 to 45°C.

[0016] Preferably, the device used in the continuous preparation method also includes a feeding system, a cooler, a receiving container and a filter; the feeding system is connected to the inlet of the high-pressure tubular reactor; the cooler is connected to the top of the tubular reactor; the receiving container is connected to the outlet of the cooler, and the filter is connected to the outlet of the receiving container.

[0017] Preferably, the feeding system is a high-pressure pneumatic conveying device.

[0018] Preferably, the method of continuously feeding metal powder and CO comprises: placing the metal powder in a high-pressure pneumatic conveying device, then introducing CO into the high-pressure pneumatic conveying device, and using CO as a carrier gas to continuously feed the metal powder to the bottom of the high-pressure tubular reactor.

[0019] The present invention provides a continuous preparation method of a metal carbonyl compound, comprising the following steps: continuously feeding metal powder and CO into a high-pressure tubular reactor for a carbonylation reaction to obtain a metal carbonyl compound; the temperature of the carbonylation reaction is 50 to 350° C. and the pressure is 5 to 70 MPa; the high-pressure tubular reactor is vertically fixed underground, and the top of the high-pressure tubular reactor is exposed from the ground surface. The present invention vertically fixes the high-pressure tubular reactor underground, which not only solves the problem that it is difficult to vertically fix a long high-pressure tubular reactor above the ground, but also has better operation safety, low explosion risk, and solves the safety problem of continuous reaction under high temperature and high pressure; and, after the metal powder and CO enter the bottom of the vertical high-pressure tubular reactor, the metal powder with larger particles is suspended in the middle and lower part of the reactor under the action of gravity and CO gas flow, and reacts with high-concentration CO, while the metal powder with smaller particles can be suspended in the middle and upper part of the reactor under the action of gravity and CO gas flow to react with the remaining CO, and the metal carbonyl compound gas generated by the reaction is discharged from the top of the high-pressure tubular reactor, and the large-particle metal powder in the middle and lower part gradually becomes smaller as the reaction proceeds, and then can also be suspended in the middle and upper part of the reactor to continue the reaction; this operation makes the reaction of the metal powder and CO more sufficient, thereby improving the reaction rate and product yield. In the traditional batch reaction of the kettle, the reaction time of the metal powder and CO usually takes more than 70 hours, while the present invention adopts a vertical high-pressure tubular reactor for reaction, and the yield at the reaction time of 20 hours can reach more than 98.5%.

[0020] In summary, the present invention continuously introduces metal powder and CO into a high-pressure tubular reactor for carbonylation reaction, which can achieve continuous feeding and continuous discharging, has high production efficiency, low cost, simple process, and is suitable for large-scale production. DETAILED DESCRIPTION

[0021] The present invention provides a continuous preparation method of a metal carbonyl compound, comprising the following steps:

[0022] Metal powder and CO are continuously fed into a high-pressure tubular reactor for carbonylation reaction to obtain a metal carbonyl compound; the temperature of the carbonylation reaction is 50 to 350° C. and the pressure is 5 to 70 MPa; the high-pressure tubular reactor is vertically fixed underground, and the top of the high-pressure tubular reactor is exposed from the ground surface.

[0023] In the present invention, the high-pressure tubular reactor is a single-tube reactor, and the inner diameter of the reaction tube of the high-pressure tubular reactor is preferably 50 to 1000 mm, more preferably 50 to 500 mm, and the length is preferably 10 to 1000 m, specifically 18 m, 50 m, 100 m, 300 m, 500 m or 1000 m; the wall thickness of the high-pressure tubular reactor can be designed according to actual needs and relevant specifications, and the present invention does not make specific restrictions. The high-pressure tubular reactor is preferably provided with a jacket or a heating belt on the outside; the jacket is used to pass heat transfer oil or cooling water to control the reaction temperature in the high-pressure tubular reactor; the heating belt is specifically an electric heating belt.

[0024] In the present invention, the high-pressure tubular reactor is preferably fixed vertically underground, and the top of the high-pressure tubular reactor is exposed from the ground surface; the fixing method preferably includes: vertically placing the high-pressure tubular reactor into a preset well, and then filling cement in the gap between the well wall and the high-pressure tubular reactor for fixing; the length of the high-pressure tubular reactor buried underground is preferably 50% to 99.5% of the total length. The top of the high-pressure tubular reactor is provided with a pipeline interface, an instrument interface, a detachable flange, etc. The present invention exposes the top of the high-pressure tubular reactor from the ground surface, which is convenient for connecting the high-pressure tubular reactor with other components.

[0025] In the present invention, the device used in the continuous preparation method preferably also includes a feeding system, a cooler, a receiving container and a filter; the feeding system is connected to the inlet of the high-pressure tubular reactor; the cooler is preferably arranged at the top of the high-pressure tubular reactor, specifically connected to the outlet of the top of the high-pressure tubular reactor; the receiving container is connected to the outlet of the cooler, and the filter is connected to the outlet of the receiving container; the feeding system is preferably a high-pressure pneumatic conveying device, more preferably a high-pressure pressure delivery tank; the receiving container is preferably a receiving tank.

[0026] In the present invention, the particle size of the metal powder is less than 100 μm, more preferably 50 to 500 nm, and further preferably 50 to 200 nm; the purity of the CO is preferably ≥90%, and more preferably ≥95%.

[0027] In the present invention, the metal powder is a transition metal powder or a lanthanide metal powder; the transition metal is preferably scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), One or more of tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au) and mercury (Hg); the lanthanide metal is preferably one or more of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).

[0028] In the present invention, the chemical formula of the metal carbonyl compound is represented by M 3 (CO) 12 、M 2 (CO) 8 、M(CO) 4 、M(CO) 5 or M(CO) 6 , wherein M is a metal element, specifically a transition metal element or a lanthanide element.

[0029] In a specific embodiment of the present invention, the metal powder is preferably cobalt powder, nickel powder, manganese powder or chromium powder, and the obtained metal carbonyl compound is cobalt carbonyl, nickel carbonyl, manganese carbonyl or chromium carbonyl. The cobalt carbonyl is specifically dicobalt octacarbonyl, with the chemical formula Co 2 (CO) 8 ; The nickel carbonyl is specifically nickel tetracarbonyl; the manganese carbonyl is specifically dimanganese decacarbonyl, and the chromium carbonyl is specifically chromium hexacarbonyl.

[0030] In the present invention, the feed rate of the metal powder is preferably 0.1-10 m / s, more preferably 1-6 m / s, and further preferably 1 m / s, 2 m / s or 4 m / s; the feed rate of CO is preferably 0.1-10 m / s, more preferably 1-6 m / s, and further preferably 1 m / s, 2 m / s or 4 m / s; the molar ratio of the metal powder to CO is preferably 1:0.5-10, and more preferably 1:1-5. In a specific embodiment of the present invention, the metal powder is preferably placed in a high-pressure pneumatic conveying device, and then CO is introduced into the high-pressure pneumatic conveying device, and the metal powder is continuously fed to the bottom of the high-pressure tubular reactor using CO as a carrier gas.

[0031] In the present invention, the temperature of the carbonylation reaction is 50-350°C, preferably 100-300°C, more preferably 150°C, 170°C or 200°C; the pressure of the carbonylation reaction is 5-70MPa, preferably 10-60MPa, more preferably 15MPa, 20MPa or 25MPa; in a specific embodiment of the present invention, the pressure of the carbonylation reaction is preferably controlled by the amount of CO introduced.

[0032] In the present invention, the metal carbonyl compound gas is obtained after the carbonylation reaction, and preferably the metal carbonyl compound gas is cooled to obtain a metal carbonyl compound liquid or solid; the cooling temperature is preferably 20 to 45° C., more preferably 25 to 30° C. When the obtained product is a metal carbonyl compound liquid, preferably the metal carbonyl compound liquid is filtered.

[0033] In a specific embodiment of the present invention, it is preferred to first replace the gas inside the high-pressure tubular reactor with an inert gas, heat it up after sealing, introduce heat transfer oil into the jacket or heat the high-pressure tubular reactor through a heating belt, and then use a high-pressure pneumatic conveying device to transport CO and metal powder to the bottom of the high-pressure tubular reactor, control the pressure in the high-pressure tubular reactor to meet the requirements of the carbonylation reaction, CO and metal powder are in gas-solid two-phase contact in the high-pressure tubular reactor, and a carbonylation reaction occurs. During the reaction, heat transfer oil or cooling water is introduced into the jacket, or a heating belt is used to control the reaction temperature so that the temperature is maintained within the temperature range required for the carbonylation reaction; the metal carbonyl compound gas generated by the reaction is discharged from the top of the high-pressure tubular reactor, cooled by a cooler and condensed into a solid or liquid. When it is solid, it can be collected and packaged, and when it is liquid, it is preferably filtered through a filter and collected and packaged.

[0034] The metal carbonyl compound prepared by the invention has high catalytic activity and can be used as a catalyst in various chemical productions.

[0035] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] The purity of the high-purity CO used in the following examples is all above 90%.

[0037] Example 1

[0038] The high-pressure tubular reactor used in this embodiment is a single-tube reactor with an inner diameter of 50 mm, a length of 18 m, and a wall thickness of 5 mm; an electric heating tape is wrapped around the outside of the high-pressure tubular reactor, which is then placed in a preset well, and the gap is filled with cement to fix the high-pressure tubular reactor; the feeding system is a high-pressure pressure tank, which is connected to the inlet of the high-pressure tubular reactor; the top outlet of the high-pressure tubular reactor is connected to a cooler, and the cooler is connected to a receiving tank and a filter in turn.

[0039] 5000g of cobalt metal powder with a specification of 50nm is taken and placed in a high-pressure pressure tank. High-purity CO is introduced from the bottom of the high-pressure pressure tank. CO is used as a carrier gas to transport the cobalt metal powder to the bottom of the high-pressure tubular reactor. The delivery rate is controlled at 1m / s. The molar ratio of cobalt metal powder to CO is 1:3. The temperature of the high-pressure tubular reactor is heated to 150°C by an electric heating belt. The pressure in the high-pressure tubular reactor is 15MPa. CO and cobalt metal powder are in gas-solid two-phase contact in the high-pressure tubular reactor, and carbonylation reaction occurs to generate carbonyl cobalt gas. The carbonyl cobalt gas is discharged from the top of the high-pressure tubular reactor. The temperature of the carbonyl cobalt gas is reduced to 25°C through a cooler, and condensed into carbonyl cobalt (octacarbonyl dicobalt) solid powder, which is collected and packaged. The reaction is continuously carried out for 20h, and the generated metal carbonyl compound is detected by ultraviolet spectrophotometry, and the yield is 98.7%.

[0040] Example 2

[0041] The device used in this embodiment is the same as that in embodiment 1.

[0042] Take 5000g of cobalt metal powder with a specification of 200nm, place it in a high-pressure pressure tank, and introduce high-purity CO from the bottom of the pressure tank. CO is used as a carrier gas to transport the cobalt metal powder to the bottom of the high-pressure tubular reactor. The delivery rate is controlled at 2m / s. The molar ratio of cobalt metal powder to CO is 1:5. The temperature of the high-pressure tubular reactor is heated to 170°C with an electric heating belt. The pressure in the high-pressure tubular reactor is 20MPa. CO and the metal powder are in gas-solid two-phase contact in the gas well, and a carbonyl reaction occurs to generate carbonyl cobalt gas. The carbonyl cobalt gas is discharged from the top of the high-pressure tubular reactor, and the temperature of the carbonyl cobalt gas is reduced to 35°C through a cooler, condensed into carbonyl cobalt (octacarbonyl dicobalt) solid powder, and collected and packaged. The reaction is continuously carried out for 20h, and the generated metal carbonyl compound is detected by ultraviolet spectrophotometry, and the product yield is 98.8%.

[0043] Example 3

[0044] The device used in this embodiment is the same as that in embodiment 1.

[0045] Take 5000g of cobalt metal powder with a specification of 500nm, place it in a high-pressure pressure tank, and introduce high-purity CO from the bottom of the pressure tank. CO is used as a carrier gas to transport the cobalt metal powder to the bottom of the high-pressure tubular reactor. The delivery rate is controlled at 4m / s. The molar ratio of cobalt metal powder to CO is 1:8. The temperature of the high-pressure tubular reactor is heated to 200°C with an electric heating belt. The pressure in the high-pressure tubular reactor is 25MPa. CO and the metal powder are in gas-solid two-phase contact in the high-pressure tubular reactor, and a carbonyl reaction occurs to generate carbonyl cobalt gas. The carbonyl cobalt gas is discharged from the top of the high-pressure tubular reactor, and the temperature of the carbonyl cobalt gas is reduced to 45°C through a cooler, condensed into carbonyl cobalt (octacarbonyl dicobalt) solid powder, which is collected and packaged. The reaction is continuously carried out for 20h, and the generated metal carbonyl compound is detected by ultraviolet spectrophotometry, and the product yield is 98.6%.

[0046] Example 4

[0047] The device used in this embodiment is the same as that in embodiment 1.

[0048] Take 5000g of nickel metal powder with a specification of 50nm, place it in a high-pressure pressure tank, and introduce high-purity CO from the bottom of the high-pressure pressure tank. CO is used as a carrier gas to transport the nickel metal powder to the bottom of the high-pressure tubular reactor. The delivery rate is controlled at 2m / s. The molar ratio of nickel metal powder to CO is 1:5. The temperature of the high-pressure tubular reactor is heated to 200°C by an electric heating belt. The pressure in the high-pressure tubular reactor is controlled to be 10MPa. CO and the metal powder are in gas-solid two-phase contact in the high-pressure tubular reactor, and carbonylation reaction occurs to generate carbonyl nickel gas. The carbonyl nickel gas is discharged from the top of the high-pressure tubular reactor, and the temperature of the carbonyl nickel gas is reduced to 25°C through a cooler, condensed into carbonyl nickel (tetracarbonyl nickel) liquid, and collected and packaged after filtering through a filter. The reaction is continuously carried out for 20h, and the generated metal carbonyl compound is detected by ultraviolet spectrophotometry, and the product yield is 98.8%.

[0049] Example 5

[0050] The device used in this embodiment is the same as that in embodiment 1.

[0051] Take 5000g of chromium metal powder with a specification of 100nm, place it in a high-pressure pressure tank, and introduce high-purity CO from the bottom of the high-pressure pressure tank. CO is used as a carrier gas to transport the chromium metal powder to the bottom of the high-pressure tubular reactor. The delivery rate is controlled at 4m / s. The molar ratio of chromium metal powder to CO is 1:8. The temperature of the high-pressure tubular reactor is heated to 100°C with an electric heating belt, and the pressure in the high-pressure tubular reactor is controlled to be 15MPa. CO and the metal powder are in gas-solid two-phase contact in the high-pressure tubular reactor, and a carbonylation reaction occurs to generate carbonyl chromium gas. The carbonyl chromium gas is discharged from the top of the high-pressure tubular reactor, and the temperature of the carbonyl chromium gas is reduced to 25°C through a cooler, condensed into carbonyl chromium (hexacarbonyl chromium) solid, and filtered through a filter and collected and packaged. The reaction is continuously carried out for 20h, and the generated metal carbonyl compound is detected by ultraviolet spectrophotometry, and the yield of the product is 98.5%.

[0052] Comparative Example 1

[0053] The reaction was carried out in batch mode, and the specific operating conditions were as follows:

[0054] Take 2000g of cobalt particles with a particle size of less than 5mm, place them in a high-pressure synthesis reactor, and introduce high-purity CO heated to 170°C from the bottom of the synthesis reactor. Control the pressure of the synthesis reactor at 25MPa. CO and cobalt particles synthesize to generate carbonyl cobalt gas. The synthesis gas is discharged from the top of the synthesis reactor. The synthesis gas temperature is reduced to 20-25°C through a heat exchanger. The carbonyl cobalt gas is condensed into carbonyl cobalt particles, which are collected by a filter and packaged. The reaction is carried out continuously for 70 hours. The generated metal carbonyl compound is detected by ultraviolet spectrophotometry. The yield of the product is 85.6%.

[0055] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A continuous preparation method of a metal carbonyl compound, characterized in that: The following steps are involved: Metal powder and CO are continuously fed into a high-pressure tubular reactor for carbonylation reaction to obtain a metal carbonyl compound; the temperature of the carbonylation reaction is 50 to 350° C. and the pressure is 5 to 70 MPa; the high-pressure tubular reactor is vertically fixed underground, and the top of the high-pressure tubular reactor is exposed from the ground surface.

2. The preparation method according to claim 1, characterized in that: The high-pressure tubular reactor is a single-tube reactor; the inner diameter of the reaction tube of the high-pressure tubular reactor is 50 to 1000 mm, and the length is 10 to 1000 m.

3. The preparation method according to claim 1 or 2, characterized in that: A jacket or a heating belt is arranged on the outside of the high-pressure tubular reactor.

4. The preparation method according to claim 3, characterized in that: The length of the high-pressure tubular reactor buried underground is 50% to 99.5% of the total length.

5. The preparation method according to claim 4, characterized in that: The fixing method comprises: vertically placing the high-pressure tubular reactor into a preset well, and then filling cement in the gap between the well wall and the high-pressure tubular reactor for fixing.

6. The continuous preparation method according to claim 1, characterized in that: The metal powder is a transition metal powder or a lanthanide metal powder; the particle size of the metal powder is less than 100 μm; the purity of the CO is ≥ 90%; The feed rate of the metal powder is 0.1-10 m / s; the feed rate of CO is 0.1-10 m / s; and the molar ratio of the metal powder to CO is 1:0.5-10.

7. The continuous preparation method according to claim 1, characterized in that: The metal carbonyl compound gas is obtained after the carbonylation reaction, and the metal carbonyl compound gas is cooled to obtain a metal carbonyl compound liquid or solid; the cooling temperature is 20-45°C.

8. The continuous preparation method according to claim 1, characterized in that: The device used in the continuous preparation method also includes a feeding system, a cooler, a receiving container and a filter; the feeding system is connected to the inlet of the high-pressure tubular reactor; the cooler is connected to the top of the tubular reactor; the receiving container is connected to the outlet of the cooler, and the filter is connected to the outlet of the receiving container.

9. The continuous preparation method according to claim 8, characterized in that: The feeding system is a high-pressure pneumatic conveying device.

10. The continuous preparation method according to claim 9, characterized in that: The method for continuously feeding metal powder and CO comprises: placing the metal powder in a high-pressure pneumatic conveying device, then introducing CO into the high-pressure pneumatic conveying device, and using CO as a carrier gas to continuously feed the metal powder to the bottom of a high-pressure tubular reactor.