The method of producing cyclopentanecarbonyl manganese and device for its implementation

 

(57) Abstract:

The invention relates to the synthesis of ORGANOMETALLIC compounds, namely, to obtain cyclopentanetetracarboxylic manganese, which can be used as antiknock motor fuels. A method of obtaining cyclopentanecarbonyl manganese by reacting the sodium derivative of cyclopentadiene and anhydrous manganese dichloride, followed by carbonyliron of the reaction mixture with carbon monoxide in an inert atmosphere in the environment of tetrahydrofuran, under heat and high pressure with stirring and the introduction of additives carbonyl transition metal, in which the carbonyl transition metal is used directionally in the amount of 0.05-0.10 mol. % and stirring is carried out at a relative speed of movement of solid and liquid components in the reaction mass not less than 10 m/s, Preferably carrying out the carbonylation at a temperature of 250-260oC and a pressure of 80-100 kg/cm2. The proposed device to implement the method, the main design features of which is the fulfillment of the mixing device as mounted on the Central shaft of each is diversified relations, that ensures a high efficiency of intensive mixing of the reaction mass and to increase the yield of the target product to 95.2% while reducing process time: 15-20 minutes 2 S. and 2 C. p. F.-ly, 1 Il., table 1.

The invention relates to the synthesis of ORGANOMETALLIC compounds, namely, to obtain cyclopentanecarbonyl manganese, which can be used as antiknock motor fuels.

A known method of producing cyclopentanecarbonyl manganese (CTM) by reacting compounds of divalent manganese salt of the cyclopentadienyl: K, Na, Li, Al, bromide by cyclopentadienylmagnesium and carbon monoxide in a solvent (tetrahydrofuran, benzene, diglyme) at a pressure of 190-200 kg/cm2and a temperature of 180-190oC (A. N.Nesmeyanov, K. N. Anisimov, N. E. Kolobov, Izvestiya an SSSR, Ser. Chemical, 1963, C. 1880). The yield of the target product in implementing this known method is only 68%, the processing time is about 15 hours, and the process is accompanied by the formation of large amounts of resinous products and unusable waste.

The closest to the essence (essential is vegetalismo USSR N 722915, C 07 F 9/00, 25.03.80), adopted as a prototype, according to which the derivatives of CARBONYLS of metals of the General formula: R M (CO)xwhere R is an unsaturated cyclic hydrocarbon containing from 5 to 15 carbon atoms; M is a transition metal V-VI groups, X = 2 - 4, produced by carbonyliron by processing carbon monoxide sodium or lithium derivative of the corresponding cyclic hydrocarbon in the presence of a salt of the transition metal, under pressure, when heated in an inert atmosphere, in an environment of tetrahydrofuran and when exposed to ultrasound from 4 to 22 kHz.

The process is carried out at a temperature of 80-170oC and a pressure of 30-280 ATM.

The sodium derivative of a cyclic unsaturated hydrocarbon can be obtained directly in the process of obtaining the target product - derived CARBONYLS of metals by the interaction of a suspension of metallic sodium in tetrahydrofuran with cyclopentadiene in the presence of transition metal carbonyl - PENTACARBONYL Fe(CO)5or using cyclopentadienide sodium - C5H5Na in the form of a suspension in absolute tetrahydrofuran.

The yield of the target product with the implementation of this method is 60-86% when the CA as a salt of the transition metal is used, the suspension of anhydrous MnCl2in the solvent (benzene) as an unsaturated cyclic hydrocarbon - sodium derivative of C5H5Na in absolute tetrahydrofuran.

To ensure an effective process of interaction of components in the system gaseous oxide of carbon, liquid solution of carbon monoxide, cyclopentadienyl sodium and the reaction product CTM particles of solid chloride of manganese is necessary to ensure mixing of the reaction mass with a high relative speed of movement of solid and liquid components.

Used in the famous decision of the ultrasonic effect on the reaction mass does not provide effective mixing Output CTM is with 80-86% and a duration of 1-3 hours.

The proposed solution is aimed at improving the efficiency of mixing of the reaction mass and, consequently, to increase the yield of the target product cyclopentanecarbonyl manganese and reducing the duration of the process.

This is achieved in that in the method of producing cyclopentanecarbonyl manganese by the interaction of the sodium derivative of cyclopentadiene and anhydrous manganese dichloride in Arganda in an inert atmosphere, in the environment of tetrahydrofuran, under heat and high pressure, with stirring and introduction of additives carbonyl transition metal as carbonyl transition metal is used directionally in the amount of 0.05 - 0.10 mole. % and stirring is carried out at a relative speed of movement of solid and liquid components of the reaction mixture not less than 10 m/sec.

This provides a high intensification of the process, the carbonylation is carried out for 15-20 min, and the output CTM is 91-93%.

Carbonylation is preferably carried out at a temperature of 150-260oC and a pressure of 80-100 kg/cm2.

The use of directionally promotes uniform distribution of reactant in the reaction mass and accelerates the carbonylation reaction.

Reducing the number of directionally below 0.05% mole. no effect on the carbonyl process, and the increase in quantity above 0.10% per mole. leads to the accumulation of by-products in the reaction mass (iron, sulfur), and lower yield of the target product.

The method of producing cyclopentanecarbonyl manganese can be carried out as follows.

Then, while stirring the reaction mass add cyclopentadiene. The stage of obtaining the sodium derivative of cyclopentadiene - C5H5Na finish after cessation of hydrogen evolution. To the reaction mass containing C5H5Na at room temperature add a suspension of manganese dichloride in a solvent is tetrahydrofuran containing directionally in the amount of 0.05-0.10% mole., and heated to 60oC. With stirring of the reaction mixture, the reactor is filled with carbon monoxide to a pressure of not lower than 80 to 100 kgf/cm2the reaction mass is heated to a temperature of 250-260oC, and the intensity of mixing increases, providing a relative speed of movement of solid and liquid components in the reaction mass not less than 10 m/sec.

The carbonyl process complete after cessation of absorption of carbon monoxide. Then turn off the heating, the reaction mass is then cooled to room temperature, complete mixing, the reaction mass is discharged and by distillation in vacuum produce the target product.

When extremeseeding devices and heat-shirt which is rinsed with an inert gas, loaded with 3.3 l of tetrahydrofuran, 253 g of sodium in the form of a suspension in tetrahydrofuran and purge with an inert gas again (all operations are carried out in an atmosphere of inert gas). At low stirring (at a relative speed of movement of solid and liquid components in the reaction mass of 0.01 m/s) and temperatures up to 10oC add 730 g of cyclopentadiene. After cessation of hydrogen evolution, which indicates the end of the process of cyclopentadienyl sodium C5H5Na, in a reactor at room temperature add 700 grams of manganese dichloride and 10.3 g (0.1 mole. %) directionally in the form of a suspension in tetrahydrofuran, the mixture is stirred, heated to 60oC and then into the reactor serves monoxide to the pressure in the reactor is not less than 80 kgf/cm2and temperatures up to 250-260oC.

The reaction mass is stirred at a relative speed of movement of solid and liquid components of at least 10 m/sec and a pressure of 80-100 kg/cm2. After 15 min the pressure drop in the reactor is stopped, which indicates the termination of the absorption of carbon monoxide and, consequently, on the termination of the reaction carbonylcyanide product CTM allocate by distillation in vacuum at a temperature of 80-95oC.

You get 1126,2 g of yellow crystals cyclopentanecarbonyl manganese, melting point which 75-76oC, and the output is 93%.

The results of the described experiment 1 and other experiments in comparison with the results obtained when implementing the method of the prototype shown in the table.

In accordance with the proposed invention is also a device that implements the above method.

It is known device described in the Author's certificate of the USSR N 1289541 (B 01 J 19/00, 15.02.87), which comprises a cylindrical housing with process connection pipes, the actuator and the Central shaft with a fixed turbine agitator.

Specified the known device has a low productivity due to low mixing intensity of the reaction mass. During operation of the turbine mixer at high speed in the Central part of the reactor on the surface of a rotating liquid occurs funnel, and the level of the peripheral part of the liquid rises. When this agitation of the liquid is slowed, and the reaction time is increased, because it does not provide the required relative movement of solid and liquid components in the reaction mass.

Most near is ASEE cylindrical body with technological nozzles, the actuator and the Central shaft attached to it mixing node. Near the walls of the reactor here installed vertical chisel edge, which forms under stirring the Central crater in the reactor is destroyed. However, near the vertical edges in the reaction mass arise stagnant zones, for which the reaction time is reduced slightly and conditions for the formation of side products.

Suggestions of the device is directed to increase mixing efficiency and productivity.

This task is solved in that the device contains a cylindrical housing with process connection pipes, the actuator and the Central shaft with a fixed site mixing, the specified node mixing is made in the form of a turbine mixer and set over her propeller stirrer, covered by a cylindrical diffuser, while the geometric dimensions of the elements of the device are connected by the following relations

D1:D = 0,4 - 0,6,

D1:D2= 1.3 to 1.7,

H1:D1= 0,5 - 0,7,

H2:D2= 1,2 - 1,6,

where D is the internal diameter of the shell,

D1- diameter turbine stirrers,

D2/BR>H2- the height of propeller stirrer above the bottom of the case.

This occurs when the stirring of the reaction mass of the Central funnel completely destroyed due to suction fluid up using a propeller stirrer and vertical circulation through the cylindrical diffuser that determines the efficiency of mixing of the reaction mass, reducing reaction time and increasing productivity.

Turbine stirrer creates a fluid circulating currents, forming two horizontal toroidal turbulent rings rotating around a Central shaft in the direction of rotation of the turbine agitators. Propeller stirrer, covered cylindrical diffuser creates circulating currents in the Central part of the reactor, forming a vertical toroidal turbulent ring. Meeting and intersecting with each other, these internal fluid flows constantly destroying each other, providing a high turbulence of the General movement of the liquid in the reactor, and increases the efficiency of mixing of the reaction mass. The total liquid level in the reactor is kept almost at the same horizontal sitelog move the solid and liquid components in the reaction mass is based on the angular speed of rotation of the Central shaft and the geometric dimensions of the agitators.

When reducing the above ratios of the sizes of the elements of the reactor, the mixing efficiency is sharply reduced, because the turbine and propeller mixers come closer together and move to the bottom of the case, and the zone of active stirring of the reaction mass is only in the lower part of the reactor.

With the increase in the above ratio of the sizes of the elements of the reactor, the mixing efficiency is also greatly reduced due to the fact that the turbine stirrer is raised too high above the bottom and in the lower part of the reactor occurs stagnant zone, and a propeller stirrer is too high, almost below the liquid level and quite far from the zone of action of the turbine agitators. When this circulation flows generated from both mixers have each other much less effect.

The drawing shows the design of the proposed device. The device comprises a cylindrical housing 1 with the technological branch pipes 2 to 5, the actuator 6 and the Central shaft 7 with a fixed mixing unit, performed with a turbine stirrer 8 and a propeller stirrer 9, covered by a cylindrical diffuser 10. The housing 1 is equipped with a heating jacket 11, is associated with thermostat shown).

The dimensions of the elements of the reactor, in particular the inner diameter of the housing 1, the diameter of the turbine mixer 8, the diameter propeller stirrer 9, the height of the turbine agitator 8 above the bottom of the case 1, the height of the propeller stirrer above the bottom of the case 1, should be linked to the above defined ratios, which is implemented efficient mixing throughout the reaction mass.

Through tubes of 2.5 is blowing with an inert gas. After closing the pipe 5 through the pipe 2 fill in tetrahydrofuran and the suspension of sodium in tetrahydrofuran. Through pipe 5 add the cyclopentadiene. Through pipe 3 serves monoxide. Discharging the reaction mixture passes through the pipe 4.

Rotation of the Central shaft 7, and with it the rotation of the blades in the mixer 8, 9 provides the desired relative speed of movement of solid and liquid components in the reaction mass.

Thus the proposed method and the device in comparison with the known solutions provide for better mixing of the reaction mass, reducing the duration of the process (15-20 min) and increases the yield of the target product (to 95.2%).

2. The method according to p. 1, wherein the carbonylation is carried out at 150 - 260oC.

3. The method according to p. 1, wherein the carbonylation is carried out at a pressure of 80 - 100 kgf/cm2.

4. A device for implementing the method according to p. 1 containing cylindrical body with technological nozzles, drive, and a Central shaft with a fixed site mixing, characterized in that site mixing is made in the form of a turbine mixer and set over her propeller stirrer, covered by a cylindrical diffuser, while the geometric dimensions of the elements of the device are connected by the following relations:

D1: D = 0,4 - 0,6;

D1: D2= 1.3 to 1.7;

H1: D1= 0,5 - 0,7;

H2: D2= 1,2 - 1,6,

where D is the inner diameter of the casing;

polozenie turbine agitator on the bottom of the case;

H1- the height of propeller stirrer above the bottom of the case.

 

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