DE2304124B2 - REACTOR FOR THE PRODUCTION OF ORGANIC ALKALINE COMPOUNDS AND METHOD FOR THE PRODUCTION OF ORGANIC LITHIUM COMPOUNDS - Google Patents

Description

The invention relates to a reactor and a method for the production of organic alkali compounds by reacting alkali metals with haloalkylenes or polycore compounds. The reactor according to the invention can be used for the production of Lithium alkyl, for example ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, Hcxyllithium, 1,5-Dilithiumpentan as well of lithium adducts with polynuclear compounds, for example dilithium naphthalene, dilithium stilbene, Dilithium anthracene oiler Dilithiumdiphenyl used will.

Devices are already known which are used for the production of organic alkali compounds by reacting alkali metals with haloalkylenes or polynuclear compounds can. These reactors are hermetically sealed Housing covered with a thermo-regulating coat / ur maintaining the imtweiuii-Ke η Temperature conditions in the reactor s · 'As mil Pipe sockets for the supply of the reagents and for the removal of the reaction products is. Within the housing, a mixer attached to a shaft is arranged.

The production of organic alkaline compounds gene is used in these devices with the use of a ready-made dispersion of an alkali metal: usually carried out in special apparatus by melting down alkali metals and dispersing them ίο ren this metal in a neutral medium for example paraffin.

The dispersion of alkali metal in the dispersant is carefully separated from the dispersant and mixed with a hydrocarbon solvent. The corresponding haloalkyl is then metered into the reaction mass with continuous mixing. The heat evolving during the formation of the organic alkaline compounds is transmitted through the walls of the reactor housing?

ao passed through the heat transfer medium circulating in the jacket. After the reaction has ended, the reaction mass is discharged from the apparatus and fed to the isolation of the end product. To this For example, the process for the production of organolithium compounds (see USA.-Patent 3 122 592) carried out, which consists in that the dispersed lithium with Additions of sodium or potassium in an amount of 0 to 1% with a corresponding haloalkyl in a hydrocarbon and in an inert atmosphere at 0 to 60 ° C.

In the production of organic alkali compounds in the known device, however, is the Use of a dispersion of an alkali metal prepared beforehand in a special device necessary. Such an alkali metal dispersion in a dispersant usually contains a considerable amount Amount of an inactive alkali metal. This is due to the difficult obstacles to overcome, those with the prevention of corrosion attacks on the surface of the dispersion during his Manufacturing. Packaging, storage and dosing are related. It turned out that, the finer the dispersion, the greater the proportion of alkali metals required for the synthesis of organic alkali Connections cannot be used.

In addition, significant losses of dispersion occur in this reactor when it is washed several times of the dispersant with the hydrocarbon.

The disadvantages of the process for the preparation of organic alkali compounds in the known Reactor is! iuich a longer incubation period of the Synthesis of organic alkali compounds to be expected with the physico-chemical processes associated with cleaning the surface of the dispersion from the corrosion products take place. The incubation time makes it much more difficult the control and monitoring of the course of the reaction and worsens the conditions a safe implementation of the manufacturing pro - /. csscs.

The end product produced in the known reactor is contaminated by finely dispersed sludge, that of an alkali metal and> ehi linen particles of the unreacted alkali metal. To clean the product produced one turns usually draining. Centrifugation or fiI-

irrigate. Carrying out the known procedures is, however, made even more difficult by the fact that a very thin suspension of alkali metal is present

In addition, ir ·, this reactor next to dcr Main reaction also a side reaction that Wurtz's synthesis takes place, the rate of which depends on the concentration of the halogenated alkyl in the reaction mass and depends on the reaction temperature.

The invention was based on the object of providing a reactor for the production of organic alkali Compounds and a process for the production of organolithium compounds in this reactor to develop which allow the loss of active alkali metal to be excluded to a considerable extent, to increase the usable yield of the end product, to increase the degree of purity of this product and reduce the time it takes to isolate it.

This object is achieved in that the reactor for the production of organic alkali compounds by reacting alkali metals with haloalkylenes or polykron compounds, which is a Hermetic, with means for supplying the reagents and discharging the reaction products as well as housing provided with means for maintaining necessary temperature conditions as well as a mixing device contains, according to the invention, a press (S) for pressing through alkali metal through a nozzle (9) in the form of strands into the interior of the reactor and a cutting device for the comminution of the alkali metal strands emerging from the nozzle (9), and as Mixing device contains a dispensing mixer.

The cutting device for shredding the alkali metal strands is expediently designed in the form of knives attached to a rotatable shaft are attached, the cutting edges of these knives arranged in the immediate vicinity of the end face of the nozzle are.

The alkali metal press and cutter are preferably used in the upper part of the reactor, the dispersicrinal arranged in the lower part of the reactor, being in the gap between these a cylindrical insert is installed, which has a directed circulation the reaction mass guaranteed from the dispersing mixer to the cutting device.

The cylindrical insert can be given away with hollow walls, which have a thermo-regulating Medium is managed. The cylindrical insert can have a confuser part. The reactor can have a paddle mixer, which has an additional Guaranteed forced circulation of the reaction mass within the apparatus. Between the wing mixer and the dispensing mixer a cutting disk is expediently arranged. Eici's Carrying out the method in the inventive Reactor by reacting metallic lithium with halogenated alkylene or with a poly-core compound ! • »indungen in the presence of a hydrocarbon in an inert atmosphere at 0 to 60 (. 'mn subsequent; Isolation of the end product is done according to the invention the metallic lithium / small and dispersed directly in the reactor. in the happy the mentioned reaction of metallic lithium with 1!, halogenoalkyl or a poly-core compound is carried out.

It is desirable that the haloalkyl be added to the reactor at a rate which is less than the rate of formation of Lithiuir.aSky! is.

When the addition of haloalkyl has ended, the reaction mass is expediently raised to 60 to 100.degree heated and held at this temperature for 1.5 to 2 hours.

The reactor according to the invention and the process according to the invention allow the economy the production of organic alkali compounds to significantly improve the yield and the quality of the end product with a significant reduction in the consumption of alkali metals to increase, as well as the working conditions of the operating personnel and the safety technology to improve.

In the following the invention is illustrated by the description of the exemplary embodiments and drawings explained. It shows

1 shows a schematic representation of the reactor according to the invention in section;

2 shows a variant of the arrangement of the cutting device for comminuting the alkali metal strands.

The reactor for the production of alkali organic Compounds by reacting alkali metals with haloalkylenes or with polynuclear compounds contains a hermetically sealed housing 1 (Fig. 1) with a cover 2 and a means for Maintaining the necessary temperature conditions in the reactor, in the form of a thermoregulatory Shell 3 is executed. A toroidal reflector 4 is attached to the cover 2, which becomes a shock-free Changing the direction of the flow of the reaction mass circulating in the reactor is used. At the lid 2 a press 5 is also arranged for pressing alkali metal into the interior of the reactor, a pressure piston 6, a cylinder 7 with a collecting vessel 8 for blanks made of alkali metal as well as a nozzle 9, through which the strands of the alkali metal to be pressed through the reactor are fed.

The reactor is also equipped with a cutting device for crushing those emerging from the nozzle 9 Provided alkali metal strands, which is in the form of knives 11 attached to a shaft 10, the cutting edges of which are arranged in the immediate vicinity of the end face of the nozzle 9. On the shaft 10 A mixing device is also attached, which is designed in the form of a dispersing mixer 12.

The dispersing mixer 12 can be of any known construction; the type of dispersing mixer should be chosen on the basis of the conditions that are particularly effective Carrying out the reaction in the media to be used are necessary. So z. B. Fig. 1 shows a Turbine-type dispersing mixer, which is preferably used when there is a Synthesis of lithium alkyl compounds in a hydrocarbon, for example in a beuzin fraction. which boils at <>> to 100 'C " host.

When carrying out the synthesis of polynuclear compounds in a hydrocarbon, for example toluene, or in the production of lithium alkyls in a viscous, neutral medium, e.g. B. V. iseline oil. it is advisable to use a dispersing mixer

used, which consists of a runner and a stander consists, which are provided with a number of mixed teeth (not shown in the figure).

The knife 11 of the cutting device can be placed on the shaft 13 (Fig. 2) with a Single drive 14 is provided; this makes it possible to achieve optimal speeds for both the shaft 13 with knives 11, as well as for the shaft 10 to which the dispensing mixer 12 (Fig. 1) is attached. to Select. Inside the housing is a cylindrical insert 15 with hollow walls for the feed of the thermoregulatory agent arranged that a directed circulation of the reaction mass of your Dispersing mixer 12 to the knives 11 then guaranteed when the knives 11 and the press S to Forcing alkali metal through in the upper part of the reactor, and the dispersing mixer in the lower part of the reactor are arranged.

The introduction of the heat carrier into the cavity walls of the cylindrical insert 15 or the removal of the heat carrier therefrom takes place in each case through the pipe socket 16 and 17.

In the case of a greater length of the reactor, a paddle mixer 18 is expediently attached to the shaft 10, which is enclosed in a guide cylinder and to ensure an additional forced circulation the reaction mass is used within the apparatus. In the space between the wing mixer 18 and the dispersing mixer 12 a cutting disk is arranged, which separates the rotating Flows of the reaction mass from the paddle mixer 18 and the dispersing mixer 12 ensured. The cover 2 of the apparatus is provided with a pipe socket 21 for the introduction of reagent and Hydrocarbon and provided with a pipe socket 22 for the introduction of an inert gas. That Housing 1 is provided with a pipe socket 23 for the discharge of the reaction products. The feed or the discharge of the heat regulating agent from the jacket 3 is in each case by the Pipe socket 24 and 25 made.

The cylindrical insert 15 is provided with a confuser part 26.

The Konfusorteil 26 serves to improve the circulation of the streams in the reactor, thereby the To eliminate congestion zones. In some cases, through the confuser portion 26 of the cylindrical insert 15 ensures the production of an easily mobile dispersion in a viscous neutral agent.

The production of organic alkali compounds by reacting alkali metals with haloalkylenes is carried out in the reactor according to the invention as follows: The reactor is through the Pipe socket 21 filled with a hydrocarbon to a level which is slightly below the upper Cut surface of the cylindrical insert 15 is located. Through the pipe socket 24, 25, 16 and 17 is the heat regulating agent is fed to the jacket 3 and the hollow walls of the cylindrical insert piece 15 or discharged from these.

A vacuum is generated and an inert gas is filled through the pipe socket 22.

The shaft 10 is set in rotation. Appropriate temperature conditions (10 up to 30 C), which ensure mechanical dispersion of the alkali metal. The blanks of the alkali metal, which are preferably a cylindrical or a spherical shape have, are fed via the collecting vessel 8 of the face 5 and by means of the Diuekkolhens 6, who performs the reciprocating movements, through a nozzle 9 in ilen interior of the reactor pressed through in the form of strands.

At the exit from the nozzle 9, the alkali metal strands crushed by the knives 11 and the resulting metal particles are through the

ίο rinsed stream of circulating solvent into the interior of the reactor. Because the particles are passed through the paddle mixer 10 and dispersing mixer 12 several times, they are further comminuted and converted into a dispersion. In this way, when dispersing alkali metal in a viscous neutral agent and when using the known dispersing mixer of the rotor and stator type, the dispersion of alkali metal is produced in the form of flat flakes with torn edges and a diameter of 5 to 200 μ .

In this case, the easy mobility of the dispersion of alkali metal in a viscous Means through the confuser part 26 of the cylindrical part 15 even at a concentration of 15 to 20 percent by weight ensures that the inert gas is entrained through the dispersing mixer 12 and is emulsified into the circulating agent. When dispersing alkali metal in gasoline and when using a dispersing mixer 12 shown in FIG. 1, the dispersion particles of alkali metal has a shape close to the spherical shape, the size of the particles being up to is 0.5 to 1.0 mm.

In connection with the high mobility of the system, the use of the Confusor part 26 not compulsory.

After the necessary initial concentration of the dispersion of in the reaction zone of the reactor Alkali metal such as lithium is made. the temperature in the reactor is from 0 to 60 ° C set and one begins haloalkyl (z. B. butyl chloride) through the pipe socket 21 into the reactor to dose.

The haloalkyl is in the reaction zone in the form of 0 to fi ()% strength solutions in hydrocarbon introduced which the synthesis of lithium alkyl is carried out.

The formation of lithium alkyl begins immediately with no incubation period. The dosage of Halogenalky! is carried out at a rate that is slower than the rate of the reaction to form lithium is alkyl; this will reduce the consumption of haloalkyl for the course Wurtz's synthesis taking place as a side reaction is reduced and the yield is increased. The Ab The heat of reaction is guided through the surface of the housing 1 and the cylindrical insert 15 by means of the circulating heat transfer medium; realized. After the finished dosing of the Ha logenalkyls the reaction mass in the apparatus is kept at 65 to 100 ° C for 2 hours.

When the reaction mass is heated, there is an aggregation of finely dispersed sludge particles in addition, the haloalkyl is also completely converted. The separation of the sludge is vot the lithium alkyl solution is significantly simplified by the process product is thus free from the Ha

logenalkyl radicals. The presence of haloalkyl in the end product leads to the formation of a thin and non-separable suspension of Lithium chloride.

The reaction mass is discharged through the pipe socket 20 and the end product is isolated fed.

The production of organic alkali compounds by reacting alkali metals with poly-core compounds is carried out as follows:

In this case, the reactor is also through the pipe socket 21 with a hydrocarbon up to filled a stand that is slightly below the upper cut surface of the cylindrical insert piece IS lies. The calculated amount of a poly-core compound is fed into the apparatus through the same pipe socket 21 introduced. The heat-regulating agent is fed in or out through the pipe sockets 24, 16 and 17. discharged.

The shaft 10 is set in rotation.

The specified temperature conditions (30 to 60 ° C.) are set and maintained in the reactor.

An alkali metal blank is fed to the press 5 via the collecting vessel 8 and by means of the pressure piston 6 pressed through the nozzle 9. At the exit from the nozzle 9, the alkali metal strands are through the Knife 11 crushed and flushed into the interior of the reactor by the circulating reaction mass.

The formation of lithium-containing polynuclear compounds is carried out with intensive mixing. An improvement in the process is achieved when the reaction mass is repeatedly through the Blade mixer 18 and the dispersing mixer 12 is performed. After the reaction has finished, this will be finished product discharged from the reactor through the pipe socket 20. The yield of finished product is 85%.

In the reactor according to the invention can Ethyllithium, IsopropylFitbium, n-Butyllithium, Sec-Butyllithium, tert-butyllitrium, hexyllithium, 1,5-dilithiumpentane, as well as lithium adducts with poly-core compounds, such as dilithium naphthalene, dilithium stilbene, Dilithium anthracene, dilithium diphenyl are produced.

example 1

In the reactor, which is filled with argon, there are 26.5! Bucket of gasoline fraction that is in a temperature range boiling from 65 to 100 ° C, introduced. The press 5 with subsequent crushing 550 g of metallic lithium, which contains 0.4% sodium, printed. That Mixture is heated to 40 ° C, after which in this mixture within 4 hours under intensive Operation of the dispersing mixer 12 3.8 I n-butyl chloride in the form of a 50% (by volume) mixture with a Benzmfraktion, which in a Boiling temperature range from 65 to 100 ° C can be entered. After completing the input of n-butyl chloride the reaction mass, which is a suspension of lithium chloride, the particles of not represents converted lithium and the n-butyllithium formed and dissolved in the hydrocarbon, held at 70 to 75 ° C for 2 hours and then to separate the n-Butyilithiumlösung from the Lithium chloride and an excess of metallic lithium filtered. The end product, a solution of n-butyllithium, represents a straw yellow 1.02 n-liquid siykcit of active lithium and a content of in active admixtures of 0.7%. The yield « of n-butyllithium. based on n-butyl chloride. amounts to 87%.

Example 2

In the reactor, which is filled with argon, 25.5 liters of a gasoline fraction, which is kept at 65 to 100 ° C

ίο is boiling, brought in. In the interior of the reactor 630 g of metallic lithium are also ge through the press 5 with subsequent comminution presses. The mixture is heated to 40 ° C, then this mixture is heated within 8.5 hours 4.25 I n-butyl chloride in the form of a 5 ()% (based on volume) mixture with a gasoline fraction that boils from 65 to 100 ° C, added After the end of the metering of n-Butylchloru becomes the reaction mass, which is a suspension

ao represents, held at 70 to 75 ° C for 2 hours and dam to separate the n-butyllithium solution from the lithium chloride and an excess of metalli schcm lithium filtered. The end product, a solution of n-butyllithium, is a 1.19 η liquid straw yellow color of active lithium and a content of inactive additions of 0.3%. Di ( Yield of n-butyllithium based on n-butyl chloride. is 89%.

Example 3

31.9 liters of a gasoline fraction boiling at 65 to 100 ° C are introduced into the reactor, which is filled with argon. In the interior of the reactor: 270 g of metallic lithium are also pressed by the press 5 with subsequent comminution. The mixture is heated to 40 ° C and then this mixture is added to this mixture within 3.5 hours with intensive operation of the dispersing mixer 12 1.86 1 sec-butyl chloride in the form of:

50% (based on the volume) mixture with a gasoline fraction boiling from 65 to 100 ° C admitted. After the addition is complete, the reaction mass, which is a suspension, is 2 hours kept at 65 ° C and then to separate the:

sec-butyllithium solution of lithium chloride and egg filtered with an excess of metallic lithium. Dai The end product, a solution of sec-butyllithium, is a colorless 0.40 η liquid of active lithium with a content of inactive additions voi 0.42%. The yield of sec-butyllithium, based on gene on sec-butyl chloride fluoride, is 79%.

Example 4

28 l of toluene and 6 kg of naphthalene are introduced into the reactor, which is filled with argon. In dei Inside the reactor are also with subsequent crushing 650 g of metallic Li thium pressed through the press 5. The Gemiscl is heated up to 30 ° C and with intensive operation of the dispersing mixer 12 held for 10 hours. Di <reaction mass, which is a suspension with purple Color represents, is carried out. The yield of dilithium naphthalene, based on naphthalene, is 85%.

Example 5

26 g of vaseline oil are introduced into the reactor, which is filled with argon. In the interior of the Re

.ictors are also printed by the pro ¹ ·· ¹ «." 5 with subsequent crushing of 500 g of metallic lithium. The mixture is heated to 42 ° C. Then 12 3.5 liters of n-butyl chloride in the form of this mixture are added to this mixture with intensive use of the dispersing mixer a? n c mixture strength (based on the Vo-! umenl in \ crbindung with Vaselinol added After the addition is complete, the reaction mass is, the ".inc suspension. Tn to 2 hours at ~ 5 ^f C gehal-

10

io: \ after which it is settled within 1b hours aiis ^ hliel.lend to separate the n-butyllithii: ni; solution \ ori the residues of the unreacted lithium is nitrated. The product of the process, a n-but-lithium solution. represents a yellow viscous 1.1) 4N liquid of active lithium with a content of iakii \ en admixtures of 0.5S ^ r. The yield of n-butyllithium, based on n-butyl chloride. entrusted ~ " ^r >

1 sheet of drawings

Claims (4)

Patent claims: 1. Reactor for the production of aikaiiorganischen Compounds through the reaction of alkali metals with haloalkylenes or polynuclear compounds, the one hermetic, with means for the supply of the reagents and the discharge the reaction products as well as means for maintaining the necessary temperature conditions provided housing, as well as contains a mixing device, characterized in that that he informs a press (5) for pressing alkali metal through a nozzle (9) of strands in the interior of the reactor and a cutting device for shredding the alkali metal strands emerging from the nozzle (9) and a dispersing mixer as a mixing device contains. 2. Reactor according to claim 1, characterized in that the press (5) for pushing through of alkali metal and the cutting device in the upper part of the reactor and the dispersing mixer (12) are arranged in the lower part of the reactor, with the space between them a cylindrical insert (15) is installed, which allows a directed circulation of the reaction mass from the dispersing mixer (12) to the cutting device. 3. Reactor according to claims 1 or 2, characterized in that it is equipped with a paddle mixer (18) is provided, which an additional forced circulation of the reaction mass within the reactor guaranteed. 4. Process for the preparation of organolithium compounds by reacting metallic Lithium with haloalkylene or with polynuclear compounds in the presence of a hydrocarbon in an inert atmosphere be: i 0 to 60 ° C with subsequent isolation of the End product, characterized in that it is in a reactor according to Claims 1 to 3 performs.