DE1118188B - Loop process for the production of ª ‡ -olefins by reacting halogen-containing organic aluminum compounds with olefins - Google Patents

Description

Circulation process for the production of olefins by converting halogen-containing organic aluminum compounds with olefins The process for Synthesis of higher olefins according to German Patent 964 642 relates on the catalytic polymerization of ethylene to butene, hexene and / or higher liquid or solid paraffin-like polymers in which the polymerization in the presence of Alumininmalkylen and nickel or cobalt, preferably very fine distributed, especially in colloidal form.

By the method of the German patent 1 034 169 this Synthesis divided into two stages.

First, higher aluminum alkyl compounds are built up by that you can add ethylene to aluminum alkyls. After the construction of an aluminum alkyl with a hydrocarbon residue of the desired chain length becomes nickel, cobalt or platinum added and again a low molecular weight olefin, especially ethylene, allowed to act on the built-up aluminum alkyl. This displaces the ethylene or the other lower olefin is that in the form of hydrocarbon radicals attached to aluminum constructed higher olefin. The starting aluminum alkyl can be reformed here will.

So the immediate reaction product of this olefin synthesis was depending on the oc-olefin used for displacement, a mixture of aluminum triethyl, -tripropyl and -tri-n-butyl etc. with olefins and small amounts of colloidal Nickel.

To the reformed lower aluminum alkyl with success in one To be able to use a new synthesis cycle, this mixture had to be separated. This posed difficulties because during the distillation in the presence of nickel one Displacement sets in, with the elimination of ethylene or others low molecular weight olefins again form higher aluminum alkyls. The nickel had to therefore it must be eliminated in any case, also because you would otherwise end up reusing it Observe a completely different course of the reaction in the structure of the aluminum alkyls would, namely a catalytic formation of butylene according to patent 964642.

A particular advance in α-olefin production brought the Belgian patent 575 992, in which the production of olefins by structure and displacement starts from compounds of the formula R2AIX in which R is any Hydrocarbon radical that does not have any on the carbon atoms bonded to aluminum contains unsaturated bond, and X is halogen. The construction of higher alkyl aluminum halides from these starting materials takes place under the catalytic effect of a compound of the formula Al (R ') 3, in which all three valences of aluminum on carbon or hydrogen are bonded and in which R 'is any hydrocarbon radical or means hydrogen.

The invention of this patent made it possible for the first time to the catalytic effect of colloidal nickel in the displacement reaction Wish to turn it on and off, so to speak. You only needed after the repression the small amounts of added or formed true aluminum trialkyl to convert a suitable additive into the no longer reactive type R2A1X, and then the mixture could be distilled without risk of displacement.

The method according to the invention also works with mixtures of compounds of the formula R2A1X and Alu'3, but in amounts of a similar order of magnitude. It also makes use of another observation made by the inventor.

In the inventor's patent specification 961 537, complex compounds of the formula K [Al R2X2j, which when heated in vacuo turns into potassium halides and cleavage of dialkyl aluminum halides (page 3, lines 81 to 100 of the patent).

The inventor has now established that this information is so far was not right when the situation in this split was more complicated and a distillate consisting of a compound R2A1X and a compound AlR3 and one of potassium halide and its complex compounds with the compound RA1X2 existing residue can be obtained.

By summing up all his mentioned earlier work, has Now the inventor has developed a particularly useful cycle process for the production of Olefins invented. A complex compound of a potassium halide is used here a compound R2A1X of the formula K [AlR2X2], this compound cleaves thermally temporarily in a vacuum into one of a compound R2 Al X and a compound Al R3 existing distillate and one from potassium halide and its complex compound with the compound R2A1X and possibly the compound R Al X2 existing distillation residue, builds up the distillate with ethylene to form higher aluminum halogenated hydrocarbons, displaced from these by ethylene or other types of olefins in the presence of nickel the olefins bound to the aluminum as hydrocarbon residues, mixes it up Displacement product with the distillation residue from the first stage separates the nickel-containing displaced olefins from the complex compound KL1 R2X2] from and returns this complex compound to the first stage. For this cycle procedure R in the compound R2AIX denotes an optionally substituted alkyl radical with at least 2 carbon atoms, the one on the carbon atoms bonded with aluminum contains no unsaturated bond and no branching.

R can therefore be an alkyl of the type indicated above, which optionally is substituted by an aryl or cycloalkyl radical, e.g. B., B-Cyclohexenyl- (3) -ethyl.

When starting this cycle process or to supplement his If the complex compound K [AlR2X2] is required, this compound can be found straight away the desired dialkylaluminum halides and potassium halides produce or but initially start with a lower molecular compound R2AlX, this in Presence of aluminum compounds of the formula Al Ra and ethylene to form higher compounds of the formula R'2AlX, in which R 'is a higher hydrocarbon radical than R means, from this built up aluminum halide hydrogen by ethylene or other, preferably low molecular weight olefins in the presence of nickel displace olefins bound to aluminum in the form of hydrocarbon residues and first add potassium halide and the compound RA1X2 to this product, after which then the cycle process can be started.

Potassium chloride or potassium bromide are used as potassium halides. Potassium iodide or potassium fluoride are not suitable for the process. For the further It is important that the melting points of the complex compounds K [Al R2X2] should be as low as possible and the melts can be slightly supercooled. The melting points of the complex compounds K [Al (C3 H7) 2 Cl2j and K [Al (C4 H9) Cl are pretty low. These complex compounds can also be melted easily subcool. Therefore, when using propylene or butylene in the displacement the formation of liquid layers of the complex compound is no problem at all. In contrast, the melting point of the particularly important complex compound K [Al (C2H5) 2Cl2j is higher at about 60 C. This complex compound is very prone to crystallization, which may give rise to disruptions in the procedure. But you can check the melting point of the Potassium chloride complex can be greatly reduced if you give it the corresponding potassium bromide complex admixed. In addition to the uniform complex compounds K [Al (C2H6) 2Cl2] and K [Al (C2Hs) 2Br2] is there another uniform mixed complex K [Al (C2H5) 2ClBr], which goes down to is liquid at room temperature. But you don't have to go that far. It A part of the potassium chloride is sufficient in the conversion of the diethylaluminum chloride Replace it with potassium bromide to reduce the melting point considerably of the pure potassium chloride complex.

The cleavage of the complex is expediently carried out in vacuo Temperatures from 160 to 200 "C, with aluminum trialkyls and dialkylaluminum halides distill off, while potassium halide and its complex compounds in the residue stay. So by splitting the starting complex one has it in the Hand, which is completely inactive in terms of the build-up and repression reaction Connect, vp R2A1X in its mixture with the fully reactive aluminum trialkyl convict. In the presence of so much aluminum trialkyl reacts like the Belgian Patent 575,992 also includes the dialkyl aluminum halide in both construction also with the repression. You can do this with a very simple treatment in a vacuum in the heat without loss of organoaluminum material and has im Distillation residue the necessary compounds for the later inactivation of the aluminum trialkyls are available in exact equivalence.

The cleavage of the potassium halide complex compound does not need up to to be carried out to the end. For technical reasons, it is more appropriate to to drive the cleavage of the complex compound only as far as the residue of Potassium halide and more complex potassium compounds, at least in the warmth represents well moving porridge. The mechanical properties of the cleavage residues become more and more unpleasant, especially when the complex compound K [A1 (C2H5) C13] is present, the further one drives the cleavage, the melting point of this complex compound is quite high. So at the end of the split you have a very firm cake of potassium chloride and this complex compound, which are very difficult to handle and which is quite high to get the last of the distillate out and must be heated for a long time, with decomposition and losses occurring. Although included other systems with propyl or butyl residues or with bromine instead of chlorine Conditions are more favorable. But even here it is better with a partial split to work. The distillation residue then naturally contains, in addition to the cleavage end products still a certain amount of the unsplit starting complex. But this is meaningless because the whole process is carried out in a cycle. You just need this fact To be taken into account in such a way that, to X parts of the non-complex aluminum compounds To achieve the cleavage distillate in the cleavage with 2 n X parts of the complex must be included, the appropriate size of the coefficient n from complex to complex varies.

The distillate is in a known manner at temperatures from 90 to 1500 C and pressures of preferably 100 atmospheres within the meaning of patent specification 1 034 169 built up. Thereupon the build-up product by ethylene or other, preferably low o; -olefins in the presence of nickel, cobalt or platinum also in the sense the patent specification 1 034 169 subject to displacement. Then the product of displacement with the entire distillation residue from the first stage mixed. Here is the aluminum trialkyl present with regression of dialkyl aluminum chloride and formation of the potassium chloride complex of the monochloride inactivated, so that ideally a Mixture of the displaced olefins and the complex compound K [Al R2 Cl2] is formed, which only needs to be separated, whereupon the complex compound enters the first stage can be traced back. In practice, especially when the displacement level and the mixing of the displacement product with the distillation residue completely or are partially exchanged for one another, mixtures are different Obtained potassium halide complex compounds with potassium halide. You can do both Completely swap levels by already mixing the build-up product with the distillation residue mixed, nickel salts and some aluminum trialkyl added to the mixture and only then carries out the displacement stage. It is even more useful to add the build-up product then add only part of the still residue and the nickel salt to carry out the displacement and finally the other part of the still residue admit. The advantage of this procedure is that even during the Displacement begins the separation into two layers. That is, provided you are with Displaced ethylene, not very important, if not harmful, but quite important when displacing with propylene and butylene. This is because there is no difference in affinity at all between the displacing olefin and the olefin to be split off (in the case of ethylene is this difference in affinity is very large), and therefore one can use an extensive Achieve displacement of higher olefins only with large excess of propylene or butylene. Under such circumstances, the course of the reaction will be in the desired direction improved when one of the reaction products by deposition in a second Phase is removed from equilibrium during the reaction. Do you want that in Potassium chloride contained in the distillation residue does not pass through the displacement stage drag through, you can get the pure complex compound from the distillation residue K [AIRX3] with a suitable solvent, such as aromatic hydrocarbons, z. B. benzene, extract. After the solvent has been separated off, this can then be used Connection for itself and the residue left behind during the extraction to the displacement product to add.

The most complete separation possible when mixing the displacement product potassium halide complex compounds formed with the distillation residue, and optionally the potassium halide itself, from the displaced olefins of the utmost importance for the economic efficiency of the process. It is therefore of It is particularly important that the product obtained is self-contained in layers separates, the lower layer of the complex compound K [Al R2X2j, while the upper one consists of the nickel-containing displaced olefin. If you work at temperatures where the lower layer has melted, e.g. B. in the presence of the complex compound K [Al (C2H5) 2Cl2j at temperatures above 60 "C, the complex compound remains molten and can be drained below. But you can also after complete separation of the layers cool down until the lower layer solidifies and the upper olefin layer is poured on. Finally, after the layers have been separated, the upper one, from the nickel-containing one, can be used distill off the displaced olefin when working with ethyl-containing One can also use another way of separating the olefins from complex compounds the complex compounds go by removing the mixture from the still residue the first stage and the displacement product allowed to cool with stirring, the Compound K [AI (C2Hs) CI2] precipitates as a crystal slurry, which by filtering under Air exclusion is separated from the olefins.

The is also decisive for the economic efficiency of the process Question to what extent in the separation of the olefins and the complex compounds, in particular by layering, the separation can be carried out, so how far with the separation creates mutually completely insoluble layers, or to the extent both Layers are mutually soluble. That is to say, there are noticeable amounts of the halogen-containing Aluminum catalysts in the olefin layer, the completeness suffers the recovery of the halogen-containing catalysts, or one must still from the distillation residue of the olefins win the catalyst fractions. It turned out that this Ratios are very favorable by the halogen content of the olefin layer in of the order of magnitude of 1 0 / o. Amazingly, this separation is also then no matter how complete it is if hexene or octene is used in the displacement phase and complex compounds of the corresponding higher aluminum alkyl halides in the lower layer are located. These small amounts of complex compounds remain in the distillation of the olefins in the nickel-containing residue and can be recovered. When the olefins are worked up by distillation, the nickel remains in the residue.

Only very small amounts enter the lower layer of the complex compounds Amount of nickel. But this is not a disadvantage, as the organoaluminum compounds, which are used to build up, in the course of the distillation of the cleaved complex compound can be preserved, eliminating any trace of nickel that has crept through to this point has remained in arrears. In this, however, the nickel can easily accumulate, since it does not bother there, regardless of whether the residue to the build-up product or is added to the displacement product. The fluid lower layers of the Complex compounds contain only small amounts of olefins. Do you want this too win from the complex compound, you only need the complex compounds saturated aliphatic hydrocarbons, e.g. B. pentane or hexane, of course after separating the olefins, to extract even the last traces of olefins from the. Eliminate complex compounds. These paraffins can, if small parts of it have entered the complex compound R, very easily again distill off.

Example 1 Tn a vacuum-tight and initially filled with nitrogen 148.5 kg of dipropylaluminum chloride and 74.5 kg beforehand by heating are added to the stirred kettle Pour in well dried potassium chloride in the muffle furnace to 400 "C and stir heated to 120 "C. Then you apply a vacuum and increase the temperature in the outermost heating jacket of the stirred kettle to 180 ° C.

The distillation is interrupted when 72 kg of distillate has passed over are and allow the residue to cool in a stirred kettle. This residue remains until easily stirrable to a temperature of 60 "C. It is first placed in a heatable storage container bottled and for later use in the course of the procedure described here deferred. The residue consists of a mixture of the two complex compounds K [Al (C3H7) 2Cl2j and K [Al (C3H7) Cl3] with potassium chloride suspended therein. The distillate has a chlorine content of 9.1% and consists of a mixture of 380% dipropyl aluminum monochloride with 62% aluminum tripropyl. 70 kg of this distillate are now on top of one Abandoned pressure-resistant reaction tower, and 2 kg are put back. In the tower will a temperature of 100 to 110 "C is maintained. The reactor is equipped with Raschig rings made of copper, and an ethylene pressure of 100 atmospheres is maintained in it. The liquid reaction product running down below is repeatedly at the top of the Tower abandoned by a pressure pump and analyzed after each pass. The halogen and aluminum content gradually decreases due to the addition of ethylene away.

An additional control of the course of the reaction can be found in the weight of the reaction product running down on the tower, if from time to time the Let the tower run completely empty and the entire reaction product decreases below.

Depending on the desired molecular size of the later final reaction products if you store more or less ethylene. A technically very useful olefin mixture as an end product in which all the odd-numbered olefins from C5 to about Cio are represented are, is obtained if one drives the addition of ethylene so far that from the 70 kg of chloride-containing aluminum tripropyl used, a total of 192 kg of liquid with a chlorine content of 40 / o are obtained.

To this 192 kg, continue carefully before the admission of air must remain protected, you now give a nickel catalyst, which in the following How has been made: 100 g of finely powdered nickel acetylacetonate will be suspended in 500 cm3 of hexane, and then the suspension is left in the absence of air flow in to half of the 2 kg of distillate put aside above, with stirring and cooling. A deep black solution or suspension is created. Made in this way with nickel higher organoaluminum compounds that have been added are now placed in a pressure vessel pumped in, which contains 700 kg of dry and oxygen-free propylene. There is now regression of aluminum propyl compounds with the release of higher ones Si-olefins instead of the organoaluminum compound. The process takes about 1 to 2 hours. It is made by stirring and gently warming the pressure vessel promoted to about 30 "C. The progress of the reaction can be followed by that small samples are withdrawn under nitrogen into vessels cooled to -sOOC, that Propylene quickly eliminated at the lowest possible temperature while applying a vacuum and then the residue is decomposed with methanol. Here propane is developed, which is collected. The ratio of propane to titratable aluminum equivalents should then be as possible close = 1. Titratable aluminum equivalents are understood to mean the amount which are immediately followed by the method of 0. Glemser and L. Thelten, Z. ang., 62, P. 269 (1950), can titrate, d. i.e., it is the part of the aluminum that originally was not bound to chlorine. If you do this several times from the beginning during this operation If samples are taken, it is found that this ratio varies from sample to sample changes and finally approaches 1.

Once this reaction stage has been completed, the pump is pumped into the the reaction vessel still under propylene pressure removes the liquefied residue from the first heat splitting of the complex compound as completely as possible and stir the mixture well. During this operation you can already start to drain the propylene from the vessel. It is liquefied again and used for later put in a storage container again for use.

After the propylene has evaporated completely, the reaction vessel is located two immiscible liquids that separate when the agitator is switched off. The lower layer consists of practically pure potassium aluminum dipropyl dichloride, in which there is still a very small amount of free potassium chloride and in which there is also a little potassium aluminum propyl trichloride present as equivalents for that which was removed in the course of the process and not completely added again Amount of the aluminum tripropyl rich distillate.

It is not absolutely necessary, but very useful, the composition adjust the lower liquid phase as described above because one then has greater certainty that in this phase of the experiment there is no free real aluminum trialkyl is more in the mix.

The lower layer is left out of the reaction vessel with further exclusion of air out and expediently brings them straight into the stirred tank to carry out the thermal Cleavage mentioned at the beginning of the example.

The next cleavage for the next reaction cycle can then take place immediately are executed. From the first repetition onwards, the small 2 kg amount is withdrawn refrain from halogenated aluminum tripropyls. The nickel catalyst is from the first rep using only 100g of fresh aluminum tripropyl to manufacture.

The upper olefin layer is colored dark by colloidal nickel. It is freed from nickel by distillation. The higher-boiling components are distilled off in vacuo. The nickel remains in the residue, can be collected and later processed into nickel acetylacetonate. The composition of the olefin layer in a test run carried out according to this example is the following: C number 4 1 5 1 6 1 7 1 8 1 9 l to 1O l 13 l 15! 17 l 19 Weight percent. . | 2.1! 5.6 1 2.4 | 14.1 | 1.9 a 21.2 1 0.3 1 19.8 j 15.1 j 9.2 | 5.2 1 2.8 The small amounts of the even-numbered olefins get into the reaction product because during the build-up of the higher aluminum alkyls in the pressure reaction tower to a small extent through the so-called displacement reaction from aluminum propyl, aluminum ethyl is formed, which in turn forms the even higher aluminum alkyls.

Example 2 The procedure is exactly as in Example 1, but used in the second reaction phase after the addition of nickel instead of propylene 1000kg α-butylene.

The olefin layer has the same composition at the end of the experiment as in Example 1, however, the complex compound K [Al (C4H9) 2Cl2] is used as the lower layer obtain. This complex compound is also liquid down to room temperature. If you heat them in a vacuum of 0.1 Torr to 180 to 200 "C, you get a distillate, which consists to about 700 / o of aluminum tributyl, and with which one with addition of ethylene then build up even higher aluminum alkyls and later even higher aluminum alkyls Can produce olefins. In this way it is possible from the synthesis of the odd a-olefins to pass over to the synthesis of the even-numbered ones. It goes without saying anytime The reverse is also possible if an aluminum compound is first introduced into the pressure reaction tower with straight-chain residues and in the second reaction stage with propylene, n-pentene or n-heptene treated.

Example 3 284 kg of potassium aluminum diethyl dibromide are added as at the beginning of Example 1, first heated in vacuo, passed to 141 kg of distillate are. The distillate contains 8.9% bromine and consists of 900% of diethylaluminum bromide and 100 / o from aluminum triethyl. The residue from this cleavage is left in vacuo simply in a stirred kettle.

The distillate is built up at 150 ° C. in a pressure reaction tower according to Example 1 with ethylene of 100 atmospheres until it has increased 700 g per kilogram. A nickel catalyst made from 500 cm3 of hexane, 80 g of nickel acetylacetonate, 80 g of aluminum triethyl is added to this mixture and the nickel-containing organoaluminum compound that has now formed is again pumped onto the reaction tower at 50 to 600 ° C. and 50 atmospheres of ethylene pressure. The progress of the reaction can be checked by hydrolyzing small amounts of the liquid drawn off below and measuring the amount of gas emerging must be largely pure ethane, and in addition 1 equivalent of ethane must be formed per equivalent of titratable aluminum. Once this point has been reached, this operation can be terminated to begin with the split of the complex potassium aluminum diethyl dibromide and heated to 40 to 50 ° C while stirring. Separation into two layers occurs again, and the further treatment is analogous to Example 1. The olefins obtained have the following composition: C number 4 to 6 l 8 l 10 l 12 Weight percent ... 37.0 ß 33.5 | 21.8 | 6.1 | 1.3 The retained complex compound can easily be cleaved again in vacuo, as described at the beginning of this example.

Example 4 120.5 kg of diethylaluminum monochloride are placed in a stirred vacuum vessel according to Example 1 with 37.25 kg of potassium chloride and 59.5 kg of potassium bromide, both salts beforehand well dried - mixed and stirred at 120 "C to a homogeneous liquid. 70 kg are distilled at a bath temperature of 160 ° C. and a vacuum of 3 mm away. The residue in the stirred kettle is allowed to solidify with stirring, this being the case Residue takes on a loose, still flexible form. The distillate contains 18.5 0 / o chlorine and 2.8% bromine and consists of 27 ° / o of aluminum triethyl and 730 / o from aluminum diethyl monochloride and diethyl aluminum monobromide. At the first time To carry out this operation, take 2 kg from the distillate and give the remaining 68 kg for reaction with the ethylene on the pressure reaction tower mentioned in Example 1. You build up with ethylene up to a weight gain of 180 kg, reactivate with colloidal nickel and treated as described in Example 3, -with ethylene from 50 atmospheres in the pressure reaction tower. The resulting mixture of regressed Ethylaluminum compound and olefins are added to the initially used for cleavage Return the stirred tank and proceed as in Example 3.

Example 5 The procedure initially followed exactly as in Example 1 up to production of the higher aluminum alkyl after reaction with the ethylene of 1q0 atmospheres in the pressure reaction tower (before adding the nickel).

Here, however, the removal of 2kg is the beginning of the cleavage to refrain from the distillate obtained.

The higher alkyl is filled into a larger pressure vessel and brought together here with nine tenths of the residue that was initially due to the split the complex compound was obtained in vacuo. A mixture is now formed out, for the most part from dialkylaluminum chloride with odd-numbered longer Alkylene and also consists of the corresponding Äluminiumtrialkyl9n. Man activated with a nickel catalyst made from 500 cm3 -hexane, 100 g Ni-acetyl-acetone, 100 g Al-tri-propyl and now proceeds according to Example 2 with the addition of 300 kg propylene. It finds now the replacement of the longer odd-numbered alkyl groups by propyl groups below Release of the odd-numbered olefins takes place, and at the same time the segregates Liquid, because the complex compound - dipropyl aluminum chloride with which can form potassium chloride. This segregation during the conversion with the propylene offers advantages because the reaction with the propylene is more complete Man Therefore, in this phase of the reaction, the amount of propylene compared to the - reduce to 50% used in Example 2. After about 2 hours you give it last tenth of the split arrears initially received added and can now process the entire reaction mixture, as described in Example 2, further.

Example 6 A mixture of 241 g of diethyl aluminum monochloride and 114 g of aluminum triethyl is in an autoclave at 125 "C and 100 atmospheres pressure shaken with ethylene. A steel bottle with ethylene is attached to the autoclave and the reaction ends when the mixture has absorbed a total of 400 g of ethylene Has. The excess pressure is blown off and a nickel catalyst is now put into the autoclave, made from 150 g nickel acetylacetonate and 120 g aluminum triethyl. Now press one again ethylene up to 40 atmospheres and warmed with shaking to about 50ob, until no more ethylene is absorbed. Now let the ethylene overpressure and fills the liquid autoclave contents with exclusion of air. Then you give 135 g of ethylaluminum dichloride and 320 g of potassium chloride are added and the mixture is stirred at 100 "C, with some of the olefins (hexene and some octene) are rapidly distilled off. For the further Work-up has three options: a) It is allowed to cool further while stirring, where the complex compound K [Al (C2Hs) 2Cl21 precipitates out as a crystal slurry that passes through Filtration with the exclusion of air can be separated from the olefins. b) One stops the temperature is so high (about 70 ° C) that the complex compound remains molten, and drains the lower layer melted. c) One leaves after complete separation of the layers cool until the lower layer has solidified compactly, and simply pour the olefins away.

The olefins are then in each case, as usual, by distillation further processed. The solid complex compound (780 g) can then be used for the repetition of the experiment are cleaved according to Example 4 in vacuo. Further processing takes place again according to the procedure just described here.

Of course, there is then no need to add monoethylaluminum dichloride and potassium chloride, because these amounts now with the cleavage residue in the Reaction product are introduced.

Claims (14)

PATENT CLAIMS: 1. Circulation process for the production of olefins by reacting halogen-containing, organic aluminum compounds of the formula R2AlX, where R is an optionally substituted alkyl radical with at least 2 carbon atoms, the carbon atoms bonded to aluminum do not have an unsaturated bond and contains no branch, and X is chlorine or bromine, in the presence of Aluminum compounds of the formula AlR'3, which have all three valences of aluminum Contain carbon or hydrogen bonded, where R 'is any hydrocarbon radical or hydrogen means with olefins, characterized in that one of Complex compound of a potassium halide with a compound R2A1X of the formula K [AlR2X2] assumes this connection is thermally converted into a compound R2A1X and a Compound A1R3 existing distillate and one from potassium halide and its complex compound with the connection R2A1X and any distillation residue present in the compound RAlX2 separates the distillate with ethylene at temperatures of 90 to 150 "C and higher Pressing to higher aluminum halocarbons builds up from these through Ethylene or other types of olefins in the presence of nickel which act on the aluminum Hydrocarbon residues displaced olefins bound, the product with the distillation residue from the first stage mixed, the nickel-containing displaced olefin from the complex compound K [AlR2X2] is separated off and this complex compound is returned to the first stage. 2. The method according to claim 1, characterized in that the Cleavage of the potassium halide complex compound drives so far that the residue of potassium halide and complex aluminum compound, at least one more Heat represents well moving porridge. 3. Process according to Claims 1 and 2, characterized in that the thermal cleavage is supported by a vacuum. 4. Process according to Claims 1 to 3, characterized in that one the displacement stage and the stage of mixing of the displacement product exchanged with the distillation residue from the first stage. 5. The method according to claim 4, characterized in that the Build-up product mixed with the distillation residue, the mixture of nickel salts and add some Al R3 and then carry out the displacement stage. 6. The method according to claim 4, characterized in that the Build-up product only adds part of the distillation residue and nickel salts and only then does the repression, whereupon the product of the repression is denoted The remainder of the distillation residue is added. 7. Process according to Claims 1 to 6, characterized in that the mixture of distillation residue from the first stage and displacement product separates in the heat by layering, with the upper from the nickel-containing displaced olefin and the lower one from the complex compound K [AlRX2i and optionally Potassium chloride. 8. The method according to claim 7, characterized in that the drains melted lower layer. 9. The method according to claim 7, characterized in that according to complete separation of the layers cools until the lower layer solidifies and the upper layer Pour off olefin layer. 10. The method according to claim 7, characterized in that according to Once the layers have separated, the upper, displaced from the nickel-containing olefin existing layer distilled off. 11. The method according to claims 1 to 6, characterized in that when working with ethyl-containing complex compounds, the mixture from the distillation residue the first stage and the displacement product allowed to cool with stirring, the Compound K [Al (C2H5) 2Cl2] precipitates as a crystal slurry, which is filtered under Air exclusion is separated from the olefins. 12. The method according to claims 1 to 11, characterized in that the organoaluminum complex compound obtained in the last stage before their re-cleavage to remove the last traces of olefins with saturated ones aliphatic hydrocarbons, e.g. B. pentane or hexane extracted. 13. The method according to claims 1 to 12, characterized in that one the complex compound K [Al R2X2] in a separate operation in known Way and then use it to introduce and supplement catalyst losses admits in the course of the cycle process. 14. The method according to claims 1 to 12, characterized in that one first from the compounds of the formula R2AlX in the presence of aluminum compounds of the formula Alu'3 and ethylene higher compounds of the formula R'2AIX, where R 'is a Hydrocarbon radical higher than R means, builds up, from this built up aluminum halohydrocarbon through ethylene or other, preferably low molecular weight oc-olefins in the presence of nickel displaces olefins bound to aluminum in the form of hydrocarbon residues, the Product mixed with potassium halide and the compound RA1X2 and only then the Circulation process according to claims 1 to 12 carries out. Considered publications: German Patent Specifications No. 961 537, 964 642, 1,034 169; Belgian patent specification No. 575 992.