BE656158A - - Google Patents

Description

  

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  "Separation procedure for trialkyl aluninium compounds"
 EMI1.2
 The present invention relates to a novel process for resenerating a complex of trialkyl aluminum and a COMPOS6 having the formula in which R or an alkyl radical; H is nitrogen, arsenic ,,
 EMI1.3
 phosphorus, sulfur, selenium or tellurium; X is
 EMI1.4
 ., a halogen and n is a1 to 3 or 4, depending on the element II considered, This invention relates to .J!:; alel! 1en'.t of new complexes of ammonium chlorides alkylc and cotaposis low-weight aluminum trialkyl tuo7Gculirot ot a process for separating low molecular weight aluminiumtriaIL-yl compounds from typo4 hydrocarbons or oysters

 <Desc / Clms Page number 2>

 
 EMI2.1
 of '.Qml) oaéa. aluminum.



  "With the aid of the fixing reaction, it is to obtain a trialkyl aluminum at mole weight" 41av, which is of great interest as an offset blade for the production of olefins by weight. high molecular and / or high molecular weight alkao.a.With regard to the production of alpha-olefins,,> ..:
 EMI2.2
 'A necessary part of the operation is to separate
 EMI2.3
 1, to,; the low molecular weight trialkyl aluminum of the relatively high molecular weight alpha-olefioea. The separation can be removed by contacting the mixture of alpha-olefin and trialkyl aluminum at low weight no-leo, with a REX compound or with a complex of trialkyl aluminum and R MX.

   The lil se j complex. , i. & 9mbine with 1 <aluminum trialkyl to form an oom-. plaxo 2-tl # these two complexes being insoluble in. . t.aha-slr5fi, as. Due to the insolubility of the -4an-alpha-olefin complexes, two phases are formed which can easily be separated from one another. The - 2: 1 complex can be heated to an elevated temperature, at which i. ë, decomposes into complex 1; 1 and aluminum trial), 71st.



  Complex 1 <1 does not readily decompose and requires a high temperature and pressure control which causes pyrolysis of the aZumi, n: 3.usn-trialkyle. As he is '-. desirable to reuse the complexing compound in the
 EMI2.4
 'process and as this product is reusable only
 EMI2.5
 "'. to OR4 forms. complex 1; 1; the process described above
 EMI2.6
 . is usually implemented by initially forming the
 EMI2.7
 'complex 1:., then then by operating with this complex.



  Accordingly, the present invention relates to an improved JC ... qua technique for the decomposition of the 2: 1 complex.



  >] # / .. ¯ '

 <Desc / Clms Page number 3>

 
 EMI3.1
 ; The "binding" reaction also consists of a reciprocal action of a low molecular weight monoolefin and a low molecular weight aluminum trialkyl =; j re. As a result of the reaction, the monoolefin is added in multiple form to the alkyl radicals of the aluminum compound.
 EMI3.2
 aluminum to form relatively higher molecular weight aluminum compounds. The fixing product can be used as the starting compound for the preparation.
 EMI3.3
 , 'duction of other interesting compounds, such as, for example, alpha-olefins and alcohols with a high molecular weight. With regard to the production of alpha-olefins there is a lack of a satisfactory process for separating alpha-olefins from the product which contains them.

   Four this
 EMI3.4
 Therefore, the production of alpha-olefins from the fixture was disproportionately expensive and in poor efficiency. Considerable research has been done to decide on an inexpensive and efficient process,
 EMI3.5
 to produce alpha-olefins from the binding product.

   The Applicant has discovered, quite unexpectedly, a process for achieving this object, and which is interesting from an industrial point of view because of the ease and economy with which alpha-
 EMI3.6
 olefins are produced. , ',', â The present invention therefore for,; Objects to provide - a process for the production of alpha-olefins from a fixing product; - a good yield process for separating alpha-olefins from aluminum compounds of relatively low molecular weight with which they are mixed;

   '- a good yield and economical process for the',

 <Desc / Clms Page number 4>

 
 EMI4.1
 decomposition of the 2: 1 complex of trialkyl aluminum eÉ'¯jj .de R MX is a 1; 1 complex and trialkyl aluminum.



  Other objects and advantages of this invention. The z will become apparent upon reading the description oi-'11, harsh and its explanation, together with the accompanying drawings. on which - the flower 1 is a schematic representation '¯,], of a device in which the present OE-1 is used']; /] vention.



  - eb Figure 2 is an achematic representation,
 EMI4.2
 
 EMI4.3
 of another device used in the present invention.



  In general, the indium "1 goals which are above are achieved by a process characterized by the fact that a complex product is brought into contact containing a complex 2; 1 of trialkyl aluminum and d 'a compound having' for formula RnMX in which R is an alkyl radical,>, M represents nitrogen, arsenic, phosphorus, dubo-sulfur, selenium or tellurium, X is halogen; and n is equal to 3 or 4, depending on the element If. considered6 ,, "this at a temperature and for a time sufficient lj 'to separate the trialkyl aluminum from complex 2:

  1.,
 EMI4.4
 In one aspect of the invention, ','
 EMI4.5
 a 2sl trialkyl aluminum complex in which the. 4.,
 EMI4.6
 Alkyl radicals have an average of about 2 to 5 carbon atoms and a trialkyl ammonium halide in which
 EMI4.7
 the alkyl radicals have an average of 1 to 5 carbon atoms approximately with an extraction solvent, for example 1 w ple with a paraffinic hydrocarbon at a temperature of between 135 to 2000 ° C. approximately, and the complex 2sl on is thus decomposed. a 1 <1 complex and an aluminum
 EMI4.8
 trialkyl.

 <Desc / Clms Page number 5>

 
 EMI5.1
 



  By contacting the complex 2s 1 with a -solvant 4'extnaation as dos paraffinized hydrocarbons,. As, it becomes possible to carry out the decomposition reaction under atmospheric pressure. Without an extraction neck, it was necessary to operate BUL3, a pressure lower than that of the atmosphere for the decomposition reaction. This represents an important advantage because it is expensive to operate industrially in a relatively high vacuum apparatus. Another''.,','
 EMI5.2
 The advantage of using the extraction solvent for the "-, -" decomposition reaction is that it shortens the reaction time required to carry out.
 EMI5.3
 extensive conversion of the 2sl complex to a 1: 1 complex and trialkylated aluminum.

   9.U advantages: e /; ' can provide the present invention make this process industrially attractive.
 EMI5.4
 Contacting the 2: 1 complex and a sol- '. Extraction such as a paraffinic hydrocarbon can be done in separate charges or continuously. In the batch process, the extraction solvent and the 2: 1 complex are retained in the pyrolysis zone.
 EMI5.5
 for a suitable period of time so that Za. , transformation desired into complex 1: 1 and aluminum ', trialkyl can be done * Then the contents are drained from the holding vessel and the products are separated for
 EMI5.6
 recover the 1: 1 complex and the aluminum trial% le.

   In continuous operation, the 2: 1 complex can be introduced into the upper section of an extraction column and allowed to flow countercurrently to the upward passage of the extraction solvent. Under the temperature conditions which are maintained in the extraction column

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 tion, the extraction solvent extracts the aluminum trialkyl from the 2: 1 complex and the two products exit in
 EMI6.1
 t8te, & 1, upper part of the column. The complex .



  The resulting 1: 1 comes out at the bottom of the column. In the case where the transformation of the complex. 2 <1 in fact in a measurement. Inner line 1 As desired, the untrained 2tl complex can be recycled to the upper part of the extraction column.



   The complexing agent which is used to implement the invention is defined by the formula '
 EMI6.2
 Rni w, where R is an alkyl radical, k1 is nitrogen, aruenio, phosphorus, sulfur, zelonium or tellurium, X is halogen and n is equal to 3 or 4, depending on the element M considered. Low molecular weight alkyl radicals are preferably used, ..
 EMI6.3
 o est-àire those which comprise from 1 to 5 atoms of. ..j.¯ carbon. As the length of the alkyl chain increases, the solubility of the complex in hydrocarbons also increases, so that the degree of separation is decreased.

   Among the elements represented by 1Ii1, ::, ':, ". And all of which are metalloids, the one that is lent -... re is nitrogen; however any other metallo! -. ,, '
 EMI6.4
 of indicated above is also effective as a6ent; ':, complexing to carry out the process of this inclusion.
 EMI6.5
 vention: any of the halogens can be used; jµ /; ¯ however, chlorides are used.



   In order to describe this invention more clearly and more usefully, the following discussion will be oriented.
 EMI6.6
 ted in the sense of tetraalkyl ammonium halides "This, however, should not be construed in a limiting sense and is within the scope of this invention -

 <Desc / Clms Page number 7>

 
 EMI7.1
 to use any other halide of
 EMI7.2
 metalloXde-ûlkyle, danp the field of the formula exposed above, Zn besides it goes without saying that one can replace:

   ¯. because nitrogen by each of the other metalloids in the ex '
 EMI7.3
 specific examples of complexing agents and
 EMI7.4
 complexes shown below. t,. The tetraalkyl ammonium halide which forms part of the complex product is one in which the 4 alkyl radicals have an average of about 1 to 5 carbon atoms. average ", danr, the case of no
 EMI7.5
 bre of carbon atoms of ammonium halide
 EMI7.6
 tetraalkyl and aluminum triallvl means the total number of carbon atoms of all alkyl radicals divided by the number of alkyl radicals.

   The tetraalkyl ammonium halide can be, for example, tetramethyl ammonium chloride, tetras methyl ammonium iodide, tetraethyl ammonium fluoride, totrabutyl ammonium bxomura, ammonium tetnamô, 11; F th3rlel ammonium tetrabutyl fluoride and ttrapropyl ammonium iodide, ar-monium chloride tetra 1. propylet etc. Tetraalkyl ammonium chloride is preferred as a component of the complex because it tends to ..)
 EMI7.7
 be less soluble in hydrocarbons to a significant extent; and, in the form of the complex, it is
 EMI7.8
 easily decomposed into 1: 1 complex and aluminum.: ..
 EMI7.9
 trialkyl. Another advantage is that we find more
 EMI7.10
 tetraalkyl ammonium chlorides readily than the other halides.

   Or. Also prefers to use, 'bzz. Ammonium chloride tetramethyl flowing component of the oom -; "e> .plex due to its tendency to be less soluble in. i, ', ¯., hydrocarbons, From the point of view of the halide to bzz, y9" ,

 <Desc / Clms Page number 8>

 
 EMI8.1
 used to make the complex, the tetramethyl ammonium halides have an advantage which is industrially important. Generally speaking,
 EMI8.2
 , tetraalkyl.onium halides can strain. complexes which are either soluble or insoluble in
 EMI8.3
 ...., \. hydrocarbons.

   With respect to the lll complex, "it is preferred that it be insoluble in the extraction solvent, so that it remains in the extract phase. It is also preferred that the 2: 1 complex is insoluble.
 EMI8.4
 in the extraction solvent) for the same reasons. "';. = / Aluminum trialkyl which is combined with
 EMI8.5
 the tetraalkyl ammonium halide to form the complex pno contains on average from 2 to 5 atoms of
 EMI8.6
 Carbon. As particular examples of aluminum .l, trialkyl, there is aluminum trietbyl, aluminum:,;. '. tripropyl, aluminum tributyl, and the like.

   From the point of view of the solubility in hydrocarbons, it is preferred that the sum of the average number of carbon atoms of the radi-
 EMI8.7
 Alkyl waters in trialkyl aluminum and tetraalkyl ammonium halide is not more than 6. When the sum of the averages of the carbon atoms exceeds 6, the complex product tends to be more soluble in hydrocarbons .

   As particular examples of complexes which can be treated according to the process of this invention, there are the following 2-aluminum
 EMI8.8
 ammonium triethylchloride t6tnamethyl, 2-aluminum triethyl-ammonium iodide tetramethyl, 2-aluminum triamyl-ammonium fluoride tetraetx, yl, 2-aluminum triisobutyl-ammonium bromide tetraethyl, '"" 2-.aluminum tributyl, o-oh.tetraethyl ammonium chloride, 2-aluminum tripropyl-tetrame ammonium fluoride.

 <Desc / Clms Page number 9>

 
 EMI9.1
 thylo, 2-aluminum triisopropyl-fluoride A'wamoni.ura7 tetrapropyl, 2 ... aluminum tributyl-ammonium iodide tetramethylo, 2-aluminiim tri, sobutyl-ammonium chloride t6traôthylo, 2- aluminum tr1étbyle-obloruro. ,;

   , tetraisobutyl ammonium, 2-aluminum triisopropyl-
 EMI9.2
 tetramethyl ammonium chloride and tri-: propyl ammonium tetraicopropyl 2-aluminum bromide. Examples pct. ^ T, Lea3ttra of compounds of other metals which may be used correspond to the compounds indicated above.
 EMI9.3
 descus.



   The 2: 1 complex is easily broken down conformably. at the time of this invention. In the decomposition reaction, the 2: 1 complex is converted to a 1: 1 complex with the release of one mole of trialkyl aluminum for each mole of complex that is decomposed. Complex 1: does not decompose easily and it requires temperature and pressure conditions which result in pyrolysis of the aluminum.
 EMI9.4
 minium trialkyl.

   Since there is an intur8t to reuse the tetraalkyl ammonium halide in the process and since this compound can only be reused in the form of a 1: 1 complex, the process is usually carried out by
 EMI9.5
 initially forming the lt1 complex, then by operating '. ; 0 'in the process with this complex, rather than with the halo ::': tetraalkyl ammonium genide. therefore, the following description and discussion are particularly directed
 EMI9.6
 the use of lil complex; however, it goes without saying that uncomplexed tetraalkyl ammonium halocene can also be used in the various embodiments of the invention.



     The 1: 1 complex is made by mixing alumi-

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 EMI10.1
 Triangle nium and the early alkylated ammonium halide and the reaction is allowed to proceed. This reaction is
 EMI10.2
 exothermic and therefore it is not necessary
 EMI10.3
 do proccrd, r 1 a heat input to continue it.



  !) In some cases, it may be beneficial to preheat the reagents in order to initiate the reaction. The reaction tum- 'p4raturu is between about 50 and 15,000 and more commonly between about 10,000. A .fy. these temperatures and m8mu outside the specified interval "
 EMI10.4
 that, the reaction is carried out under a pressure which can
 EMI10.5
 Being less) equal to or greater than that of the atmosphere. phere. Usually the reaction is approximately atmospheric. For the 1: 1 complex, quantities are needed for
 EMI10.6
 equal weight of trialkyl aluminum and halogen
 EMI10.7
 tetraalkyl ammonium ro. In practice, we operate with stoochiomtral proportions or with a very low one. exa $ a dtaluhilnium trialkylo, in order to avoid the need
 EMI10.8
 to purify the complex. , '.
 EMI10.9
 



  The 2: 1 complex is formed rapidly by the reaction between the 1: 1 complex and the trialkyl aluminum a r ', low molecular weight which is described above. The reaction between the lil complex and the triaUnrI6 aluminum is
 EMI10.10
 exothermic and therefore it is not necessary
 EMI10.11
 to heat to maintain the reaction. In general, the temperature at which complex 2: 1 is formed is 00 ° M. taken between about 50 and 150 ° C, and more usually between about 50 and 10,000.

   The pressure under which the reaction takes place can also vary within a); 1
 EMI10.12
 large measure from a pressure greater than that of
 EMI10.13
 the atmosphere, passing through that of the atmosphere, up to a pressure lower than atmospheric pressure

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Pressure is usually atmospheric pressure. The reaction time is relatively short, but it can vary between approximately 0.25 and 30 minutes.



   As indicated above, the 11: 1 complex is used to separate trialkyl aluminum from a mixture also containing alpha-olefins. The mixture of trialkyl aluminum and alpha-olefins is obtained in the displacement reaction involving a pro-. addition line. In order to better understand how the present invention is used, a description will be given below of the binding reaction, and of the subsequent displacement reaction.



   The binding reaction consists of a reaction between a mono-olefin or low molecular weight alkylene, such as ethylene, propylene, butene, etc., and a low molecular weight aluminum trialkyl, as per example a trialkylo aluminum in which the alkyl substituents contain from 2 to 4 carbon atoms approximately.



  The fixing product obtained is constituted by a compound. se trialkyl in which the molecular weight of the alkyl groups varies considerably. We can represent the equa-; tion of fixation by the following reaction;
 EMI11.1
 where x, y and z represent whole numbers between 0 and 14 approximately ot the sum x + y + z is equal to a small "n" The fixing reaction can be carried out by passing the mono-olefin, such as of

 <Desc / Clms Page number 12>

 
 EMI12.1
 11 ethylene in an aluminum tr, a3.r3, a aorcua 1; a.txzz..s';

   
 EMI12.2
 nium triethyl, preferably a diluent is present, '
 EMI12.3
 , w under various reaction conditions, the reaction temperature can be between 65 and 150 110 e't .X¯ the nailometric pressure between 14 and 350 kg / cm approximately and more commonly the temperature is About 90 to 12000 and the nanometric pressure of 70 to 245 kE / om 'Il¯,
 EMI12.4
 The binding reaction provides a distribution '
 EMI12.5
 statistics of the lengths of the chains alkyl, oaraotâr ..

   Xie by the Poisson relation, which can be expressed as follows ,, y¯f, ..:
 EMI12.6
 
 EMI12.7
 where p (n) is the probability that a Y "\ * /, 7 \ JI
 EMI12.8
 certain hydrocarbon radical is formed by "n" additions
 EMI12.9
 . t1 of ethylene on the primitive ethyl aluminum bond - '. j (. bzz ment present, and m is the average number of additions.: 1:. of ethylene per attachment chain. The following table. ruz. 1 \ 4ft. Contains an illustration of a type of distribution that,; ", J¯. One obtains in the binding reaction! 1 'jµ1]

 <Desc / Clms Page number 13>

 
 EMI13.1
 TABLE '"1 Ù;' r v 7, J..f .. fI, ....
 EMI13.2
 



  Group e.iklo on 29 '' 3 ',.



   2 0.04. ",> Fr ::;:.> '04 t -il' .. ', \., 1.." ;,' .- ,. ".>. Q 'c6 3.37, y4u: y. yt A'f 'This ..' / 9; w .- :.; ..,; ',: ..;' ,, 2Ot42 \ ..) .. ') t "'11.



  , - ..., '. .; 3.



   14 16.20. ¯e '"C16 11 61.' , '. ,,;' .



  "16 11.61, \.



  C, ig 6.21 "",; t. ;; ... '1 "..,' I-,". "'." t ':. , ....; "," '.. c 20; J :. 47 '<"3 7;: -' i'f.



  1925. : ,, l,, ... "r ,, ',, t' c24 p '.1 t.",' ': 1 ;, 026 0010 -..-' \ - :: r 'C 0.05 . l, '. : "f, ', t
 EMI13.3
 The binding reaction can be carried out in '
 EMI13.4
 a diluent which may be a paraffinic, - ,,,. <.; ... cycloparaffiniquo or aromatic hydrocarbon, such as for example .l3soootanQ, cyclohexane, bonzena, xylene, "'
 EMI13.5
 kerosene, alkylate, naphtha, etc. The diluent
 EMI13.6
 ¯ S
 EMI13.7
 facilitates the control of the reaction temperature,
 EMI13.8
 which is exothermic and also serves as a solvent for bzz
 EMI13.9
 the fixing product. The diluent used in the reaction
 EMI13.10
 binding tion can also be the alpha-olefin which
 EMI13.11
 . has been described above.
 EMI13.12
 



  The attachment product has allyl substituents containing from about 2 to 40 carbon atoms or more. It is subjected to a displacement reaction with a low molecular weight mono-olofin comprising back

 <Desc / Clms Page number 14>

 
 EMI14.1
 2 to 4 carbon atoms. Low molecular weight monoolefins can be eg exumplo. 8tbyl $ no, propylene or buteno, Hence the displacement reaction znatao-.o3.t, n takes the place of the high molecular weight alkyl components of the aluminum compound. Of
 EMI14.2
 00 fact) the product of the displacement reaction comprises a t: 4 -alkylo molecular weight in which / - the alkyl substituents comprise from about 2 to 4 carbon atoms and alpha-oletinos which have from 2 to 40 carbon atoms. carbon or more.



   The displacement reaction can be carried out in the absence of a catalyst by the spray technique.



  In this process, the charge is atomized in a well-known manner when it is introduced into the sound system of the displacement reaction. We keep the temperature below
 EMI14.3
 of approximately 37QOC, plus cot.arar.ont between 4tri ot 370 C oÉ, approximately, and preferably between 200 and 30,000 approximately. The absolute pressure of the reaction is kept below .-
 EMI14.4
 do about 14 kg / cm 2 and it may be lower than that of the atmosphere, and for example as low as
 EMI14.5
 0.07 kg / cm 2 absolute.

   The reaction pressure preferably varies between about 1.4 and 7 kg / cm a absolute. the du-. The reaction time can be between 30 seconds and about 15 minutes, more commonly between about 1 and 10 minutes, and preferably between 2 and 7 minutes.



   As regards the fear-spraying process for aluminum olkyls, various techniques can be used. For example, conventional hollow cone nozzles can be used and the atomization is obtained. '
 EMI14.6
 maintaining a pressure difference in the nozzle, '.-ô "

 <Desc / Clms Page number 15>

 In some cases, the atomization of aluminum alkylo
 EMI15.1
 is favored by using an atomizing gas, which,; For the purposes of the present invention, it may be the alkylen which is used in the displacement reaction. There is
 EMI15.2
 nt4rdt to introduce the aluminum alkyls at a high temperature due to the lowering of the viscosity.

   In general, the aluminum alkyls are preheated to a temperature below the reaction temperature, for example up to about 340 °. Before atomization, we '. Preferably preheats the aluminum alkyls to bring their temperature to 90 to 160 C.
 EMI15.3
 In a non-catalytic operation, in which the charge of the displacement reaction is not atomized.
 EMI15.4
 It is preferred that the temperature be 200 to 320 ° C for the displacement reaction.
 EMI15.5
 It is then preferable to carry out the displacement reaction under a gauge pressure of between 10.5 and 21 kg / cm2, and the duration of the reaction could vary between 0.1 and 10 seconds.
 EMI15.6
 The displacement reaction can also be carried out in the presence of a catalyst.

   For this purpose, it is preferred that the reaction temperature varies between
 EMI15.7
 50 and 150 0 approximately and that the gauge pressure is between 1, 5 and 70 kg / cm. The duration of the reaction can vary between 1 and 30 minutes approximately. A catalyst ''
 EMI15.8
 suitable for use in the reaction may include any of the so-called reduction catalysts, such as compounds of nickel, cobalt, palladium and. iron.

   The preferred catalyst is a nickel compound which reacts with the trialkyl aluminum compound. ;
 EMI15.9
 Particular nickel-based catalysts include

 <Desc / Clms Page number 16>

 
 EMI16.1
 metallic nickel finely divided nickel from,., rf ..,.,, Raney, nickel acetyl econate, naphthenate deze
 EMI16.2
 nickel, etc.

   We can however vary in a
 EMI16.3
 The amount of catalyst used in the reaction is very large, "and it is usually 0TOOI at 0.1 -Yf = based on the weight of the fixing product. -y 7 =. ' In the displacement reaction, one acts on the amount of mono-olefin or low molecular weight alkylene used to achieve a total replacement of the alkyl substituents of the high molecular weight aluminum alkyl. consequently operate with a stoichiometric quantity of mono-ol6fine at low weight ¯,, ¯ ,:

  However, it is preferred to use a stoichiometric excess of about 200-2000 mole percent / ± g of the low molecular weight monoolefin per mole of '. fixation product in the case of thermal displacement and about 1 100 mole percent in the case of "catalytic displacement.,;," The displacement product described above is. It is brought into contact with a II complex so that the trialkyl minimum which is found reacts to form the 2sl complex. The resulting reaction mixture is composed. o6 of two phases, the upper phase containing practically all the alplia-olefins and the lower phase,
 EMI16.4
 comprising the complex product, of which the complex 2; 1 and
 EMI16.5
 some alpha-olefins.

   To treat the alpha-ol6f.nes., W with the 1: 1 complex, it is preferred to use an excess of the lil complex in addition to the stoichiometric amount n6 ...: .- necessary to react with all of the trîw aluminum.
 EMI16.6
 alkyl that is found in the displacement product. We
 EMI16.7
 in general uses a molar excess of about 5 to 10 eo '. ",

 <Desc / Clms Page number 17>

 in the processing of the displacement product.
 EMI17.1
 



  The complex product containing the 2: 1 complex can be contaminated with alpha-016tin. This contamination can be substantially removed by treating the complex product with a paraffinic hydrocarbon. Hydro-
 EMI17.2
 Papuffin carbide can have from about 5 to 12 carbon atoms. As specific examples of paraffinic hydrocarbons there are pontane, hexane,
 EMI17.3
 19octanct nonane, etc. 0.1 to 2.0 volumes of paraffinic hydrocarbon per unit volume of the complex product is used for washing. In general, the product
 EMI17.4
 The complex may contain as an impurity from about 2 to 5 alpha-ol4finej3, before washing with the panaffinic hydrocarbon.

   Washing can be carried out at a temperature of about 5 to 1 won. The pressure under which the washing is carried out may be lower, dirty or Duperiouro than that of the atmosphere, provided that the products remain liquid during the washing and that there is noticeably no decomposition of the product. complex.



   The complex product containing; the 2: 1 complex is subjected to heat treatment in the presence of an extraction solvent. We can maintain the temperature
 EMI17.5
 ture of the decomposition reaction between 100 to 20V C ', approximately, and more commonly between 150 and 1750C approximately.



  The pressure under which the decomposition of the
 EMI17.6
 2: 1 complex can vary to a great extent within the scope of the present invention. To this end, the preasion can be lower, equal to or higher than that of the atmosphere; however, it is usually roughly equal to atmospheric pressure.

   As we have ...

 <Desc / Clms Page number 18>

 
 EMI18.1
 As indicated above, one of the advantages of the control process of the present invention is that it can be applied at atmospheric pressure or at higher Prussian, thus eliminating the technique.
 EMI18.2
 This involves maintaining a vacuum in the decomposition sound system, The duration of residence of the complex s 1 in the decomposition zone this from 1 to 60 minutes approximately, and more usually from 5 to 15 minutes approximately, The solvent for extraction accelerates the decomposition of
 EMI18.3
 complex 2: 1 in lily and trialkyl aluminum complex.

   The amount of the extraction solvent in the extraction zone can be varied widely. In general, about 1 to 40 volumes of extraction solvent are used per unit volume of complex product; however, approximately 2 to 10 volumes of extraction solvent are more commonly used per unit volume of complex product.
 EMI18.4
 Parrffin3quo hydrocarbon to be used as an extraction solvent in the decomposition reaction of complex 2;

  1 has a boiling point which is higher than the temperature at which the decomposition reaction occurs. The extraction takes place in the liquid phase, and the trialkyl aluminum comes into solution with the extraction solvent, while the resulting complex 11 is preferably soluble in the 2: 1 complex or formed.
 EMI18.5
 an insoluble phase. Particular examples of hyciro paralinic carbides which can be used as an extraction solvent are nonai and cyclohexane, decane, dodecane, tetrad4can and met, ylayo.o. pentane, methylcyclohexane, hexadocane, etc.

   Water, many types of compounds can be used as solvents

 <Desc / Clms Page number 19>

 
 EMI19.1
 d extraction and they include for example hdro, -; . unsaturated carbides, such as nonene, decene, oo * '. tene, oyolohexene and similar monoolefin acs ¯, ¯¯ ,. f '. i T generally corresponding to the nyarocurouroo ''. * I '' paraffinics that can be used. In addition, the unsaturated hydrocarbons serving as solvents include., Diolefinic hydrocarbons such as 7, haxad3.enet, heptadiene, iloctadiene, etc. Although many saturated and unsaturated hydrocarbons with a suitable boiling point can be used as extraction solvents, generally speaking these solvents contain 4 with about 20 carbon atoms and more, 7¯.t ..,.

    ,. commonly from $ to about 20 carbon atoms. ) j..¯f "We choose the extraction solvent based on it.
 EMI19.2
 .1 ,, ¯. He
 EMI19.3
 on the fact that it is soluble with the trialkyl aluminum which is formed due to the decomposition of the complex, .... ",. 2: 1. It is preferred to use an extraction solvent which bzz
 EMI19.4
 
 EMI19.5
 can be used in the binding reaction. A cat; '- indeed paraffinitlues hydrocarbons are particularly well suited, and in particular los fractions. .., ij¯; çi., boiling oil in the range of naphtha and pu- z
 EMI19.6
 kerosene fractions, petroleum and petroleum fractions,
 EMI19.7
 lampant have an initial ASTM distillation point of, ¯ ".



  120 to 140 C and an end point of about 200 to 25,000 ..; The raffinate from the extraction process, which contains the trialkylated aluminum and the extractive solvent, can be passed in whole or in part to the fixation reaction. In some cases, some of the dextraction solvent can be separated from the raffinate before entering. , ra ,, in the fixing reactor. ,.: / i /] '' 1, "., Laboratory tests were carried out in the;: .... i:

 <Desc / Clms Page number 20>

 
 EMI20.1
 aim to establish the value of α7, iphatiue hydrocarbons as extraction solvents to regenerate complexes. ,. f 1, from complexes 2; 1. '., <.. ,, u:', kv / 'Yiyrry / # k EXAMPLE 1,' i; ,;

   Is introduced into a round bottom flask, free from humidity and air, 31 G. of a complex 211 of tri4thy.a aluminum and tetramethyl ammonium chloride, in which the ratio of aluminum to chloride is bzz 1.94. To the complex product was added 10 ml (the n-od40an and the mixture warmed to 15,000. The mixture was stirred and samples were periodically pooled at 15 minute intervals.

   After taking -. ,, zaza from each 4-sample, 5 ml of. '; fresh dodecane, After 45 minutes, it was found that 996% of the aluminum triethyl had been extracted ¯, i '= /, EXAMPLE 24?': 4 The test of Example 1 was repeated with this difference that the extraction temperature is 19OÇYI, l. to liou of 15000 and also that the extraction solvent '. o. '' is h'-tetradecanCt After 45 minutes, we find;

   that 17% of the triethyl aluminum was extracted from the 2: 1 complex product. bzz
 EMI20.2
 In order to give a more understanding -
 EMI20.3
 perfect do of the present invention, we will zeporter-to the attached Fleure 1, which represents a diagrammatic diagram: F tick of a device for the implementation of the present invention.
 EMI20.4
 A displacement product in which one initially uses a fixing product whose value of
 EMI20.5
 '1 ..,

 <Desc / Clms Page number 21>

 
 EMI21.1
 * m * is 4.0 and containing about 20% aluminum, triethyl, 20% kerosene; as solvent and 60% of alpha-016tinos comprising between 4 and 26 carbon atoms, is charged into a complexation vessel 5 through line z at a rate of 63.4 kg / hour.

   A lil complex of triethyl aluminum and t6-tramethyl ammonium chloride is loaded into the complexation vessel 5 μh leads it to 7 at a rate of 2791 kg / hour. The displacement product and the 1: 1 complex are introduced into the complexation vessel 5 at approximately its middle part, so that the displacement product, substantially free of trithyl aluminum, can exit.
 EMI21.2
 to the sonnet through line 8, and that the insoluble phase,> 'of the complex product exits through the bottom of the complexing vessel 5 through line 9.

   The a2pha-ol.t, na phase exits at the top of the complexation vessel 5 rez reason, -from z, 5 kg / hour, while the complex product exits ,, 1 "; '" through the bottom of the vessel 5à rate of 61.6 kg / hour. "'.,
 EMI21.3
 The temperature in the plotting vessel is maintained at about 60 ° C. under a pressure which is approximately that of the atmosphere. The residence time of the displacement product is approximately 15 minutes, before exiting, as the head product through line 8.



   The complex product which exits from the bottom of the complexation regimen 5 enters through the upper part of a washing tower 10. A washing solvent such as n-hexane is introduced to the lower part of the washing tower. washing 10 through line 11, at a rate of 20.4 kg / hour.



   The washing solvent circulates from bottom to top in countercurrent contact with the complex product and it extracts from the latter all the alpha-olefins and all the petroleum.

 <Desc / Clms Page number 22>

 
 EMI22.1
 The complex product which it contains, on entering the washing tower, contains about% al-ph-a.cfinea and kerosene which are easily removed therefrom by the washing solvent. The washing solvent enriched in alphu-olefin3 and in kerosene leaves the solamet of the washing tower zij via line 12, while the complex pmlult d3barraaa5 of a.pha-oJ.3finos and,
 EMI22.2
 do lump oil comes out of the bottom of the washing tower by
 EMI22.3
 conduit 14.

   The enriched wash solvent stream flowing through line 12 contains about 10% of al. j phu-ol6f, nes and kerosene, which have been extracted '
 EMI22.4
 of the complex product. In the washing tower we maintain
 EMI22.5
 temperature at about 60 ° C under a pressure which is approximately atmospheric, the washed complex product circulating in the drain 14 is introduced into the upper part of an extraction vessel 15 through a conduit 16. A solvent '' -. Extraction such as hexadecune is introduced into the lower part of the extraction vessel 15 through a conduit 17, at a rate of 13G kp / hour. The complex product ',
 EMI22.6
 flows from top to bottom in countercurrent contact with) 1;
 EMI22.7
 the extraction solvent and triethyl aluminum is thereby extracted from the complex product.

   The extraction solvent enriched in triethyl aluminum comes out of the. The upper part of the container 15 through line 18 at a rate of 146 khoure. The triethyl alumina complex product has been removed from the bottom of the container 15 through line 19 at the rate of 32, 6 kg / hour The complex product regdn6r6 contains approximately 68 - b of 1: 1 complex In certain operations, it may be advantageous to recycle part of the complex product exiting the.

 <Desc / Clms Page number 23>

 bottom of the extraction vessel via a conduit 20 provided with a valve.

   The recycled complex product flowing through line 20 combines with the fresh complex product flowing in line 14, and the combined stream flows through line 16 to the upper part of extraction vessel 15. Can, in regeneration or extraction treatment, operate with a recycling ratio, measured in volumes of complex product recycled per volume of fresh complex product introduced into the extraction vessel, from 0.2 to 10.0:

  1. In the container 15, the temperature is maintained at about 160 ° C. and under a pressure which is approximately that of the atmosphere. The residence time of the complex product in the extraction vessel is approximately 10 minutes.



   The complex regeneration product from line 19 flows into line 7 and is consequently recycled to complexation vessel 5.



   The overhead products exiting the complexing vessel 5 and the washing tower 10, which circulate in the conduits 8 and 12 respectively, meet and circulate in the conduit 22 before entering a fractionation apparatus 23. In the Fractionation apparatus 23, which operates in a conventional manner, the alpha-olefins, the fixing solvent used in the fixing reaction and the washing solvent are separated from each other. The washing solvent stream
24 is then recycled to the washing tower 10, with or without make-up solvent, and the fixing solvent 25 is reused in the fixing reactor (not shown) The olefins exit at 26.



   We generally hit the others

 <Desc / Clms Page number 24>

 
 EMI24.1
 of the invention -by a prooàd6 characterized by ta11, '. /, which separates low molecular weight br1al3yl aluminum from various products, comprising; (1) a pr () of the 11th '; A.



  , 1 /: displacement P1 contains alpha-olefins, (2) to "1'µbl) A '.. non-olefinic hydrocarbons and (3) a dia3: U.' ,: dialkylated alcohol, by contacting the product with
 EMI24.2
 an aluminum trialkyl complexing agent. low weight, '(.



  >. <molecular and then separating from oo produces the "<" 1;], i; (.. j ;.



  ; ') -: ": I .complex containing trialkyl aluminum. The 13.5ent', oom;! T., .Plexant which is used is a compound having for
 EMI24.3
 formula R MX or a complex of MX and an aluminum i ;. trialkyl, low molecular weight, in the molal ratio
 EMI24.4
 re of 1: 1, where R is a radical, alkyl, M is nitrogen, arsenic, phosphorus, sulfur,
 EMI24.5
 selenium or tellurium; X is halogen and n is equal to "* -r d 3 or 4, depending on the element M considered.

   The preferred complexing asenbs are ammonium heJ.oa; 6nides. '. ] j, (-, f.il. tetraalkyl. 1- .. i ', l tetraalkyl'
In another 'aspect' of the invention, a product
 EMI24.6
 displacement comprising alpha-olefins containing. alpha-olefins containing an average of 4 to 30 ato-
 EMI24.7
 mes of carbon mixed with a trialkyl aluminum ', which contains alkyl radicals having an average of 2
 EMI24.8
 with about 5 carbon atoms, but on average less F 'r; j:

   of carbon atoms that there are in the alPha.-olefinl3i: i is treated with a complex of a halide of P ammonium '';, p tetraalkyl in which the alkyl radicals contain, on average from 1 to 5 approximately carbon atoms and a trialkyl aluminum in which the alkyl radicals contain an average of 2 to 5 carbon atoms, the ratio. molar from second to first being 1: 1, and we produce)

 <Desc / Clms Page number 25>

 thus a complex in which the predicted molar ratio
 EMI25.1
 ast dv 211, Dansa an autro aspect? still 1'invention, we Bouaet lo complex 211 to a heat treatment manibce he can étro d; canpaar on aluminima tri-alkyl and! a complex 1 s 1.

   The lil ost oneuite complex .r4uttlia4 for the treatment of the displacement product ooaNû on the oxpoois above,; In yet another aspect of the invention, the 2: 1 complex which is slpaned from the alpha-ol4fins can be used - form as an impurity a small quantity of alpha-old "fines. This impurity can be easily removed from the 2s complex 1 by treating it with a para4lfinic hydrocarbon containing approximately 4 to 30 carbon atoms;

   the alpha-o16fmes are therefore dissolved in lava hydrocarbon, leaving the complex 2: 1 component free of impurities. In other aspects of this invention, the complexing agents described above are used to
 EMI25.2
 . the separation of solvent hydrocarbons, particularly from saturated hydrocarbons, from low molecular weight trialkyl aluminum and in the separation of dialkylated aluminum alcohols from low molecular weight trialkylated aluminum.



   As has been pointed out above, coats, invention aims, in its most general aspect, to
 EMI25.3
 calves complex of alyl-aHsonium chlorides & low weight. molecular and low molecular weight trialuminum compounds. We can define these complexes by the following formula

 <Desc / Clms Page number 26>

 
 EMI26.1
 a (R, Al) .R'4NOl in which R have a recoil ul) Qrle ront'orJ.1ant dice 2 to 5 shames of oarbbne, 9 ast 6al to 1 or 2;

   at is an allzyl radical comprising from 1 to µ carbon terminals and R + Re does not disperse 6 atoms of oarbono, As a particular example of complexes beyond the scope of the vetion there is the complex of 2 aluminum triethyl and
 EMI26.2
 tGtram4tyl ammonium chloride, tripontyl aluminum and tetrwn4thyl ammonium chloride, triethyl aluminum and tetrapropyl ammonium chloride and 2 aluminum tripropyl and tetraethyl ammonium chloride 2 aluminum triisobutyl ot of am- chloride
 EMI26.3
 monium t (; trù.l1lôtb; ylc, aluminum tributyl and ammonium chloride tetraethylo, aluminum 2 tricthyl and, ammonium chloride tetrapropyl, aluminum triethyl and chloride a:

  Ammonium tetranthyl, and aluminum triisobutyl and ammonium t3tram3-thyl chloride. Although any of the complexes encompassed in the generic formula are within the scope of the present invention, the preferred complexes are those in
 EMI26.4
 which enter tetnanethyl ammonium chloride and alkyl aluminum compounds having no more than 4 carbon atoms.
 EMI26.5
 



  The complexes of this invention are oaracteri-J. its by the fact that they are practically insoluble in: ',:
 EMI26.6
 aliphetic compounds, that is to say in pardttinic and o16tinic compounds. For example, the 1: 1 and 2: 1 plexes of triethyl aluminum and methyl ethyl ammonium chloride. have a solubility less than, - ..



  1 part of complex per 100 parts of solvent. These

 <Desc / Clms Page number 27>

 complexes are also characterized by their high thermal stability. for example, the 2: 1 complex of alu-minima triethyl and tetramethyl ammonium chloride
 EMI27.1
 begins to decompose at 140 C and under pressure do, '.



   20 mm. These complexes can exist in the solid or liquid state, depending on their composition and depending on the temperature.
 EMI27.2
 Room temperature * The 1: 1 complex of triethyl aluminum and tetramethyl ammonium chloride has a melting point of about 4700. On the other hand, the 2sl complex has [µ a melting point of approximately 90 C.

   The conditions gene-. preparation lines and decomposition of complexes, - ';;' 2: 1 are set out in the detailed discussion below) ', which is oriented in the direction of the application of the above complexes and other complexes in the process.
 EMI27.3
 This invention:: '' ¯ of this invention ..-; - '. '' '' j <; 'j / ;; The complexing agents which are made a9pel ', i <± to implement the process of this 3nvention are' .; generally defined by the formula RnMx, wherein R is an alkyl radical; M is arsenic, phosphorus, sulfur, selenium or tellurium; X
 EMI27.4
 is halogen; and n is equal to j or to 4, depending on ltélé. ment M considered.

   The radicals are preferably used
 EMI27.5
 low molecular weight alkyl, i.e. those which
 EMI27.6
 contain 1 to 5 carbon atoms. As the length of the alkyl chain increases, the solubility of the complex in hydrocarbons also increases, so that the degree of separation decreases. Among the elements represented by M, and of which all are metalloids, the preferred element is nitrogen, however any other metalloid among those listed is also effective as a complexing agent.
 EMI27.7
 ¯ ,,,.; Mi "." 'M w 1 ..i

 <Desc / Clms Page number 28>

 
 EMI28.1
 implements the process of this invention.

   We can use!?; any of the halogens, however it is preferred
 EMI28.2
 chlorides. ,, ta ;; = ;:
In order to more clearly and usefully describe the invention, the following discussion will deal with
 EMI28.3
 tetraalkyl ammonium halides; However, it is within the scope of this invention to use any other metallotalethyl halide corresponding to the formula given above.

   It also goes without saying that the nitrogen can be replaced by each of the other 0 metalloids in the specific examples of the agents, - complexing agents and of the complexes described below,
The displacement product containing alpha-
 EMI28.4
 olefins is treated with a ttra- ammonium halide. y 6; alkyl or with a complex of tetraalkyl ammonium halide and trialkyl aluminum. When using the.
 EMI28.5
 -. '' '' * complex, it is formed with a trialkyl aluminum in which the alkyl radicals contain on average from 2 to
About 5 carbon atoms, The sum of the average number of alkyl radicals of the two compounds is preferably ,,,, - ,, -
 EMI28.6
 not greater than 6.

   For the purposes of this description, O.! . ,,; J, 6,.



  :> it ". the terms - the average alkyl radical" are taken in the sense of ¯; .¯, of the average of all the alkyl radicals which are found ,. present in the particular composa in questions
The reaction between trialkyl aluminum and tetraalkyl ammonium ha logenide takes place in a molar ratio of 1: 1 and 2: 1. This reaction can take place at a temperature of approximately 50 to 150 ° C., and more commonly between approximately 50 and 10 ° C. The pressure under which the reaction takes place can be less, equal or greater.
 EMI28.7
 lower than that of the atmosphere, & l general however; , '

 <Desc / Clms Page number 29>

 
 EMI29.1
 , C.i, the reaction takes place at atmospheric pressure. The 'bzz formation of complexes does this: in a lapse of tsaps' re ,,.



  Bonnablemont runs; therefore they can force themselves in 0.25 F. 30 minutes and more commonly in about 0.5 to 10 minutes. As particular examples of ammonium tutraalkyl halides which may be employed in the preparation of the complex, there is aonium ttrwethyl chloride 3. tetramethyl ammonium iodide, tetraethyl ammonium fluoride, t4trabutyl ammonium bromide, tetraethyl ammonium chloride, t3trabutyl ammonium fluoride, amzaon3ura r iodide. tetrapropyl, ammonium tetrapropyl chloride i etc,. Aluminum trialkyl which r4ogit with 1 halo3turo of had '"' '.. monium tatraalkylo is for example aluminum tridthylol
 EMI29.2
 Aluminum tripropyl, aluminum tributyl, etc.

   The*
 EMI29.3
 Particular examples of the complexed include the 2-aluminum tri6thyl-ammonium chloride tetra- .a methyl 2-aluminum triethyl-ioduro plex compound of 2-aluminum triethyl-ioduro d 1 a = onium t- .. tramrithyl # of 2-aluminum trirmyl-fluo 8lvaoniuw. ,, <tetrauthyl, 2-aluminum triisobutyl-ammonius tetra-butyl, 2-aluminum tributyl-elum.tium chloride ,, ir tetrabutyl, 4-aluninium tripropyl-fluoride-ammonium tetrabutyl. , ij .. 'nium tetramathylet of 2-aluminum triinopropyl-, tluorutb
 EMI29.4
 
 EMI29.5
 d 1 a = onium ttrapropyl, from 2-aluminum triethyl e-iod uro from ammonium ttrapropyl, from 2-aluminum triisopropyl- "., 'ch1orSa> e dla = oni, 2m, t.trapropylae from 2-aluminum tridthy- 'tW,., tetrainobutyl amnoniun chloride, 2-aluminum triie> propylo-a = oni = tetramthyl and 2 = alm4r4un;', 1 ',' j, ¯ / ", é, ii;] tripropyl - Amnonium bromide betraathy18.

   Lee examples
 EMI29.6
 particulars of compounds of other metalloids, que'lion,
 EMI29.7
 . can use, correspond to composta expoa6s c3 - ': ât,' s 5.7%

 <Desc / Clms Page number 30>

 above. Of course, it goes without saying that the examples
 EMI30.1
 Particulars include 4Galoment Complexes 181, the 2: 1 complex easily decomposes by subjecting it to the action of heat under pressure
 EMI30.2
 lower than atmospheric pressure.

   In the decomposition reaction, the 2: 1 complex is transformed into coa-p3.axa'1s1, with release of one mole of aluminum. triethyl for every mol of complex that is decomposed. The ltl complex does not easily decompose and requires temperature and pressure conditions which result in pyrolysis of the trialkylated aluminum.

   Since it is desirable to reuse the halo-
 EMI30.3
 t4trual ammonium gnide] Vledin the process and as this product is reusable only in the form of the complex.
 EMI30.4
 11, the process is usually carried out by forming; initially the lil complex, then then operating ,, =. / ",, with this complex rather than with the ammonium haloconide; tt-traalkyl, Consequently, the description and the exposes' above are particularly oriented in the sense of., - the use of the 1: 1 complex; however it goes without saying that the ammonium halide t4traalk can also be used in the various embodiments of the 'invention..



   The 1: 1 complex described above is reacted with the trialkylated aluminum which exists in the displacement product. Aluminum trialkyl contains radicals? ' alkyl having an average of about 2 carbon atoms
 EMI30.5
 ron.

   The trialkyl aluminima and the ,,. 'Can be reacted. complex 1% 1 t a temperature of about 50 to 1500, and) more commonly between about 5U and 10C, The reaction pressure can vary to a great extent, such

 <Desc / Clms Page number 31>

 so that it may be less, equal or greater than atmospheric pressure. The reaction time may be from about 0.25 to 30 minutes and more usually from about 0.5 to 10 minutes.

   The relative proportions of trialkyl aluminum and the 1: 1 complex can vary considerably in the process of the present invention. The 1: 1 complex can be used in a stoichiometric proportion to react with all of the aluminum. trialyl, or it can be used in excess so that the 1: 1 complex is found in the product together with the 2: 1 complex. For the purposes of the present invention, it is preferred to operate with a 1: 1 excess of complex, so as to obtain the advantage of mass action. Usually, about 1.05 to 1.20 moles of complex 1.1 are used for each mole of trialkyl aluminum present in the displacement product.



   The treatment product of the displacement product containing uncombined trialkylated aluminum. with the 1: 1 complex occurs as two phases. The upper phase consists mainly of hydrocarbons, with or without a trialkyl aluminum louse and / or other complexes, while the lower phase is mainly constituted by the complex, with or without, of small quantities. hydrocarbon, catalyst. travel, etc.

   In the event that the complex phase contains an impurity, the latter can be eliminated by treating with a paraffinic hydrocarbon. For this purpose, the paraffinic hydrocarbon may contain from 5 to,
12 or more carbon atoms. There is interest in that. paraffinic hydrocarbon contains fewer atoms of

 <Desc / Clms Page number 32>

 
 EMI32.1
 carbonaceous than alpha-o16tin. In this way, the hydro ''.



  Paraffinic carbide can easily be separated from alpba-ololine by distillation. We use a, 4 '.: # J. paraffinic hydrocarbon which contains from 2 to 6 atoms., j]: J; of carbon about less than. ' a2pha-al; f3.ne that 110.11, recovered in the process. As specific examples of paraffinic hydrocarbons there are pentane, lthena7, ne, heptane, octane, nonane, etc. The quantity of paraffinic hydrocarbons used is from 01 to
 EMI32.2
 About 10.0 parts and more feed the Ot2 to about 1.0% by volume, per unit volume of the complex. The complex may contain from 1 to 5% by weight approximately, and more usually from 2 to 4% by weight approximately.
 EMI32.3
 ron of alpha-olufin present as an impurity.

   The treatment of the M61ang6 complex of impurotô with paraffinic hydrochloric acid can be carried out at room temperature or at a temperature of about 50 to 200 C, and
 EMI32.4
 more commonly about 50 to 10,000, depending on the hydrocarbon used.
 EMI32.5
 ment may be less than, equal to or greater than the ''.; '. atmospheric pressure. bzz The complex product that contains the complex
 EMI32.6
   2: 1 is subjected to heat treatment for the '. transform a complex 1; 1 and into trialkyl aluminum. The pyrolysis of the complex can be carried out at a temperature between 110 and 225 C and preferably between
 EMI32.7
 130 and 19000.

   The pyrolysis treatment is carried out at a pressure lower than the atmospheric pressure which, for the purposes of this invention, may be about 5 to 30 mm of mercury.



   You can also use the complex!: For?

 <Desc / Clms Page number 33>

 separating an aluminum-trialkyl in which the radical. The middle alkyl contains 1 to 5 carbon atoms derived from the non-lfinic hydrocarbon, for example, from the solvent or diluent used in the binding reaction.

   The hydrocarbon used as the solvent in the fixing reaction is present during the teaps where the displacement reaction is carried out. The alpha-olefins thus produced are separated from the solvent hydrocarbon, and from the trialkylated aluminum. low molecular weight by conventional methods, such as, for example, by distillation * The remaining low molecular weight hydrocarbon and trialkyl aluminum are then treated with the 1: 1 complex described above to produce a complex product comprising the 2: 1 complex When the 2: 1 complex is formed, two phases appear, one of the solvent hydrocarbon and the other of the complex product.



   The complex product is then separated from the hydrocarbon solvent and pyrolyzed to regenerate the 1: 1 complex in the same manner as described above, so that it can be reused to process still other mixtures. of hydrocarbon and trialkyl aluminum.



   Although the separation process is generally applicable to non-olefinic hydrocarbons, it is preferably used in the separation of saturated hydrocarbons from trialkyl aluminum. are less frequently used as diluents or as solvents and these products are also more difficult to separate, since they can be to some extent soluble with the 1: 1 and 2: 1 complexes.

 <Desc / Clms Page number 34>

 



   The complex product containing the 2: 1 complex can optionally be treated with a paraffinic hydrocarbon less miscible with the complex product but more miscible with the non-olefinic hydrocarbon which contaminates it. than with the complex product: The paraffinic hydrocarbon which is used for washing may contain preferably from 5 to 10 carbon atoms approximately, and the hydrocarbon which serves as the fixing solvent, comprises more of carbon atoms or has a higher boiling point than the washing agent.

   The conditions for the treatment of the mixture of non-olefinic hydrocarbon and low molecular weight aluminum trialkyl 4 with the complex 1; 1 are the same as those described above for the treatment of the mixture of alpha-olefin and aluminum. trialkyl. Likewise, the washing of the complex product with a paraffinic hydrocarbon can be carried out under the same conditions as those described above in the case of washing of the complex product which results from the treatment of the mixture of alpha-olefins and trialkyl aluminum.



   The trialkyl aluminum which was used in. fixation and displacement reactions and who is. obtained is easily partially oxidized in the presence of oxygen, for example in air. The result is that the fixation and displacement products are very often contaminated with small amounts of dialkyl aluminum alcoholate. It is also within the scope of this invention to separate these alcoholates from the aluminum trialkyl compounds of low molecular weight by using. Complexing agents $.



   Olefins can also be made by using

 <Desc / Clms Page number 35>

 skip an aluminum dialkyl alcoholate in the binding reaction, in place of a trialkyl aluminum.



   -In a reaction of this kind, the attachment is to the two alkyl radicals, the olefins being displa-. cées in the displacement reaction.



   Low molecular weight trialkyl aluminum can be present in any reaction mixture described above and can be effectively separated therefrom by the process of this invention.



   The dialkylated aluminum alcoholate to be separated usually has an average of about 2 to 5 carbon atoms for each alkyl group, and the alcohol group contains about 2 to 5 carbon atoms. The mixture can be treated with a 1: 1 complex of the type described above to form a product consisting of two phases, i.e. an upper phase of mono-aloolate and a lower phase. of a complex product containing the 2: 1 complex.

   The complex product can optionally be washed and pyrolyzed in the same manner as that described above in the case of the recovery of trialkyl aluminum and its separation from either the alpha-olefin or the non-alpha-olefin. -olefinic.



     In the case where a displacement catalyst is used for the production of alpha-olefins in the manner described above, there is no advantage in subjecting the displacement product to heat, since a reaction - reverse tion has a clear tendency to occur.

   The reverse reaction consists of a mutual action of the alpha-olefins and the low molecular weight aluminum trialkyl to give the high molecular weight fixation product. Thanks to the present invention, the reaction

 <Desc / Clms Page number 36>

 reverse is deleted because the displacement product is treated with the 1: 1 complex to remove the low molecular weight trialkyl aluminum. The alpha-olefin phase containing the catalyst can then be subjected to the action of heat, without fear of the reverse reaction occurring.

   Nickel and the nickel-containing catalysts described above are particularly effective in promoting the reverse reaction; it follows that the present invention is articu larly applicable to a catalytic system of this Son-- re
The following examples are presented to illustrate the present invention.



   EXAMPLE One added dropwise over 5 minutes, 16.1 g. aluminum triethyl to a mixture of 15 g. of dodecene and 16.2 g of anhydrous tetramethyl ammonium chloride. The temperature of the reaction mixture rises to 59 C and on cooling the whole mass solidifies. ¯ The reaction mixture is slowly heated again to 100 C and two liquid phases are then formed. The temperature of the reaction mixture is maintained at this high level for two hours to ensure that the complex reaction is complete. The reaction mixture is then cooled slowly, whereupon the lower phase solidifies at the temperature of.
Approx. 47 C.

   A lower phase sample was analyzed and found to be substantially free of minium and chloride. The lower phase contains the 1: 1 complex of triethyl aluminum and halide

 <Desc / Clms Page number 37>

 tetramethyl ammonium
The reaction mixture is warmed to 70 ° C., then 17.0 g is added. aluminum triethyl. The purpose of this part of the assay is to prepare a 2: 1 complex of the two reagents.

   The temperature of the reaction mixture is maintained at 70 ° C. The reaction mixture solidifies when the first drop of triethyl aluminum is added and the recto solid is laid, while the triethyl aluminum is added. This solid product mows between 85 and 95 C At 100 C, there are two liquid phanes. A sample of the upper phase contains 0.63% by weight aluminum and less than 0.1% chlorine. The lower phase contained .795 wt. Aluminum and 5.88 wt.% Chlorine.

   The molar ratio of aluminum to chlorine in the lower phase is 1.97
Another test is carried out to determine how well the 2: 1 complex can be pyrolyzed to produce the 1: 1 complex and the trialkyl aluminum compound EXAMPLE 4
In a 125 mg round bottom flask with a thermowell and a vacuum distillation head separated by a 20 cm glass column, is introduced
50 g of a complex, 2: 1 of triethyl aluminum and tetramethyl ammonium chloride in which the molar ratio of aluminum to chlorine is 1.99 'There is no packing in the glass column.

   The complex is heated to a temperature of 140 under the pressure of
20 mm before triethyl aluminum begins to

 <Desc / Clms Page number 38>

 boil at reflux. We slowly turned up the heat
 EMI38.1
 until the complex reached the temperature of 150 C and the pressure was lowered to 1 mm. After 5 hours, very little product was distilled from the complex. A total of 14.1 g is collected. do passing product
 EMI38.2
 in all. in analysis of the product do ttto ot we find that it 'ant'ba 21.7% ulin1um and less than 0.1% chlorine The overhead product is tPiethylo aluminum and it forms in a round of ? 2; c.



   In order to determine the amount of complex that would be retained in the hydrocarbon phase in use.
 EMI38.3
 Combating various types of haluren in the complex, the test before EXAMPLE 5 was added 21.9 g. do chloride Tetraethyl anmonium,, c, 5 g. ttr., 3tkyla and z Fo of tetrantethyl anonium iodide, each in three separate flasks. We add in each of the three
 EMI38.4
 79 S flasks, of a solution of $ 2.5% by weight of triethyl aluminum in n'-dod4cene <Each of said flasks is stirred for 30 minutes at a temperature between-
 EMI38.5
 be 50 and 6000.

   We separate from. each balloon phase ron.,:, forming dodecene. Aluminum is assayed in dodecene in order to determine how much has been retained there.



  In the table below the amount of aluminum present in the halogen complex serves as the basis and all other aluminum dosages are reported as ratios relative to the number serving as the basis.

 <Desc / Clms Page number 39>

 
 EMI39.1
 
<tb>



  * <SEP> Dosage <SEP> of <SEP> aluminum <SEP>. <SEP>
<tb>
<tb>
<tb>
<tb>



  Complex. <SEP> in <SEP> the <SEP> dodcene
<tb>
<tb>
<tb>
<tb>
<tb> Complex <SEP> chloride <SEP> 1.0
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> bromide <SEP> 1.6 complex
<tb>
<tb>
<tb>
<tb> Complex <SEP> iodide <SEP> 5.2
<tb>
   * The dosage of aluminum is expressed in relation to and related to the dosage of chloride. It emerges from these dosages of the aluminum contained in the hydrocarbon phase that it is the chloride complex which gives the best results. The worst results are obtained with the iodide complex.



   In the following test, a nickel-containing displacement product is subjected to the practice of the present invention to determine if any adverse effect can be expected.



   EXAMPLE 6 "" In the case of the displacement catalyst, nickel naphthenate is activated with the fixing product and then inhibited with 15 parts of propargyl alcohol per part of nickel. The displacement product is treated with an amount of nickel solution such as to give a final concentration of 20 millionths (ppm) of nickel. 1.040 g is used in this test. of the product .. displacement.

   The displacement product is formed from an attachment product in which the value of "m" is 3.7. The displacement product containing nickel is maintained at 15 ° C. and then 515 g of a 1: 1 complex of triethyl aluminum and tetramethyl ammonium chloride The temperature of the mixture rises

 <Desc / Clms Page number 40>

 
 EMI40.1
 5000 and stirred at this temperature for 10 mi-1 ''. nutes. The olefin layer is analyzed at various times to determine the extent to which the reverse displacement has occurred. The following table gives the z / "¯.



   . results of this work. ruz '
 EMI40.2
 
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 EMI40.3
 ment in- Alpha Oleins Oleins
 EMI40.4
 
<tb> verse <SEP> Internal <SEP> olefins attached <SEP>
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 EMI40.5
 used 92.6 1.7 5 ,? 2. Layer of olefins 1,? 5,? after 10 minutes. - "...; '-; at 5C C in the presence,': 1 'ofAlTE / CATM 0.5 -92.6 2.5' 4.9 ¯) .¯.



  µ, Olefin layer,: .. ,, '. , "f 1.t" 'h,> ...



  "coming from 2, after, \ .., ...", '-, 1,>' ... r 3 days at tempe-, ar: days temp- ':: / (":' .: erased ambient '.., '92, 0 .2.6 "5.4; ..e' 4. Olefin layer '>', / Jlli j 'coming from 2, after';, -" t yt ;.



  11 days at temperature, ''. 'g> ;,' ambient temperature 91 t 7 .. tO j5.0 '; /) ¯)) 5. Olefinoa layer - 'l v, v Wa 1 i1v. 'coming from 2, after. 1 Ô ") lÙ 'temp- days." ... 1 l' \. t .., gold.



  14 days the tempe-. f. 1 j ',, 1) a [;)', ambient erasure - '- "91,6. 2,8' 5, ij .µ ') r'; 6. Control sample, ',' '',, ' "'; l * ap: cés ninutos' ....'" '", after 10 minutes'; . '¯ Î' i / 1 (50 C (without ALr'8 / C.ATM) 1.5. 91.7 1. 2,, l, ", 6.0 l": ': i ....



  12NI4 Nuclear Magnetic Resonance., * '-. '' \ '3Í: A.1TE a Aluminum triethyl. -. g, ..
 EMI40.6
 
<tb> CATM <SEP> Tetramethyl <SEP> Aluminum <SEP> Chloride.
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 <Desc / Clms Page number 41>

 



    EXAMPLE 9
In this example, the displacement product forms aluminum triethyl, alpha-olefins and dialkylated aluminum mono-alooolate. One operates with an excess of the 1: 1 complex of triethyl aluminum ot tetramethyl ammonium chloride to ensure complete reaction with all of the aluminum compound which was in the displacement product. After the reaction of formation of the complex, the two phasses thus formed are separated.

   A sample of the olefin layer is subjected to a hydrolysis treatment in order to determine if it contains monc-alcoholate if it does. * As for the hydrolysis product, there is 0.058 mole alcohol in the aqueous layer and 0.045 mole of alcohol in the oletins layer. The total of 0.103 moles of alcohol indicates that the aluminum compound is in the form of dialkylated aluminum monoalcoholate. This test also demonstrates that the complex product has no influence on mono-acloolate EXAMPLE 8
In this test, the layer of complex product resulting from the complexation reaction is washed with normal heptane.

   For this purpose, 1 to 2 parts of normal heptane are used for 9 parts of complex product *
Substantially all of the olefins in the complex product are removed by washing twice with normal heptane.



   EXAMPLE 9 It turns out that the complexes formed in

 <Desc / Clms Page number 42>

 Reaction of tetramethyl ammonium chloride with either triethylaluminum or tributylated aluminum are practically insoluble in the olefins of the displacement product or in decene and in normal heptane.



  However, when tetramethyl ammonium chloride is complexed with trihoxylated aluminum, it is found that. the complex is partially soluble in the same parafinic and olefinic substances
Oven to give a better understanding of the present invention, reference will now be made to the attached FIG. 2.



   In the drawing, the 1: 1 complex of sorted aluminum. thyl and tetramethyl ammonium chloride is recycled to a storage tank 5 through a line 6. Fresh tetramethyl ammonium chloride and aluminum triethyl are introduced separately into the storage tank 5, respectively through the conduits 7 and 8 The 1: 1 complex is evacuated from the storage tank 5 via a conduit 9 at a rate of 81.5 kg per hour. The 1: 1 complex is combined with the displacement product which is supplied through line 10 at the rate of 219.7 kg per hour.



  The combined streams are introduced into a complexing vessel 12 through a supply line 13.



  In complexing vessel 12, the 1: 1 sc] complex combines with the triethyl aluminum present in the displacement product and thereby forms a complex porous phase which is surmounted by an olefin phase and. , ', solvent. The solvent which is used in the binding reaction is kerosene having an ASTM initial boiling point of 195 ° C and an end point of 225 ° C. The complex product continuously exits from the bottom of the vessel.

 <Desc / Clms Page number 43>

 complexation at a rate of 125 kg / hour.

   The hydrocarbon phase leaves continuously through the top of the complexation vessel 12 through a conduit 14 at a rate of
176.2 kg / hour. The phase of hydrocarbons flowing in. the conduit 14 is introduced into a distillation apparatus 16 in which the various products are separated. The products leave the 16% ion distillation apparatus through a 17 'pipe
The complex product which exits the complexing vessel 12 passes through the conduit 18, which is in communication with an olefin extraction vessel 20.



   Normal hoptan is introduced into this container through line 21 at a rate of 62.5 kg / hour. The complex product is contaminated with olefins and solvent which are practically removed by normal heptane. In the olefin extraction vessel 20 two phases are formed, namely the upper hydrocarbon phase and the lower complex phase. The hydrocarbon phase is continuously discharged from the olefin extraction vessel 20 through line 22 at a rate of 65.4 kg / hour.



   The washed complex product exits the extraction vessel 20. tion of olefins through line 23 at a rate of 124 kg / hour. The washed complex product from line 23 is introduced into a pyrolysis vessel 25. In the pyrolysis vessel 25, the temperature is maintained at 175 ° C. and under a pressure of 10 mm. The complex product remains in the pyrolysis vessel 25 for about 2 minutes. ron. The result is that the 2: 1 complex is decomposed into the 1: 1 complex and aluminum triethyl.

   Triethyl aluminum is removed from the pyrolysis zone via line 25 at a rate of 37.6 kg / hour. The complex product

 <Desc / Clms Page number 44>

 remaining, essentially consisting of the 1: 1 complex, exits the pyrolysis vessel 25 through line 6 and is recycled to storage vessel 5, as one '
The regenerated triethyl aluminum which exits the pyrolysis vessel enters the storage vessel at a rate of 81.5 kg / hour.
27, then exits the storage vessel 26a and enters the fixation reactor 28.

   Fresh kerosene as a solvent is fed to the fixing reactor 28 through line 30 to. at a rate of 39 kg / hour In the fixing reactor, the temperature is maintained at
100-120 C approximately and the gauge pressure between 70, and 140 kg / cm2 The residence time of the reaction mixture in the growth reactor is approximately 3 hours. ,
The binding reaction takes place to an extent which gives a Poisson index of 3.7. The binding product exits the binding reactor through a line 31 and is introduced into a displacement reactor 32 at a rate of. 192 kg / hour. Fresh ethylene is introduced into displacement reactor 31 through line.
33 at a rate of 30 kg / hour.

   In the displacement reactor 32, the temperature is maintained at about 110 ° C. and -. the gauge pressure at approximately 35 kg / cm2. The residence time of the reaction mass is about 5 minutes. ron before exiting through conduit 10 and then being mixed with the 1: 1 complex which flows in conduit 9.



   The displacement product leaves the reactor 32 at a rate of 220 kg / hour.



   We can see from the previous example; .that the present invention applies in a unique way to a device in which olejni products

 <Desc / Clms Page number 45>

 ques are obtained by the fixing reaction. The aluminum triethyl which comes out of the base on which the molecule is built is continuously used in the reaction.



   Quite unexpectedly, the same triethyl aluminum readily forms a complex with the ammo halide. nium tetraalkylo to form a 1: 1 complex and with lo complex 1: 1 to form a 2: 1 complex, all soft:. being insoluble in the olefinic product. This provides a simple and economical process for separating aluminum triethyl from hydrocarbons.



   The invention having been thus deorit with the aid of particular examples, it goes without saying that no restriction or limitation should be deduced therefrom and that numerous variants and modifications are! within the reach of those skilled in the art.

 

Claims (1)

ABSTRACT A.- Process for regenerating a complex of trialkyl aluminum and a compound having the formula RnMX in which R is an alkyl radical, M represents nitrogen, arsenic, phosphorus, sulfur, selenium. or tellurium; X is halogen and n is equal to 3 or 4, depending on the element M considered, this process being characterized by the following points, taken alone or ', in combinations! 1.) A complex product containing a complex 2 is brought into contact: 1 of an aluminum trialkyl with a compound having the formula R n MX in which R, M, X and n have the meaning given above, at a temperature and for a time sufficient to separate the trialkyl aluminum from complex 2 : 1 .. ' 2.) A complex product containing a 2: 1 complex of a trialkyl aluminum in which the alkyl radicals contain on average from 2 to 5: approximately carbon atoms and a tetralkyl halide in which the alkyl radicals contain on average :, from 1 to 5 carbon atoms with a non-reactive and insoluble extraction solvent, at a temperature between-¯¯, tre 100 and about 200 C, and for 1 to 60 minutes, to remove trialkyl aluminum from the 2: 1 complex. 3.) Tetraalkyl ammonium halide is etraaaklyet ammonium chloride 4.) The complex product containing a 2: 1 aluminum trialkyl complex in which the alkyl radicals contain on average from 2 to 5 carbon atoms, and a tetraalkyl halide in which the alkyl radicals contain on average from 1 to <Desc / Clms Page number 47> 5 carbon atoms in the upper part of an elongated extraction zone; an insoluble and unreactive extraction solvent is passed through the lower part of the extraction zone; the solvent. extraction thus circulating from bottom to top and against the current of the complex product; the extraction zone is maintained at a temperature of approximately 100 to 200 ° C. under a pressure which is approximately atmospheric pressure, the complex prudence having a residence time of approximately 1 to 60 minutes in the extraction zone. tion; an extraction solvent enriched in trialkyl aluminum is withdrawn from the upper part of the extraction zone, and a complex product enriched in 1: 1 complex is withdrawn from the lower part of the extraction zone 5.) The complex product enriched in complex 1: 1 leaving the extraction zone is divided in such a way that a part is recycled to the extraction zone, the recycling rate being between 0.2 and 10: 0: 1 6.) Aluminum trialkyl is aluminum triethylo and ammonium tetraalkyl halide is ammonium tetramethyl chloride 7 ') A displacement product containing -.,; ment alpha-olefins comprising from 2 to 30 carbon atoms approximately, an aluminum trialkyl in which the: alkyl radicals comprise on average from 2 to 5 carbon atoms approximately and a solvent hydrocarbon for fixing in a complexation zone; a product chosen from the group is passed through the complexation zone. consisting of a tetraalkyl ammonium halide and Un / 1 <Desc / Clms Page number 48> complex 1; 1 of a trialkyl aluminum in which the. Alkyl radicals comprise on average from about 2 to 5 carbon atoms and a tetraalkyl ammonium halide in which the alkyl radicals have an average of 1 to 5 carbon atoms, so that said product combines with the aluminum trialkyl in the displacement product to form a 2: 1 complex and a displacement product which is insoluble in the complex product; . the displacement product freed from trialkyl aluminum is separated from the complex product: the complex product is washed with a hydrocarbon washing solvent, to remove therefrom any hydrocarbon entrained from the complexation zone; the washed complex product is passed through an extraction zone; an insoluble non-reactive extraction solvent is passed through this extraction zone; the temperature of the extraction zone is maintained at approximately 100-200 ° C., the complex product having in the extraction zone a residence time of approximately 1 to 60 minutes; the extraction solvent thus removing 'Ç. the trialkyl aluminum of the 2: 1 complex, leaving the 2: 1 complex, a solvent enriched in trialkyl aluminum is removed from the extraction zone; a complex product enriched in complex 1: 1 + is removed from the extraction zone and the enriched complex II1 is passed through the complexation zone. 8.) The extraction solvent is a paraffinic hydrocarbon containing about 4 to 20 carbon atoms. 9) The washed solvent is a paraffinic hydrocarbon containing about 8 to 20 carbon atoms. 10,) We pass a displacement product containing <Desc / Clms Page number 49> keeping alpha-olefins comprising from about 2 to 30 carbon atoms, aluminum triethyl and kerosene in a complexation zone; a complex product comprising a 1: 1 complex of aluminum triethyl and tetramethyl ammonium chloride is passed through the complexation zone thereby reacting the 1: 1 complex and aluminum triethyl in the displacement product to form a 2: 1 complex: a product enriched in .complex is removed from the complexation zone 2: 1; the displacement product freed from triethyl aluminum is removed from the complexation zone; the complex product enriched with the complex 2: 1 is passed through a washing zone, a paraffinic hydrocarbon containing from 4 to 20 carbon atoms is passed through the washing zone and thus all the residues are removed from the complex product. hydrocarbons that may be there; the washed complex product is passed through an extraction zone; a paraffinic hydrocarbon comprising from 8 to 20 carbon atoms is passed through the extraction zone; a temperature of approximately 100 to 200 C and a gauge pressure of approximately 0 to 1.05 kg / cm3 is maintained in the extraction zone, the residence time of the complex product in the extraction zone being 1 to 60 minutes approximately; one mole of the aluminum triethyl from the 2: 1 complex being thus removed by the paraffinic hydrocarbon, thus forming a complex: 1: a complex product enriched with complex 1 is removed from the extraction zone. : 1; the paraffinic hydrocarbon enriched in aluminum triethyl is removed from the extraction zone and the complex product enriched in complex 1 is passed through the complexation zone: <Desc / Clms Page number 50> II) To at least one product is added, a complex chosen from the group consisting of a displacement product comprising alpha-olefins and an aluminum trial. low molecular weight kyl, a non-olefinic hydrocarbon containing a low molecular weight aluminum trialkyl. lecular and a trialkyl aluminum dialcoholate containing a low molecular weight aluminum trialkyl, a complexing agent for this low molecular weight triaalkyl aluminum selected from the group consisting of RnMX is a complex of RnMX and a low molecular weight aluminum trialkyl, in the molar ratio of 1: 1 wherein R is an alkyl radical; M is an element consisting of nitrogen, arsenic, phosphorus, sulfur, selenium or tellurium; X is halogen and n varies between 3 and 4, in an amount sufficient to react with and form a complex with at least a significant amount of this low molecular weight aluminum trialkyl and the complex is separated from this product, 12.) The complexing agent is selected from the group consisting of a tetraalkl ammonium halide and a complex of tetralkl ammonium halide and tetraalkyl aluminum in the molar ratio of 1: 1. 13.) This product is a displacement product. 14.) This product is a non-olefinic hydrocarbon 15.) This product is a dialkyl aluminum dialcoholate. 16.) Alkyl radicals are displaced from a relatively higher aluminum trialkyl, in which the alkyl radicals contain from 4 to 30 carbon atoms, by a mono-olefin having from 2 to 5 carbon atoms. approximately carbon and containing fewer carbon atoms <Desc / Clms Page number 51> than the above-mentioned trialkyl aluminum, thereby forming a displacement product comprising relatively high molecular weight alpha-olefins and relatively low molecular weight aluminum trialkyl; the displacement product is baited with a complexing agent ¯ ,, "for this low molecular weight aluminum trialkyl, 'selected from the group consisting of a halide and a complex of tetraalkyl ammonium halide and this trialkyl aluminum low molecular weight, in a molar ratio of 1: 1 in an amount sufficient to combine with at least a significant amount of Relatively low molecular weight trialkyl aluminum to form a complex having a molar ratio of trialkyl aluminum to tetra ammonium halide; zij¯ alkyl is 2: 1 and the 2: 1 complex is separated from the displacement product. 17) A displacement product containing alpha-olefins comprising approximately 4 to 30 carbon atoms and an aluminum trialkyl comprising alkyl radicals containing approximately 2 to 5 carbon atoms, but having less than 5 carbon atoms, is treated. 'carbon atoms as the average number of carbon atoms of alpha-olefins, with a complex of a tetraalkyl ammonium halide having alkyl radicals of from about 1 to 5 carbon atoms and a trialkyl aluminum in in which the alkyl radicals comprise from 2 to 5 carbon atoms approximately, the sum of the average number of carbon atoms of the alkyl radicals of the ammonium halide tetraalkyl and of the average of the carbon atoms of the alkyl radicals of the trialkyl aluminum not being greater than about 6 and the molar ratio of ammonium <Desc / Clms Page number 52> EMI52.1 trialkyl halide being equal to .3., and forming. thus a complex in which the molar ratio is,. EMI52.2 2; 1 and the 211 complex is separated from the alpha-olefins. '¯ ,, J 18.) The 2: 1 complex is pyrolyzed to produce the complex 1 s 1 and an aluminum trialkyl and used'] / (the complex It to process the product of ùp.acQmr3nt,; 19.) The processed displaced product comprises two phases an upper phase of alpha-olefins and a lower phase. EMI52.3 higher 2: 1 complex contaminated with alpha-olof.ne; the phases are adapted and the soiled 2: 1 complex is treated with EMI52.4 a paraffinic hydrocarbon containing from 5 to 12 carbon atoms approximately, but having on average fewer atoms ,,; than the alpha-olefin, to separate the alpha-olefins therefrom, then the 2: 1 complex of the paraffinic hydrocarbon containing the alpha-olefin is separated. > ¯] ". 20) A mixture of a trialkyl aluminum is treated EMI52.5 comprising alkyl radicals having an average of 2. ':'; 5 carbon atoms and an aluminum monoalcoholate 1 EMI52.6 dialkyl with an aluminum trialkyl complex compares - ,,, ning alkyl radicals having an average of 2 to 5 atoms. of carbon and of a tetraalkyl ammonium halide in which the alkyl radicals have on average from 1 to 5 carbon atoms, the molar ratio of trialkyl aluminum to tetraalkyl ammonium being 1: 1 and one thus forms a phase containing substantially dialkylated aluminum monohydric alcoholate and a second phase of a complex product containing a 2: 1 aluminum complex. EMI52.7 , trialkyl to tetraalkyl ammonium halide, and "..: 7 separates the two phases. 21.) Tetraalkyl ammonium halide is the EMI52.8 tetrualkylet ammonium chloride <Desc / Clms Page number 53> 22) A mixture of paraffinic hydrocarbons and an aluminum trialyl in which the alkyl radiates have on average 2 to 5 carbon atoms is treated with a trialkyl aluminum complex in which the alkyl radicals have an average of 2 5 carbon atoms, and a tetraalkyl ammonium halide in which the alkyl radicals have on average from 1 to 5 carbon atoms, the molar ratio of trialkyl aluminum to tetraalkyl ammonium halide being from 1: 1 about 1, thereby forming one phase containing substantially all of the hydrocarbon and another phase containing substantially a complex product comprising a 2: 1 complex of trialkyl aluminum and tetraalkyl ammonium halide, and separating both phases. :: 23) An aluminum trialkyl in which the alkyl radicals contain approximately 2 to 4 carbon atoms is reacted with a mono-olefin comprising from 2 to ' About 5 carbon atoms under conditions such that an attachment product containing a high molecular weight aluminum trialkyl is formed, the alkyl radicals of which have an average of 4 to 30 carbon atoms; the fixing product is treated with a mono-olefin comprising from 2 to 4 carbon atoms approximately, under conditions such as to determine a displacement of the alkyl radicals of the trialkyl aluminum by the monoolefin and a product is thus formed of displacement con-. holding high molecular weight olefins and an alu-. .. low molecular weight minium trialyl; the displacement product is treated with an aluminum trialkyl complex in which the alkyl radicals have an average of 2 to 5 carbon atoms and an ammonium halide <Desc / Clms Page number 54> tetraalkylo in which the alkyl radicals have an average of from 1 to 5 carbon atoms, the molar ratio of the first to the second being about 1: 1, thus forming a phase containing substantially all of the alpha-olefin and a phase containing substantially all the complex product comprising a 2: 1 complex of trialkyl aluminum and tetraalkyl ammonium halide; the complex product is separated from the alpha-olefin phase; the complex is pyrolyzed under conditions such that the 2: 1 complex is decomposed to trialkyl aluminum and a 1: 1 complex; The trialkyl aluminum is separated from the 1: 1 complex using the trialkylated aluminum separated in the aforementioned attachment reaction, and the separated 1: 1 complex is reused for the reaction with the displacement product. 24.) The complex product is washed with a hydrocarbon. Paraffinic bure before pyrolyzing it to decompose the 2: 1 complex. 25.) Aluminum triethyl is reacted with ethylene in a binding zone to produce a binding product comprising a high molecular weight aluminum trialkyl, in which the alkyl groups have 4 to 30 carbon atoms. about; the attachment product is passed through a displacement zone where it is reacted with ethylene to form a displacement product containing aluminum triethyl and alpha-olefins containing 4 to 30 carbon atoms. carbon approximately; the displacement product is treated with a complex of triethyl aluminum and tetramethyl ammonium halide, the molar ratio of the first to the second being 1: 1, thereby forming a <Desc / Clms Page number 55> alpha-olefin phase and a complex product phase containing a complex of 2: 1 triethyl aluminum and tetramethyl ammonium halide; the complex product is washed with a paraffinic hydrocarbon containing About 6 to 12 carbon atoms to remove any alpha-olefins contained therein; the washed complex product is pyrolyzed to decompose the 2: 1 complex to triethyl aluminum and a 1: 1 complex; the triethyl aluminum is separated from the complex 1: 1; the separated triethyl aluminum is passed through the binding zone, and the complex is passed through the displacement zone 1: 1 separate, 26.) Tetramethyl ammonium halide is tetramethyl ammonium chloride, 27) Tetramethyl ammonium halide is tetramethyl ammonium bromide 28.) Tetramethyl ammonium halide is the hard tetramethyl ammonium halide. B. - As a new industrial product: an oomposi-. . tion characterized by the following points, taken singly or in combination 29) It has the formula: a (R3A1) R4NC1 in which R is an alkyl radical having from 2 to 5 'carbon atoms, a is equal to 1 or to 2; r 'is an alkyl radi cal having 1 to 3 carbon atoms and R + R' does not exceed 6 carbon atoms. R is an ethyl radical; a is equal to 1 and r 'is a methyl radical. 31) R is an ethyl radical, is equal to 2 and R. is a methyl radical *