PL47177B1

PL47177B1 -

Info

Publication number: PL47177B1
Application number: PL47177A
Authority: PL
Filing date: 1960-05-04
Publication date: 1963-06-15

Description

Ra¬ zem wydziela sie w przestrzeni anodowej na kazda amperogodzine 5,7 g AWCfHsJa. 3/4 tej ilosci pochodzi z elektrolitu. Ta czesc ponownie przeksztalca sie w czteroetylinosód' na drodze reakcji z NaH i etylenem w temperaturze 180°C i przy cisnieniu etylenu wynoszacym 10 atm.Przyklad II. Otrzymany sposobem wedlug opisu patentowego N.RF. nr 917*006 (przyklad IV) czteropropyloglinosód wlewa sie do apara¬ tury elektrolitycznej wedlug zalaczonego rysun¬ ku, celowo w stanie stopionym. Podczas elek¬ trolizy temperatura elektrolitu wynosi okolo 100°C. Natezenie pradu ustala sie na 15 A przy napieciu na zaciskach 8 V, co odpowiada ano¬ dowej gestosci pradu 4 A/dm2 i katodowej ge¬ stosci pradu 10 A/dm2. Powstajacy na katodzie sód splywa cienka warstewka po powierzchni katody do dolnej przestrzeni katodowej, skad od czasu do czasu jest odbierany w stanie sto¬ pionym. Wyplyw z przestrzeni anodowej jest tak ustalony, ze odplywa z niej mieszanina re¬ akcyjna zawierajaca okolo 20% trójpropylogli¬ nu. Takie stezenie uzyskuje sie, gdy na godzine odbiera sie z przestrzeni anadowej lacznie okolo 550 ml. Doplyw stopionego czteropropyloglino- sodu do przestrzeni katodowej jest tak ure¬ gulowany, ze poziom cieczy w przestrzeni kato¬ dowej jest o 4 do 5 cm wyzszy niz w przestrze¬ ni anodowej.W wyparce filmowej oddziela sie trójpropylo- glin od czteropropyloglinosodu (w temperatu¬ rze 100°C i cisnieniu 1 tora). 1/4 otrzymanego destylatu jest nowopowstalym trójpropyloglinem.Czesc te odprowadza sie w sposób ciagly. Po¬ zostale 3/4 otrzymanej ilosci trójpropyloglinu przeksztalca sie sposobem podanym w opisie patentowym N.R.F. nr 917.006 za pomoca wo¬ dorku sodowego i propylenu w czteropropylo¬ glinosód i doprowadza sie ponownie do elektro- lizera. Na kazda amperogodizine otrzymuje sie 1,8 g nowoutworzonego trójpropylo-glinu (94°/o wydajnosci teoretycznej).Przyklad III. Postepuje sie analogicznie jak w przykladzie II, stosujac jednak czterobu- tyloglinosód jako elektrolit i odbierajac co go¬ dzine mieszanine 30*/« trójbutyloglinu i cztero- butyloglinosodu, otrzymujac po odpowiedniej obróbce czysty trójtoutyloglin (temperatura wrze¬ nia 100°C przy cisnieniu 0,5 tora).Przyklad IV. Postepujac jak opisano w przykladzieIpoddaje sie elektrolizie NaA.l(ClHs)* w opisanej temperaturze, uzywajac jednak gra¬ nulowanego magnezu jako materialu anodowe¬ go. Temperatura elektrolizy wynosi 100°C. Na¬ tezenie pradu przy napieciu 6 V na zaciskach ustala sie na 15 A. Powstajacy w anodzie zwia¬ zek o skladzie Mg(CtH*)t. 2 Al(C2Hs)s rozpuszcza sie tylko w malym stopniu w czteroalkilo-glino- sodzie (okolo 10°/a i gromadzi sie w postaci kro¬ pli na powierzchni elektrolitu, stwarzajac druga faze ciekla, która od czasu do czasu odbiera sie).Otrzymany zwiazek MgiCtHz)* • 2 AZ(C2Hó)3 ogrzewa sie w wysokiej prózni do temperatury 100°C. Trójalkiloglin oddestylowuje przy tym calkowicie. Pozostalosc jest czystym dwuetylo- magnezem.Na kazde 26,8 amperogodzin uzyskuje sie 39 g Mg(CtHs)i, co stanowi 95°/o wydajnosci teore¬ tycznej.Przyklad V. Stosuje sie elektrolizer, któ¬ ry sklada sie z mocnego prózniowego naczynia stalowego, w którego srodku umieszczona jest katoda z blachy miedzianej, a po obu jej stro¬ nach w odleglosci okolo 1 do 2 cm znajduja sie anody z mocnych plyt aluminiowych. Ano¬ dy sa izolowane. Katoda jest polaczona ze sta¬ lowym plaszczem naczynia metalowym prze¬ wodnikiem. Katoda jest tak dluga, ze dotyka u dolu dna naczynia, natomiast pomiedzy dol¬ nym koncem anody, a dnem naczynia jest wol¬ na przestrzen okolo 20 cttl Do naczynia wlewa — 4 —sie w atmosferze azotu elektrolit, skladajacy sie z 80°/o czteroetyloglinopotasu i 20*/o cztero- etyloglinosodu. Naczynie jest poprzez pochylona ku dolowi chlodnice polaczone z chlodzonym odbieralnikiem i pompa prózniowa. Stalowe naczynie ogrzewa sie do temperatury 130 do 140°C i wytwarza próznie mozliwie ponizej 0,1 tora. Nastepnie wlacza sie prad i doprowadza przez specjalny polaczony z naczyniem przewód, stopiony, czteroetyloglinosód w ilosci zaleznej od natezenia pradu. Natezenie pradu dolewa sie tak, aby gestosc wynosila 10 do 30 A/dm2. Na kazde 26,8 aimperogodzin doprowadza sie do na¬ czynia 166 g czteroetyloglinosodu.Powstajacy na anodzie trój etyloglin oddesty- lowuje w sposób ciagly w ilosci 150 g na kazde 26,8 amperogodzin. W tej ilosci zawarte jest 38 g nowopowstalego trójetyloglinu (100V» wydaj¬ nosci teoretycznej). W urzadzeniu tym elektro¬ lit zawierajacy zwiazki kompleksowe sodu i potasu pozostaje praktycznie niezmieniony. W naczyniu rozklada sie jedynie dolewany cztero¬ etyloglinosód. Stopiony sód zbiera sie w ilosci 23 g na kazde 26,8 amperogodzin na dnie na¬ czynia. Elektrolize prowadzi sie tak dlugo, az sód w naczyniu podniesie sie tak wysoko, ze doprowadzic moze do zwarcia katody z anoda¬ mi glinowymi. Oczywiscie po przerwaniu próz¬ ni i wylaczeniu doplywu pradu sód mozna ode¬ brac z aparatury w stanie cieklym. 1/4 ilosci destylatu oddziela sie jako nowopowstaly trój- etyloglin. Pozostala ilosc poddaje sie reakcji z wodorkiem sodowymi i etylenem, jak to opisa¬ no w przykladzie I, w celu wytworzenia cztero¬ etyloglinosodu, który moze byc ponownie uzyty do elektrolizy.Ze wzgledu na wrazliwosc elektrolitu i pro¬ duktów reakcji na dzialanie powietrza i wody wszystkie operacje powinny byc prowadzone z wylaczeniem wilgoci w atmosferze obojetnej na przyklad w atmosferze azotu lub argonu. PLIn total, 5.7 g of AWCfHsJ is released in the anode space for each ampere-hour. 3/4 of this amount comes from the electrolyte. This part re-transforms to tetraethyl sodium by reaction with NaH and ethylene at 180 ° C and an ethylene pressure of 10 atm. Example II. Obtained by the method according to the patent description of N.RF. No. 917 * 006 (Example IV) sodium tetrapropyl is poured into the electrolytic apparatus according to the attached drawing, intentionally in a molten state. During the electrolysis, the temperature of the electrolyte is approximately 100 ° C. The current becomes 15 amps at a terminal voltage of 8 volts, which corresponds to an anode current density of 4 amps / dm2 and a cathode current density of 10 amps / dm2. The sodium formed on the cathode flows down a thin film over the cathode surface to the lower cathode space, from where it is removed from time to time in a solid state. The outflow from the anode space is set so that a reaction mixture containing about 20% of tripropylaluminum flows out of it. Such a concentration is obtained when a total of about 550 ml are withdrawn from the anadic space per hour. The inflow of molten sodium tetrapropyl aluminum to the cathode space is so regulated that the liquid level in the cathode space is 4 to 5 cm higher than in the anode space. In a film evaporator, tripropyl aluminum is separated from sodium tetrapropyl aluminum (at the temperature of 100 ° C and pressure of 1 torr). 1/4 of the distillate obtained is newly formed tripropylaluminum. Part of this is continuously discharged. The remaining 3/4 of the obtained amount of tripropylaluminum was transformed as described in the patent specification N.R.F. No. 917,006 to sodium tetrapropylaluminum with sodium hydride and propylene and fed back to the electrolyser. For each amperogodizine 1.8 g of newly formed tripropyl aluminum are obtained (94% of theoretical yield). Example III. The procedure is analogous to that in Example II, but using sodium tetrasbutylaluminum as electrolyte and receiving every hour a mixture of 30% aluminum tetra-butylaluminium and sodium tetra-butyl aluminum, after appropriate treatment (boiling point 100 ° C at a pressure of 0 5th Torah) Example IV. Following the example described in the example, the electrolysis of NaAl (ClHs) is carried out at the described temperature, but using granulated magnesium as the anode material. The electrolysis temperature is 100 ° C. The current voltage at 6 volts at the terminals becomes 15 A. The compound formed in the anode is Mg (CtH *) t. 2 Al (C2Hs) s dissolves only slightly in tetraalkyl aluminum sodium (about 10%) and accumulates as drops on the surface of the electrolyte, forming a second liquid phase which is collected from time to time. compound MgiCtHz) * • 2 AZ (C2H6) 3 are heated under high vacuum to 100 ° C. In the process, the trialkylaluminum distils completely. The remainder is pure diethylmagnesium. For every 26.8 ampere-hours, 39 g of Mg (CtHs) are obtained, which is 95% of theoretical yield. steel, with a cathode made of copper sheet in the center, and on both sides of it at a distance of about 1 to 2 cm there are anodes made of strong aluminum plates. The anodes are isolated. The cathode is connected to the steel mantle by a metal conductor. The cathode is so long that it touches the bottom of the vessel at the bottom, while between the lower end of the anode and the bottom of the vessel, there is a space of about 20 ct. tetramethylaluminopotassium and 20% tetraethylaluminosodium. The vessel is connected to a cooled receiver and a vacuum pump via a downward inclined cooler. The steel vessel is heated to a temperature of 130 to 140 ° C and builds a vacuum as low as possible 0.1 Torr. Then the electricity is turned on and fed through a special cable connected to the vessel, melted tetrafluoroaluminium in the amount depending on the current strength. The current is added so that the density is 10 to 30 A / dm2. 166 g of tetraethylaluminium is fed to the vessel for every 26.8 ampere hours. The triethylaluminum formed at the anode continuously distills 150 grams for every 26.8 ampere hours. This amount contains 38 g of newly formed triethylaluminum (100 volts theoretical). In this device, the electrolyte containing sodium and potassium complexes remains practically unchanged. Only the added tetraethylaluminium is decomposed in the vessel. The molten sodium is collected in an amount of 23 grams for every 26.8 ampere-hours at the bottom of the vessel. The electrolysis is carried out until the sodium in the vessel rises so high that it can short-circuit the cathode with the aluminum anodes. Of course, after breaking the vacuum and turning off the power, the sodium can be withdrawn from the apparatus in a liquid state. 1/4 of the amount of distillate separates as newly formed triethylaluminum. The remainder is reacted with sodium hydride and ethylene, as described in Example 1, to produce sodium tetraethyl, which can be reused for electrolysis. Due to the sensitivity of the electrolyte and the reaction products to air and water, all operations should be carried out excluding moisture in an inert atmosphere, for example nitrogen or argon. PL

Claims

Claims 1. A process for the electrowinning of di-alkylmagnesium or trialkylaluminum by electrolysis of electrolytes containing tetraalkylaluminium compounds, characterized in that a complex compound of the general formula MeAl (R) i, in which Me is sodium or a mixture of sodium and potassium, The R - alkyl residue, in particular containing from 2 to 6 carbon atoms, is electrolysed using a magnesium or aluminum anode, respectively, and a metal cathode that does not melt with the sodium that is released on the cathode during electrolysis, the content of the aqueous aluminum trialkyl in the electrolyte near the cathode, it is maintained at a level lower than 3% / t, especially by separating the cathode space from the anode space by means of a diaphragm, by carrying out electrolysis in a vacuum, or by continuous extraction of the electrolyte by means of an extraction medium ¬ free alkyl metal.

2. Way according to satrz. The process of claim 1, wherein the electrolysis is carried out under a vacuum in the production of aluminum alkyl, in particular at a pressure of less than 1 m Hg.

3. The method according to p. The method of claim 1, characterized in that in order to separate from the electrolyte of organometallic compounds remaining on the anode, the electrolyte is rinsed during the electrolysis in a manner that is continuously incompatible with the electrolyte saturated with hydrocarbon, especially aliphatic or hydroaromatic.

4. The method according to p. A process as claimed in any one of claims 1 to 3, characterized in that, in the preparation of alkylmagnesium, the mixture of dialkyl magnesium and aluminum trialkyl formed on the anode is separated from the electrolyte and the mixture is separated into its components, in particular by distilling the volatile aluminum trialkyl under a vacuum.

5. The method according to p. 1-4, when using a circular cycle, characterized in that the organometallic compounds formed on the anode are separated from the electrolyte, from which a part of the aluminum alkyl is separated from the decomposition of the electrolyte, and then this part of the aluminum cathode-separated sodium is converted to compounds of the general formula MeAl (R) t by treatment with hydrogen and the appropriate olefins, and then the compounds of the formula MeAl (R) A are recycled to electrolysis.

6. The method according to p. A method according to any of the claims 1-5, characterized in that the electrolysis is carried out at a temperature of 100 to 140 ° C, with a voltage of 0.5 to 5V and a current density not higher than 80 A / dm *.

7. The method according to p. A compound according to any of the claims 1-6, characterized in that the electrolyte used is complex compounds of the general formula MeAl (R) *, in which Me is a mixture of sodium and potassium, the potassium content being up to 80% by weight. Prof. Dr. Karl Ziegler Deputy: Dr. Andrzej Au Patent Attorney For patent description No. 47177 ^ F.W.H. disposable pattern. residing PL / Ke, Czst. residing 1420 18.V.63 100 copies of letters. ki. III PL