DE936630C - Process for the production of aluminum hydrocarbons - Google Patents
Process for the production of aluminum hydrocarbonsInfo
- Publication number
- DE936630C DE936630C DEZ3509A DEZ0003509A DE936630C DE 936630 C DE936630 C DE 936630C DE Z3509 A DEZ3509 A DE Z3509A DE Z0003509 A DEZ0003509 A DE Z0003509A DE 936630 C DE936630 C DE 936630C
- Authority
- DE
- Germany
- Prior art keywords
- aluminum
- alkyl
- cryolite
- fluoride
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 17
- -1 aluminum hydrocarbons Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229930195733 hydrocarbon Natural products 0.000 title claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 16
- 229910001610 cryolite Inorganic materials 0.000 claims description 15
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 6
- HRXSKIOIHQEGAI-UHFFFAOYSA-M diethylalumanylium;fluoride Chemical compound CC[Al](F)CC HRXSKIOIHQEGAI-UHFFFAOYSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/064—Aluminium compounds with C-aluminium linkage compounds with an Al-Halogen linkage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
Das Patent 921450 und das Zusatzpatent 934649 betreffen ein Verfahren zur Herstellung von Aluminiumkohlenwasserstoffen, insbesondere Aluminiuiiitrialkylen, aus Aluminiumhalogenalkylen, wobei als Nebenprodukt, abgesehen von Kochsalz, Kryolith — Na3 Al F6 -— erhalten wird. Gemäß diesen Verfahren wird beispielsweise Diäthylaluminiumchlorid zunächst mit Natriumfluorid in Diäthylaluminiumfluorid umgewandelt und dieses dann mit Natriumfluorid im Molverhältnis 1:1 erhitzt. Hierbei bildet sich zunächst eine Komplexverbindung zwischen Diäthylaluminiumfluorid und Natriumfluorid von der Zusammensetzung NaAl(C2Hg)2F2, worauf diese in Kryolith und Aluminiumtriäthyl gespalten wird.The patent 921 450 and the additional patent 934649 relate to a process for the production of aluminum hydrocarbons, in particular aluminiumitrialkylenes, from aluminum haloalkylenes, with cryolite - Na 3 Al F 6 - being obtained as a by-product, apart from common salt. According to this process, for example, diethyl aluminum chloride is first converted into diethyl aluminum fluoride with sodium fluoride and this is then heated with sodium fluoride in a molar ratio of 1: 1. In this case, a complex compound is initially formed between diethyl aluminum fluoride and sodium fluoride with the composition NaAl (C 2 Hg) 2 F 2 , whereupon this is split into cryolite and aluminum triethyl.
3 NaAl (C2H5)2F2 = Na3AlF6 + 2 Al (C2H5)3 3 NaAl (C 2 H 5 ) 2 F 2 = Na 3 AlF 6 + 2 Al (C 2 H 5 ) 3
Der Vorteil dieser Verfahren gegenüber anderen, schon länger bekannten Prozessen besteht darin,The advantage of this process over other processes that have been known for a long time is that
daß das Nebenerzeugnis Kryolith ein verwertbares Handelsprodukt ist, das für die elektrolytische Erzeugung von Aluminium Bedeutung hat.that the by-product cryolite is a commercial product that can be used for electrolytic production of aluminum is important.
Ein anderer für die Technik des Aluminiums wichtiger Stoß; ist das Aluminiumfluorid. Es wird für die Aluminiumelektrolyse laufend in gewissem Umfang zur Ergänzung der Fluorverluste des Elektrolyten gebraucht, während der Kryolith lediglich bei der Inbetriebnahme eines neuen Bades eingesetzt wird. Für die Aluminiumerzeugung wird Aluminiumfluorid in größerer Menge benötigt als Kryolith.Another impact important for the technology of aluminum; is the aluminum fluoride. It will for aluminum electrolysis continuously to a certain extent to supplement the fluorine losses of the Electrolytes are needed, while cryolite is only used when starting up a new bath is used. Aluminum fluoride is required in large quantities for the production of aluminum as cryolite.
Es wurde nun gefunden, daß sich das Verfahren des Patents 921 450 in der Weise modifizieren läßt, daß Aluminiumkohlenwasserstoffe neben Aluminiumfluorid anfallen. Erfindungsgemäß setzt man den gemäß dem Verfahren des Patents 921 450 anfallenden Kryolithrückstand mit Alkyl- oder Arylaluminiumhalogeniden um, trennt die gebildetenIt has now been found that the method of patent 921 450 can be modified in such a way that that aluminum hydrocarbons occur in addition to aluminum fluoride. According to the invention, one sets the cryolite residue with alkyl or aryl aluminum halides obtained according to the process of patent 921 450 um, separates the educated
Alkyl- oder Arylaluminiumfluoride von dem bei der Umsetzung entstandenen festen Bodenkörper ab, verarbeitet die Organqaluminiumfluoride gemäß Patent 921450 weiter und behandelt den aus Alkalihalogenid und Aluminiumfluorid bestehenden Bodenkörper zweckmäßig nach einer vorhergegangenen Calcination mit Wasser, wobei das ungelöst bleibende Aluminiumfluorid in seinem Zustand erhalten wird.Alkyl or aryl aluminum fluorides from the solid sediment formed during the reaction, processes the organqaluminum fluoride according to patent 921450 and treats it Alkali halide and aluminum fluoride existing soil bodies expediently after a previous one Calcination with water, whereby the aluminum fluoride which remains undissolved is retained in its state will.
Hat man daher eine Umsetzung nach dem Verfahren des Patents 921 450 zu Ende geführt, so läßt man den im Reaktionsgefäß trocken zurückbleibenden Kryolith unmittelbar wiederum mit Alkyl- bzw. Arylaluminiumfluoriden, z. B. mit Diäthylaluminiumchlorid reagieren, worauf sich dann im Sinne der GleichungIf you have therefore brought an implementation according to the method of patent 921 450 to the end, so the cryolite that remains dry in the reaction vessel is left with it again immediately Alkyl or aryl aluminum fluorides, e.g. B. react with diethylaluminum chloride, whereupon then in terms of the equation
Na3 Al F6 + 3 Al (C2 H5) 2 ClNa 3 Al F 6 + 3 Al (C 2 H 5 ) 2 Cl
= 3 Al (C2H5)2F + 3 NaCl + AlF3 das Aluminiumfluorid neben Diäthylaluminiumfluorid und Kochsalz bildet. Diese Reaktion läßt sich entweder mit konzentriertem Diäthylaluminiumchlorid unter Rühren ausführen, oder man arbeitet in dieser Phase bei Gegenwart eines indifferenten Lösungsmittels, beispielsweise Chlorbenzol oder o-Dichlorbenzol. Hat man zunächst ohne Lösungsmittel gearbeitet, so setzt man zweckmäßig nach der Reaktion ein geeignetes - Lösungsmittel zu, z. B. eines der eben genannten oder auch ein anderes, z. B. Benzol, und trennt dann die Lösung von der Mischung Kochsalz—Aluminiutnfluorid durch Filtration. Ebenso gut kann man aber, auch, insbesondere dann, wenn man ohne Lösungsmittel gearbeitet hat, das Diäthylaluminiumfluorid im Vakuum aus der Reaktionsmischung abdestillieren. In jedem Fall erhält man schließlich Diäthylaluminiumfluorid, sei es als Lösung, sei es in Substanz. 1 Mol dieser Substanz wird, mit ι Mol Natriumchlorid zur Komplexverbindung Na Al (C2 H5) 2 F2 vereinigt und erneut der Spaltung zugeführt. Dabei erhält man eine Mischung von ι Mol Aluminiumfluorid auf 3 Mol Kochsalz. Diese Mischung wird zwecks Gewinnung reinen Aluminiumfluoride zweckmäßig calciniert, wobei das AIuminiumfluorid in eine beständige und durch Wasser weniger leicht angreifbare Form übergeführt wird, Dann' löst man mit Wasser das Kochsalz heraus und gewinnt das Aluminiumfluorid durch Filtration. = 3 Al (C 2 H 5 ) 2 F + 3 NaCl + AlF 3 which forms aluminum fluoride in addition to diethyl aluminum fluoride and common salt. This reaction can either be carried out with concentrated diethylaluminum chloride with stirring, or one works in this phase in the presence of an inert solvent, for example chlorobenzene or o-dichlorobenzene. If you have initially worked without a solvent, it is expedient to add a suitable solvent after the reaction, e.g. B. one of the just mentioned or another, z. B. benzene, and then separates the solution from the mixture of common salt and aluminum fluoride by filtration. However, it is just as easy to distill off the diethylaluminum fluoride from the reaction mixture in vacuo, especially if you have worked without a solvent. In any case, diethylaluminum fluoride is finally obtained, either as a solution or as a substance. 1 mol of this substance is combined with ι mol of sodium chloride to form the complex compound Na Al (C 2 H 5 ) 2 F 2 and fed to the cleavage again. This gives a mixture of 1 mole of aluminum fluoride to 3 moles of sodium chloride. This mixture is expediently calcined for the purpose of obtaining pure aluminum fluoride, the aluminum fluoride being converted into a stable form that is less susceptible to attack by water. The common salt is then dissolved out with water and the aluminum fluoride is recovered by filtration.
Bei der Umsetzung des Kryoliths mit dem Alkyl- oder Arylaluminiumhalogenid, z. B. mit Diäthylaluminiumchlorid, die sich ja zwischen einem schwer loslidhen festen Reaktionspartner und einer flüssigen Phase abspielt, hat es sich herausgestellt, daß die Reaktion gegen Ende, wenn die Konzentration des Diäthylaluminiumchlorids in der Reaktionsmischung nur noch gering ist, langsam verläuft, so daß der vollständige Umsatz des Kryoliths gewisse Schwierigkeiten macht.When the cryolite is reacted with the alkyl or aryl aluminum halide, e.g. B. with diethyl aluminum chloride, which is between a hard to get rid of solid reactants and one liquid phase plays, it has been found that the reaction ends when the concentration of the diethylaluminum chloride in the reaction mixture is only small, proceeds slowly, so that the complete conversion of the cryolite causes certain difficulties.
· Man kann diese Schwierigkeit sehr leicht dadurch überwinden, daß man die Umsetzung zwischen Kryolith und Alkylaluminiumhalogenid in zwei oder mehreren Stufen derart durchführt, daß man die Reaktion bei noch unvollständigem Umsatz unterbricht, wenn die Reaktionsgeschwindigkeit zu gering geworden ist. Es werden die organischen Aluminiumverbindungen, sei es durch Lösung, sei es durch Destillation, vom Bodenköirper abgetrennt, und es wird der noch nicht vollständig umgesetzte Bodenkörper mit neuem Alkylaluminiumhalogenid behandelt, worauf dann die vollständige Umwandlung in Aluminiumfluorid und Natriumchlorid rasch erfolgt, während die noch nicht vollständig in Fluor id umgewandelten organischen Aluminiumverbindungen mit frischem Kryolith weiter umgesetzt werden. Auch dieses Verfahren läßt sich in einer ununterbrochenen Folge von Einzeloperationen ausführen, die unter alleiniger Verwendung von beispielsweise Diäthylaluminiumchlorid und Natriumfluorid die folgende Bruttogleichung zu verwirklichen gestatten:· One can overcome this difficulty very easily by doing the implementation between Carries out cryolite and alkyl aluminum halide in two or more stages such that the reaction is interrupted when the conversion is still incomplete when the reaction rate is too high has become low. It will be the organic aluminum compounds, be it through solution it is separated from the bottom body by distillation, and it becomes the not yet completely reacted sediment with new alkyl aluminum halide treated, followed by complete conversion to aluminum fluoride and sodium chloride occurs rapidly, while the organic aluminum compounds which have not yet been completely converted into fluorine id can be further implemented with fresh cryolite. This procedure can also be used in perform an uninterrupted sequence of individual operations using for example, diethyl aluminum chloride and sodium fluoride give the following gross equation to realize:
3Al(C2H5)2Cl + 3 Al (C 2 H 5 ) 2 Cl +
= AlF3 + 3 NaCl + 2 Al (C2H5)3 = AlF 3 + 3 NaCl + 2 Al (C 2 H 5 ) 3
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEZ3509A DE936630C (en) | 1952-07-28 | 1953-06-12 | Process for the production of aluminum hydrocarbons |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE779873X | 1952-07-28 | ||
| DEZ3509A DE936630C (en) | 1952-07-28 | 1953-06-12 | Process for the production of aluminum hydrocarbons |
| US370655A US2839556A (en) | 1952-07-28 | 1953-07-27 | Production of aluminum hydrocarbons |
| US683002A US2909547A (en) | 1952-07-28 | 1957-09-10 | Organo aluminum compounds, especially fluorides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE936630C true DE936630C (en) | 1955-12-15 |
Family
ID=32398044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEZ3509A Expired DE936630C (en) | 1952-07-28 | 1953-06-12 | Process for the production of aluminum hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE936630C (en) |
-
1953
- 1953-06-12 DE DEZ3509A patent/DE936630C/en not_active Expired
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