DE1068683B - Process for the production of pure zirconium tetrachloride by sublimation - Google Patents
Process for the production of pure zirconium tetrachloride by sublimationInfo
- Publication number
- DE1068683B DE1068683B DENDAT1068683D DE1068683DA DE1068683B DE 1068683 B DE1068683 B DE 1068683B DE NDAT1068683 D DENDAT1068683 D DE NDAT1068683D DE 1068683D A DE1068683D A DE 1068683DA DE 1068683 B DE1068683 B DE 1068683B
- Authority
- DE
- Germany
- Prior art keywords
- zirconium tetrachloride
- sublimation
- production
- hydrocarbons
- pure zirconium
- 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.)
- Pending
Links
- DUNKXUFBGCUVQW-UHFFFAOYSA-J Zirconium(IV) chloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 title claims description 18
- 238000000859 sublimation Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- -1 propylene, butylene Chemical group 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Stearin Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/04—Halides
Description
Verfahren zur Herstellung von reinem Zirkontetrachlorid durch Sublimation Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von hochreinem, wasserfreiem Zirkontetrachlorid aus Roh-Zirkontetrachlorid, das durch Chloride anderer Elemente, wie Eisen, Aluminium, Titan, Silicium usw., verunreinigt ist. Process for the production of pure zirconium tetrachloride by sublimation The present invention relates to a process for the production of high purity, anhydrous zirconium tetrachloride from raw zirconium tetrachloride, which is replaced by chlorides of others Elements such as iron, aluminum, titanium, silicon, etc. is contaminated.
Die üblichen Verunreinigungen des Zirkontetrachlorids können durch einfache Sublimation nicht abgetrennt werden, da die Sublimationspunkte ihrer Chloride zu nahe bei dem Sublimationspunkt des ZrCl liegen. Die geläufigen Verfahren zum Abtrennen störender Fremdelemente sind Umkristallisieren oder Ausfällen verschiedener Zirkonverbindungen. Diese Operationen sind technisch schwierig durchzuführen und in jedem Falle mit größerem Aufwand verbunden als Sublimationen. The usual impurities of the zirconium tetrachloride can through simple sublimation cannot be separated because the sublimation points of their chlorides too close to the sublimation point of the ZrCl. The common procedures for Separation of interfering foreign elements are recrystallization or precipitation of various Zirconium compounds. These operations are technically difficult to perform and in any case associated with greater effort than sublimations.
Verfahren, bei denen Zirkontetrachlorid in Gegenwart von Wasserstoff oder Metalisulfiden sublimiert werden, führen nicht zu befriedigenden Reinheitsgraden und haben andere verfahrenstechnische und prinzipielle Nachteile.Process in which zirconium tetrachloride in the presence of hydrogen or metal sulfides are sublimed, do not lead to satisfactory degrees of purity and have other procedural and principle disadvantages.
Durch Sublimation von Zirkontetrachlorid in Gegenwart schwerflüchtiger, organischer Stoffe (z. B. Fette, Stearin, Schweröl) erhält man ein sehr reines Produkt. Das Verfahren ist jedoch schwierig kontinuierlich durchzuführen und erfordert einen verhältnismäßig großen, technischen Aufwand, da die organischen Stoffe in Form von Lösungen in Tetrachlorkohlenstoff, Benzin od. dgl. mit dem Zirkontetrachlorid gemischt werden müssen und die Sublimation erst nach dem Abdestillieren des leichter flüchtigen Lösungsmittels durchgeführt werden kann.By subliming zirconium tetrachloride in the presence of non-volatile, Organic substances (e.g. fats, stearin, heavy oil) result in a very pure product. However, the process is difficult to operate continuously and requires one relatively large, technical effort, since the organic substances in the form of Solutions in carbon tetrachloride, gasoline or the like mixed with the zirconium tetrachloride must be and the sublimation only after distilling off the more volatile Solvent can be carried out.
Es wurde nun unter Vermeidung der angeführten Nachteile gefunden, daß auch aus unreinem Ausgangsmaterial auf einfache Weise hochreines Zirkontetrachlorid gewonnen werden kann, wenn in einer Kohlenwasserstoff enthaltenden Atmosphäre sublimiert wird, wobei einschränkend als Kohlenwasserstoffe dabei solche mit mehr als einem C-Atom und einem Siedepunkt unter 60° C in Frage kommen. Ungeeignet ist der einfachste Kohlenwasserstoff, das Methan. Besonders bewährt haben sich Äthan und Äthylen, aber auch Propan und Propylen, Butylen oder Gemische, auch mit Inertgasen, z. B. It has now been found, avoiding the disadvantages mentioned, that even from impure starting material, high-purity zirconium tetrachloride is simple can be recovered when sublimed in a hydrocarbon-containing atmosphere is, with limiting as hydrocarbons here those with more than one C atom and a boiling point below 60 ° C come into question. The simplest is unsuitable Hydrocarbon, the methane. Ethane and ethylene have proven to be particularly effective, however also propane and propylene, butylene or mixtures, also with inert gases, e.g. B.
Leuchtgas.Coal gas.
Führt man die aus erhitztem Rohmaterial aufsteigenden Dämpfe mit einem gerichteten, z. B. Äthanstrom, in einen relativ kühleren Raum, so erhält man dort ein reinweißes Zirkontetrachlorid, das in Wasser jonogen löslich und frei von Hydrolyseprodukten ist. Im dunkelgefärbten Sublimationsrückstand verbleiben die Fremdelemente zum Teil in wasserlöslicher, zum Teil in wasserunlöslicher Form, unabhängig davon, ob bei Normaldruck oder im Teilvakuum oder bei erhöhtem Druck sublimiert wird. Im allgemeinen wird man wegen des notwendigen Aufwands davon absehen, im Vakuum zu arbeiten. If you carry the vapors rising from the heated raw material with you a directed, e.g. B. Äthanstrom, in a relatively cooler room, so you get there a pure white zirconium tetrachloride, which is soluble in water and free of ionic Hydrolysis products is. The remains in the dark-colored sublimation residue Foreign elements partly in water-soluble, partly in water-insoluble form, independently whether sublimed at normal pressure or in a partial vacuum or at elevated pressure will. In general, one will refrain from doing this in a vacuum because of the effort required to work.
Das nach Abscheiden des Zirkontetrachlorids verbleibende Gasgemisch bzw. Gas kann abgezogen und erneut dem Äthanstrom hinzugefügt werden. Die beste Ausnutzung erzielt man mit solchen Kohlenwasserstoffen, die bei Zimmertemperatur gasförmig sind bzw. die einen Siedepunkt von unter 500 C besitzen. Es empfiehlt sich, sie mit Inertgas in etwa vergleichbaren Mengen zu mischen.The gas mixture remaining after the zirconium tetrachloride has been deposited or gas can be withdrawn and added again to the ethane stream. The best Exploitation can be achieved with such hydrocarbons at room temperature are gaseous or have a boiling point below 500 C. It recommends to mix them with inert gas in approximately comparable amounts.
Das erfindungsgemäße Verfahren soll durch nachfolgende Beispiele näher erläutert werden: Beispiele 1. 14 kg erdbraungefärbtes Roh-Zirkontetrachlorid (1,6010 Fe, 1,70je Al, 0,013°/o Ti, 0,25°/o Si, jeweils bezogen auf Zr) wurden unter Normaldruck in einem Äthylenstrom sublimiert. Es wurde ein reinweißgefärbtes Sublimat mit Gehalten von 0,0010/0 Fe, 0,087010 Al, <0,001010 Ti und 0,0060/, Si erhalten. The method according to the invention is illustrated by the following examples the following are explained in more detail: Examples 1. 14 kg of raw zirconium tetrachloride, colored earth-brown (1.6010 Fe, 1.70 per Al, 0.013% Ti, 0.25% Si, each based on Zr) were under Normal pressure sublimed in a stream of ethylene. It became a pure white colored sublimate with contents of 0.0010 / 0 Fe, 0.087010 Al, <0.001010 Ti and 0.0060 /, Si.
2. 11 kg des im Beispiel 1 genannten Roh-Zirkontetrachlorids wurden in einem Gasstrom, der Äthylen und Stickstoff im Volumenverhältnis 1:1 enthielt, sublimiert. 2. 11 kg of the crude zirconium tetrachloride mentioned in Example 1 were in a gas stream containing ethylene and nitrogen in a volume ratio of 1: 1, sublimated.
Die Konzentrationen der Fremdelemente im Sublimat betrugen 0,010010 Fe, 0,035010 Al, 0,0050/, Ti und 0,005°/0 Si.The concentrations of the foreign elements in the sublimate were 0.010010 Fe, 0.035010 Al, 0.0050 /, Ti and 0.005 ° / 0 Si.
3. 12 kg Roh-Zirkontetrachiorid (1,6 0je Fe, 1,70/0 Al, 0,050/, Ti) wurden im Äthanstrom sublimiert. Das Sublimat enthielt noch 0,0020/, Fe, 0,0300/, Al, <0,001010 Ti. 3. 12 kg raw zirconium tetrachloride (1.6 per Fe, 1.70 / 0 Al, 0.050 /, Ti) were sublimated in the ethane stream. The sublimate still contained 0.0020 /, Fe, 0.0300 /, Al, <0.001010 Ti.
4. 40 g Roh-Zirkontetrachlorid (0,09°/0 Fe, 1,3 0je Ti) wurden im Propanstrom sublimiert. Die Endkonzentrationen in Sublimat betrugen 0,01301, Fe, 0,0840/, Ti. 4. 40 g of crude zirconium tetrachloride (0.09% Fe, 1.3% per Ti) were in the Propane stream sublimed. The final concentrations in sublimate were 0.01301, Fe, 0.0840 /, Ti.
5. 40 g Roh-Zirkontetrachlorid mit einem Gehalt von 1,6 0je Fe, 0,013 01, Ti und 1,7 0je Al wurden im Stickstoffstrom, der bei 35° C mit Petroläther (Siedebereich 40 bis 600 C, Hauptbestandteil C5 und C6) gesättigt war, sublimiert. Das Sublimat enthielt noch 0,04 0je Fe, 0,0010/, Ti und 0,06 0/o Al. 5. 40 g of crude zirconium tetrachloride with a content of 1.6% per Fe, 0.013 01, Ti and 1.7 Al were in a stream of nitrogen, which at 35 ° C with petroleum ether (boiling range 40 to 600 C, main components C5 and C6) was saturated, sublimed. The sublimate still contained 0.040% Fe, 0.0010% Ti and 0.06% Al.
Das Verfahren der Erfindung läßt sich auch sehr leicht kontinuierlich gestalten, ein sehr wichtiger technischer Vorteil. Dabei wird es sich empfehlen, zumindest mit eilweiser Rückführung der Kohlenwasserstoff enthaltenen Gase zu arbeiten. Wird schließlich allerreinstes Material verlangt (bei stark verunreinigtem Rohstoff), o kann die Sublimation ohne großen Aufwand leicht viederholt werden. The process of the invention can also be very easily carried out continuously shape, a very important technical advantage. It is recommended to at least with partial recirculation of the hydrocarbon contained Working gases. Ultimately, the purest material is required (if it is heavily contaminated Raw material), o the sublimation can easily be repeated without great effort.
Claims (3)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1068683B true DE1068683B (en) | 1959-11-12 |
Family
ID=593976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1068683D Pending DE1068683B (en) | Process for the production of pure zirconium tetrachloride by sublimation |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1068683B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188810A (en) * | 1991-06-27 | 1993-02-23 | Teledyne Industries, Inc. | Process for making niobium oxide |
| US5211921A (en) * | 1991-06-27 | 1993-05-18 | Teledyne Industries, Inc. | Process of making niobium oxide |
| US5234674A (en) * | 1991-06-27 | 1993-08-10 | Teledyne Industries, Inc. | Process for the preparation of metal carbides |
| US5284639A (en) * | 1991-06-27 | 1994-02-08 | Teledyne Industries, Inc. | Method for the preparation of niobium nitride |
| US5322548A (en) * | 1991-06-27 | 1994-06-21 | Teledyne Industries, Inc. | Recovery of niobium metal |
| US5468464A (en) * | 1991-06-27 | 1995-11-21 | Teledyne Industries, Inc. | Process for the preparation of metal hydrides |
-
0
- DE DENDAT1068683D patent/DE1068683B/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5188810A (en) * | 1991-06-27 | 1993-02-23 | Teledyne Industries, Inc. | Process for making niobium oxide |
| US5211921A (en) * | 1991-06-27 | 1993-05-18 | Teledyne Industries, Inc. | Process of making niobium oxide |
| US5234674A (en) * | 1991-06-27 | 1993-08-10 | Teledyne Industries, Inc. | Process for the preparation of metal carbides |
| US5284639A (en) * | 1991-06-27 | 1994-02-08 | Teledyne Industries, Inc. | Method for the preparation of niobium nitride |
| US5322548A (en) * | 1991-06-27 | 1994-06-21 | Teledyne Industries, Inc. | Recovery of niobium metal |
| US5468464A (en) * | 1991-06-27 | 1995-11-21 | Teledyne Industries, Inc. | Process for the preparation of metal hydrides |
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