DE845500C - Process for the purification of crude, volatile metal chlorides obtained by chlorinating oxidic ores - Google Patents
Process for the purification of crude, volatile metal chlorides obtained by chlorinating oxidic oresInfo
- Publication number
- DE845500C DE845500C DEP14065D DEP0014065D DE845500C DE 845500 C DE845500 C DE 845500C DE P14065 D DEP14065 D DE P14065D DE P0014065 D DEP0014065 D DE P0014065D DE 845500 C DE845500 C DE 845500C
- Authority
- DE
- Germany
- Prior art keywords
- crude
- chlorides
- metal chlorides
- gases
- purification
- 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
- 229910001510 metal chloride Inorganic materials 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 12
- 238000000746 purification Methods 0.000 title claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 201000009032 substance abuse Diseases 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1231—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes treatment or purification of titanium containing products obtained by dry processes, e.g. condensation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/06—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
- C01G23/024—Purification of tetrachloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
Description
AUSGEGEBEN AM 31. JULI 1952ISSUED JULY 31, 1952
p 14065IVb/12 η Dp 14065IVb / 12 η D
Die vorliegende Erfindung betrifft ein Verfahren zur Reinigung von rohen, durch Chlorieren oxydischer Erze erhaltenen, flüchtigen Metallchloriden, insbesondere von Titan- und Zirkontetrachlorid.The present invention relates to a process for the purification of crude, oxidic by chlorination Volatile metal chlorides obtained from ores, especially titanium and zirconium tetrachloride.
Die hierbei als Ausgangsmaterialien dienenden rohen flüchtigen Metallchloride werden dadurch erhalten, daß die Erze der entsprechenden Metalle, deren Chloride in reiner Form gewonnen werden sollen, mit Reduktionskohle vermischt, bei höheren Temperaturen mit Chlorgas behandelt und die dabei entstehenden Dämpfe kondensiert werden. Die auf diese Weise gewonnenen flüchtigen Rohchloride sind durch Chloride und Oxychloride der ihr Metall im Erz begleitenden Nebenmetalle stark verunreinigt und gefärbt. Sie enthalten außerdem wechselnde Mengen von Chlor, Phosgen, Chlorwasserstoff, Kühlenoxyd und anderen Gasen in gelöster Form.The crude volatile metal chlorides used as starting materials are obtained by that the ores of the corresponding metals, the chlorides of which are obtained in pure form should, mixed with reducing carbon, treated with chlorine gas at higher temperatures and the thereby resulting vapors are condensed. The volatile crude chlorides obtained in this way are heavily contaminated by chlorides and oxychlorides of the secondary metals accompanying their metal in the ore and colored. They also contain varying amounts of chlorine, phosgene, hydrogen chloride, Cooling oxide and other gases in dissolved form.
Unter den Chloriden sind zu unterscheiden: einerseits Chloride, deren Dämpfe sich bei Atmosphärendruck zu einer Flüssigkeit kondensieren lassen, wie z. B. die Tetrachloride von Silicium und Titan, andererseits Chloride, die bei Atmosphärendruck keine flüssigen Phasen bilden und sich daher nicht destillieren, sondern nur sublimieren lassen, wie Zirkontetrachlorid und Aluminiumtnchlorid.Among the chlorides are to be differentiated: on the one hand chlorides, whose vapors are at atmospheric pressure let condense into a liquid, such as. B. the tetrachlorides of silicon and Titanium, on the other hand chlorides, which do not form liquid phases at atmospheric pressure and therefore do so do not distill, just allow to sublime, such as zirconium tetrachloride and aluminum chloride.
Um nun die Chloride im reinen Zustand zu erhalten, müssen sie einem Reinigungsverfahren unterworfen werden. Bei flüssigen Chloriden geschieht dies bisher in einer Weise, die an einem Beispiel, nämlich der Reinigung von Titantetrachlorid, im nachfolgenden näher beschrieben wird. Das rohe Titantetrachlorid, das infolge der in ihm noch gelösten oder suspendierten Chloride und Oxychloride der Fremdmetalle, insbesondere vonIn order to keep the chlorides in their pure state, they have to go through a cleaning process be subjected. In the case of liquid chlorides, this has so far been done in a way that Example, namely the purification of titanium tetrachloride, is described in more detail below. The crude titanium tetrachloride, which as a result of the chlorides still dissolved or suspended in it Oxychloride of foreign metals, especially of
Vanadin, Chrom und Eisen, stark gefärbt und trübe ist, während das gereinigte Titantetrachlorid klar und farblos ist, wird zunächst mechanisch yorgereinigt, indem man durch Filtrieren oder durch Absetzenlassen und Dekantieren die darin suspendierten festen Verunreinigungen ausscheidet. Sodann läßt man das so vorgereinigte, aber noch gefärbte Rohchlorid mit den darin gelösten Chloriden, Oxychloriden und Gasen verdampfen und in Dampf- oder Gasform durch eine Schicht von Adsorptionsmittel, z. B. Aktivkohle u. dgl., strömen. Dabei werden die Verunreinigungen durch Adsorption, zum Teil nach vorgängig erfolgter chemischer Reaktion, beseitigt, so daß das Titantetrachlorid die Adsorpt5 tionskolonne gereinigt verläßt. In gewissen Fällen ist es nämlich notwendig, hierbei den Chloriddämpfen noch Wasserstoff zuzusetzen. In anderen Fällen genügt eine Kolonne mit oberflächeninaktiven Füllstoffen, die von den Chloriddämpfen unter ao Wasserstoffzusatz zu durchstreichen sind.Vanadium, chromium, and iron are strongly colored and cloudy, while the purified titanium tetrachloride is clear and is colorless, is first mechanically purified by filtering or by Allowing to settle and decanting eliminates the solid impurities suspended therein. Then if the crude chloride, which has been pre-cleaned but still colored, is left with the chlorides dissolved in it, Oxychlorides and gases evaporate and in steam or gaseous form through a layer of adsorbent, e.g. B. activated carbon and the like., Flow. Be there the contamination through adsorption, partly after a previous chemical reaction, eliminated so that the titanium tetrachloride the adsorpt5 tion column cleaned leaves. In certain cases it is necessary to use the chloride vapors still add hydrogen. In other cases, a column with surface-inactive ones is sufficient Fillers that have to be crossed out by the chloride vapors with the addition of hydrogen.
Nach allen diesen Methoden verläuft jedoch die Reinigung nicht mit der für die technische Ausführung notwendigen Gleichmäßigkeit und Sicherheit; einerseits ist die Geschwindigkeit, mit welcher J5 die Entfernung der färbenden Chloride und Oxychloride erfolgt, sehr großen und sehr oft plötzlichen Schwankungen unterworfen, andererseits läßt die Aufnahmefähigkeit der Kolonne in den meisten Fällen auffallend rasch nach. Die deshalb erforderlichen großen Reinigungsapparaturen und der übermäßig große Verbrauch an Adsorptionsmitteln standen daher bisher einör technisch und wirtschaftlich tragbaren Durchführung des Reinigungsprozesses im Wege.According to all these methods, however, the cleaning does not proceed with the uniformity and safety necessary for the technical execution; on the one hand, the speed is carried out with which J 5 the removal of the coloring chlorides and oxychlorides, subjected to very large and very often sudden fluctuations, on the other hand the capacity of the column can be remarkably by rapidly in most cases. The large cleaning equipment required for this and the excessive consumption of adsorbents have therefore hitherto stood in the way of a technically and economically viable implementation of the cleaning process.
Es wurde nun gefunden, daß als Ursache dieser Mißstände jene Gase zu betrachten sind, welche, wie z. B. Chlor, Phosgen, Kohlenmonoxyd u. dgl., im Chlorid gelöst sind, und daß die Reinigung gleichmäßig sicher und mit andauerndem Erfolg dann durchzuführen ist, wenn die genannten Gase vor der Reinigung des rohen Chlorids entfernt wer-, den. Ist dies einmal geschehen, so arbeiten die oben beschriebenen Reinigungsverfahren mit voller Zufriedenheit, mit guter Ausnutzung der Adsorptionsfähigkeit der Adsorbentien und überdies noch bei wesentlich gesteigerter Strömungsgeschwindigkeit in der Adsorptionskolonne.It has now been found that the cause of these abuses are those gases which such as B. chlorine, phosgene, carbon monoxide and the like. Are dissolved in the chloride, and that the cleaning can be carried out consistently safely and with lasting success if the gases mentioned be removed prior to purification of the crude chloride. Once this is done, those above work described cleaning process with full satisfaction, with good utilization of the adsorption capacity of the adsorbents and, moreover, at a significantly increased flow rate in the adsorption column.
Eine einfache, für alle vorkommenden Rohchloride anwendbare, aber nicht sehr wirksame Entgasung besteht darin, daß die rohen Metallchloride gegebenenfalls unter Erhitzung derselben mit Vakuum von den in ihnen gelösten Gasen befreit werden. Eine bessere Entgasung kann bei den leicht flüchtigen, flüssigen Rohchloriden dadurch erzielt werden, daß die rohen Metallchloride durch Erhitzen am Rückflußkühler bei normalem oder vermindertem Druck von den in ihnen gelösten Gasen befreit werden. Bei Chloriden, die bei Atmosphärendruck keine flüssige Phase aufweisen, wie z. B. Zirkonchlorid, kann die Entfernung der Gase dadurch verbessert werden, daß die festen Chloride bei Drucken unter ι atü durch Erhitzen bis auf Temperaturen, bei denen bereits ein Teil der festen Chloridemit den Gasen verflüchtigt wird, von den in ihnen gelösten Gasen befreit werden. Schwer fluchtige Chloride, deren Schmelz- und Siedepunkte "nicht weit auseinanderliegen, wie z. B. Niobpentachlorid, können sowohl im festen Zustand durch teilweise Verflüchtigung des festen Chlorids bei Drucken unter 1 atü als auch in flüssigem Zustand durch Erhitzen am Rückflußkühler von den in ihnen gelösten Gasen befreit werden. Die Entgasung braucht nicht unbedingt vollständig zu sein, sondern nur bis zu einem gewissen Gasgehalt durchgeführt zu werden, welcher bei dem sich anschließenden Reinigungsverfahren nicht mehr schädlich ist. Nach Versuchen liegt diese Grenze für Chlor bei etwa 0,1 %>, für Phosgen bei etwa 0,2%. Es ist deshalb auch möglich, einen Teil der Gase durch Adsorption an Aktivkohle oder einem SiO2-haltigen Adsorptionsmittel bei Temperaturen knapp über dem Siedepunkt bzw. Sublimationspunkt zu binden, bei denen die störenden Chloride und Oxychloride der Fremdmetalle noch nicht adsorbiert werden, um dann erst das noch nicht völlig entgaste Metallchlorid bei höheren Temperaturen oberhalb 250 bis 3000 in einer zweiten Adsorptionskolonne von dem Rest der störenden Chloride und Oxychloride zu befreien. Diese Entgasungsverfahren sind auf alle flüchtigen Chloride anwendbar, so also auch auf die Tetrachloride von Silicium und Zinn, auf Aluminium u. dgl.A simple, but not very effective degassing, which can be used for all crude chlorides that occur, consists in releasing the gases dissolved in them from the crude metal chlorides, if necessary by heating them with a vacuum. Better degassing of the volatile, liquid crude chlorides can be achieved in that the crude metal chlorides are freed from the gases dissolved in them by heating them in a reflux condenser at normal or reduced pressure. In the case of chlorides that do not have a liquid phase at atmospheric pressure, such as. B. zirconium chloride, the removal of the gases can be improved in that the solid chlorides are freed from the gases dissolved in them at pressures below ι atm by heating up to temperatures at which a part of the solid chlorides is already volatilized with the gases. Hardly volatile chlorides whose melting and boiling points are "not far apart, such as niobium pentachloride, can be removed from them both in the solid state by partial volatilization of the solid chloride at pressures below 1 atmospheric pressure and in the liquid state by heating in a reflux condenser The degassing does not necessarily have to be complete, but only to be carried out up to a certain gas content, which is no longer harmful in the subsequent cleaning process. According to tests, this limit for chlorine is around 0.1%> , for phosgene at about 0.2%. It is therefore also possible to bind some of the gases by adsorption on activated carbon or an adsorbent containing SiO 2 at temperatures just above the boiling point or sublimation point at which the interfering chlorides and oxychlorides the foreign metals are not yet adsorbed, only then to the not yet completely degassed metal chloride at higher To free temperatures above 250 to 300 0 in a second adsorption column from the rest of the interfering chlorides and oxychlorides. These degassing processes can be used for all volatile chlorides, including the tetrachlorides of silicon and tin, aluminum and the like.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH627904X | 1946-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE845500C true DE845500C (en) | 1952-07-31 |
Family
ID=4524532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP14065D Expired DE845500C (en) | 1946-06-27 | 1948-10-02 | Process for the purification of crude, volatile metal chlorides obtained by chlorinating oxidic ores |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE845500C (en) |
| FR (1) | FR947580A (en) |
| GB (1) | GB627904A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2467821A1 (en) * | 1979-10-18 | 1981-04-30 | Zaporozhsky Titano Magnievy | DEVICE FOR SEPARATING TITANIUM TETRACHLORIDE FROM A VAPOR-GAS MIXTURE |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820698A (en) * | 1954-06-25 | 1958-01-21 | Du Pont | Process for purifying silicon halide |
| US2813008A (en) * | 1954-06-25 | 1957-11-12 | Du Pont | Method of purifying silicon tetrafluoride |
| US2804377A (en) * | 1954-06-25 | 1957-08-27 | Du Pont | Preparation of pure silicon |
| US2805133A (en) * | 1954-06-25 | 1957-09-03 | Du Pont | Preparation of pure silicon |
| US2931709A (en) * | 1956-09-17 | 1960-04-05 | Robert S Aries | Decarburizing silicon tetrachloride |
| NL235008A (en) * | 1958-01-11 | |||
| NL246431A (en) * | 1958-12-16 | 1900-01-01 | ||
| DE1155098B (en) * | 1960-06-10 | 1963-10-03 | Siemens Ag | Process for the extraction of the purest silicon |
| US3161474A (en) * | 1960-06-21 | 1964-12-15 | Siemens Ag | Method for producing hyperpure semiconducting elements from their halogen compounds |
| DE10030252A1 (en) * | 2000-06-20 | 2002-01-03 | Degussa | Separation of metal chlorides from their suspensions in chlorosilanes |
-
1947
- 1947-06-02 GB GB14587/47A patent/GB627904A/en not_active Expired
- 1947-06-06 FR FR947580D patent/FR947580A/en not_active Expired
-
1948
- 1948-10-02 DE DEP14065D patent/DE845500C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2467821A1 (en) * | 1979-10-18 | 1981-04-30 | Zaporozhsky Titano Magnievy | DEVICE FOR SEPARATING TITANIUM TETRACHLORIDE FROM A VAPOR-GAS MIXTURE |
Also Published As
| Publication number | Publication date |
|---|---|
| GB627904A (en) | 1949-08-18 |
| FR947580A (en) | 1949-07-06 |
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