DE145748C - - Google Patents
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- Publication number
- DE145748C DE145748C DENDAT145748D DE145748DC DE145748C DE 145748 C DE145748 C DE 145748C DE NDAT145748 D DENDAT145748 D DE NDAT145748D DE 145748D C DE145748D C DE 145748DC DE 145748 C DE145748 C DE 145748C
- Authority
- DE
- Germany
- Prior art keywords
- cyanide
- gases
- hydrogen
- cyanides
- oxidation
- 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.)
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- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229910052813 nitrogen oxide Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001913 cyanates Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative Effects 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N Sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- VLYFRFHWUBBLRR-UHFFFAOYSA-L potassium;sodium;carbonate Chemical compound [Na+].[K+].[O-]C([O-])=O VLYFRFHWUBBLRR-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- -1 sodium rhodium Chemical compound 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/10—Simple alkali metal cyanides
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Gegenstand vorliegender Erfindung bildet ein Verfahren, die bei der Oxydation von Rhodansalzen mit Salpetersäure entstehenden blausäurehaltigen Gase, denen Sauerstoff der Luft und Stickoxyd beigemischt ist, zwecks Bildung von Cyaniden, statt, wie bisher üblich, durch kaustische Alkalien absorbieren zu lassen, über alkalische Karbonate bei höherer Temperatur, am besten dunkler Rotglut, zu leiten.The present invention provides a method that in the oxidation of Rhodane salts with nitric acid result in gases containing hydrocyanic acid, to which oxygen the Air and nitrogen oxide is mixed in to form cyanides instead of, as has been the case up to now, to be absorbed by caustic alkalis, via alkaline carbonates at higher temperatures, best of dark red heat to conduct.
Es . ist allerdings aus der Patentschrift 132999, Kl. 12 (vergl. r. Sp. Beispiel) bekannt, ein Gemisch von Blausäure und Wassergas über ein Gemenge gleicher Moleküle Kaliumkarbonat und Natriumkarbonat bei verhältnismäßig hohen Temperaturen, nämlich solchen, die über dem Schmelzpunkt der betreffenden Cyanide liegen, zu leiten (vergl. auch das Patent 134102, Kl. 12). Es handelt sich hierbei um Gasgemische, welche neben Blausäure Wasserstoff und Kohlenoxyd, also reduzierende Gase enthalten. Daß Gasgemische, welche neben Blausäure überschüssigen Sauerstoff oder Stickoxyd enthalten und also bei höherer Temperatur energisch oxydierend wirken, in technisch verwertbarer , Weise Cyanide und nicht Cyanate liefern würden, war aber aus den besagten Patentschriften nicht zu ersehen und durchaus nicht zu schließen. 'It. is, however, known from patent specification 132999, class 12 (see r. Sp. example), a mixture of hydrogen cyanide and water gas over a mixture of the same molecules of potassium carbonate and sodium carbonate at relatively high temperatures, namely those above the melting point of the respective Cyanide are to conduct (see also the patent 134102, cl. 12). It deals These are gas mixtures which, in addition to hydrogen cyanide, are hydrogen and carbon oxide, i.e. contain reducing gases. That gas mixtures which, in addition to hydrocyanic acid, excess Contain oxygen or nitrogen oxide and therefore energetically oxidizing at higher temperatures act in a technically usable manner would deliver cyanides and not cyanates, but could not be seen from the patent specifications mentioned and was by no means closed conclude. '
Das vorliegende Verfahren hat zuerst die Möglichkeit dargetan, aus oxydierenden Gasgemischen direkt durch Alkalikarbonate bei höherer Temperatur Cyanide zu erhalten. Ferner wird im Gegensatz zu dem bekannten Verfahren das gebildete Cyanid in der Blausäureatmosphäre nicht geschmolzen, wodurch Verluste aller Art entstehen würden, vielmehr wird die Temperatur möglichst niedrig bemessen, um das Cyanid während der ganzen Reaktionsdauer tief unter seinem Schmelzpunkt zu halten.The present process first demonstrated the possibility of using oxidizing gas mixtures to obtain cyanides directly from alkali carbonates at higher temperatures. Furthermore, in contrast to the known The process does not melt the cyanide formed in the hydrogen cyanide atmosphere, as a result of which Losses of all kinds would arise, rather the temperature is set as low as possible, in order to keep the cyanide well below its melting point during the entire reaction period.
Arbeitet man z. B. mit Natriumkarbonat, so hält man zweckmäßig eine Temperatur von etwa 450° ein und behandelt das trockene Karbonat in methodischer Weise mit den blausäurehaltigen Gasen, bis die Umwandlung vollendet ist. Man erhält so ein etwa 98 bis 990 Cyannatrium als feines Pulver, welches in Wasser fast momentan löslich ist und, wenn gewünscht, leicht umgeschmolzen werden kann. Es enthält nur wenig Cyanat.Do you work z. B. with sodium carbonate, it is advisable to keep a temperature of about 450 ° and treat the dry carbonate methodically with the hydric acid-containing gases until the conversion is complete. Is obtained as an approximately 98 to 99 0 sodium cyanide as a fine powder, which is currently almost soluble in water and, if so, can be easily remelted desired. It contains very little cyanate.
Die Temperatur von etwa 450 ° ist die günstigste für die Ausnutzung der Blausäure; es entsteht hierbei keine Spur von Ammoniak und wenig Cyanat. Zu bemerken ist jedoch, daß bereits unter 200 ° Cyanidbildung stattfindet, wenn auch nur langsam und unter Bräunung, während bei Temperaturen von etwa 500° bis zur Schmelzung des Karbonats die Bildung von Cyanat und Ammoriiak immer mehr hervortritt und die Ausbeute beeinträchtigt; dagegen fällt das Produkt um so weißer aus als die Temperatur höher ist.The temperature of about 450 ° is the most favorable for the utilization of hydrogen cyanide; there is no trace of ammonia and little cyanate. It should be noted, however, that cyanide formation already takes place below 200 °, albeit slowly and below Browning while at temperatures of about 500 ° until the carbonate melts the formation of cyanate and ammonia becomes more and more prominent and affects the yield; on the other hand, the product turns out whiter as the temperature is higher.
Arbeitet man mit kohlensaurem Kali statt mit Soda, so kann man eine etwas niedrigere Temperatur einhalten.If you work with carbonate of potash instead of soda, you can use a slightly lower one Maintain temperature.
Das Gasgemisch, welches durch Oxydation von Rhodannatrium mittels Salpetersäure beiThe gas mixture produced by the oxidation of sodium rhodium by means of nitric acid
Gegenwart von überschüssiger Luft entstand und nach dem Trocknen neben Stickstoff etwa io Prozent HCN und 7 Prozent freien Sauerstoff enthielt, wurde in methodischer Weise über fein verteiltes, wasserfreies Natriumkarbonat bei 45 o° geleitet. Zur vollständigen Umwandlung war ungefähr die vierfache Menge der theoretisch berechneten Blausäure notwendig. Es war genug überschüssigen Sauerstoffs vorhanden, um fünfmal so viel als die zu erhaltende Menge Cyanid vollständig in Cyanat zu. verwandeln. Das Produkt enthielt aber nur 1 bis 2 Cyanat, neben 98 bis 99 Prozent Cyanid.The presence of excess air resulted and after drying contained about 10 percent HCN and 7 percent free oxygen in addition to nitrogen, it was passed in a methodical manner over finely divided, anhydrous sodium carbonate at 45 °. About four times the amount of the theoretically calculated hydrocyanic acid was necessary for complete conversion. There was enough excess oxygen to convert all of the cyanide into cyanate five times what was to be retained. transform. However, the product only contained 1 to 2 cyanates, in addition to 98 to 99 percent cyanide.
Ähnliche Resultate wurden mit dem Gemisch von Blausäure und Stickoxyd erhalten, welches . bei der Oxydation von Rhodansalzen mittels Salpetersäure bei Luftabschluß entsteht.Similar results were obtained with the mixture of hydrogen cyanide and nitrogen oxide, which . arises from the oxidation of rhodan salts by means of nitric acid in the absence of air.
Claims (1)
Publications (1)
Publication Number | Publication Date |
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DE145748C true DE145748C (en) |
Family
ID=413069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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Country Status (1)
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE972009C (en) * | 1943-10-13 | 1959-05-06 | Degussa | Process for the removal of hydrocyanic acid from low blue acid, ammonia and optionally further components containing gas mixtures |
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0
- DE DENDAT145748D patent/DE145748C/de active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE972009C (en) * | 1943-10-13 | 1959-05-06 | Degussa | Process for the removal of hydrocyanic acid from low blue acid, ammonia and optionally further components containing gas mixtures |
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