DE1070603B - Process for removing oxygen from carbon dioxide or gas mixtures containing carbon dioxide - Google Patents
Process for removing oxygen from carbon dioxide or gas mixtures containing carbon dioxideInfo
- Publication number
- DE1070603B DE1070603B DENDAT1070603D DE1070603DA DE1070603B DE 1070603 B DE1070603 B DE 1070603B DE NDAT1070603 D DENDAT1070603 D DE NDAT1070603D DE 1070603D A DE1070603D A DE 1070603DA DE 1070603 B DE1070603 B DE 1070603B
- Authority
- DE
- Germany
- Prior art keywords
- carbon dioxide
- copper
- mixtures containing
- gas mixtures
- removing oxygen
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 19
- 239000007789 gas Substances 0.000 title claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 14
- 239000001301 oxygen Substances 0.000 title claims description 14
- 229910052760 oxygen Inorganic materials 0.000 title claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 7
- 239000001569 carbon dioxide Substances 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 title description 7
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 229910002090 carbon oxide Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPPSCXPWECCHRD-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Cu+2].[Fe+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Cu+2].[Fe+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] QPPSCXPWECCHRD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Description
DEUTSCHESGERMAN
KL.12i 34 ^KL.12i 34 ^
INTERNAT. KL. C OlINTERNAT. KL. C Ol
PATENTAMTPATENT OFFICE
C01B -31/1»C01B -31/1 »
ANMELDETAG.REGISTRATION DAY.
B 50588 IVa/12 iB 50588 IVa / 12 i
3. OKTOBER 1958OCTOBER 3, 1958
BEKANNTMACHUNG
DER ANMELDUNG
UND AUSGABE DER
AUSLEGESCHRIFT: 10. DEZEMBER 1959NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: DECEMBER 10, 1959
Es ist bekannt, Kupier-Eisen-Yerbindungen zur Entfernung verschiedener Verunreinigungen von Gasen zu verwenden. Es ist auch bekannt, Kupfer-Eisen-Verbindungen zur Entfernung von Sauerstoff aus kohlenoxydhaltigen Gasen heranzuziehen. Bei 5 diesen bekannten Verfahren gelingt es jedoch nicht, den Sauerstoffgehalt der zu reinigenden Gase unter die Grenze von 30 ppm zu bringen. Bei der Entfernung von Kohlenoxyd aus technischen Gasen durch Tiefkühlung mit flüssigem Stickstoff darf jedoch der Sauerstoffgehalt der zu reinigenden Gase diese Grenze nicht überschreiten, da es sonst zur Bildung explosiver Gasgemische kommt.It is known to use Kupier-Eisen-Yerbindungen to remove various impurities from To use gases. It is also known to be copper-iron compounds to be used for the removal of oxygen from gases containing carbon oxide. However, with these known methods it is not possible to to bring the oxygen content of the gases to be cleaned below the limit of 30 ppm. At the distance of carbon dioxide from technical gases by deep-freezing with liquid nitrogen, however, is allowed Oxygen content of the gases to be cleaned do not exceed this limit, otherwise it leads to the formation of explosive Gas mixture comes.
Es wurde nun gefunden, daß man die zur Entfernung von Sauerstoff verwendete Kupfer-Eisen-Masse beträchtlich aktivieren kann, wenn man ihr geringe Mengen Gold bzw. Goldverbindungen zugibt.It has now been found that the copper-iron mass used to remove oxygen can be used can activate considerably if you add small amounts of gold or gold compounds to it.
Durch den Goldzusatz wird nicht nur die Umsetzungstemperatur wesentlich herabgesetzt, sondern auch eine beträchtliche Verlängerung der Aktivität der Kupfer-Eisen-Masse erreicht. Es ist vorteilhaft, die mit Gold aktivierte Kupfer-Eisen-Masse mit Kohlenoxyd bzw. kohlenoxydhaltigen Gasgemischen vor ihrer Verwendung zu behandeln. Durch diese Vorbehandlung wird eine weitere Aktivierung erzielt. Diese Vorbehandlung kann beispielsweise so erfolgen, daß man über die Kupfer-Eisen-Masse Kohlenoxyd hinwegführt oder die Kupfer-Eisen-Masse längere Zeit, z. B. eine oder mehrere Stunden in einer Kohlenoxydatmosphäre, vorteilhaft bei geringem Überdruck. z.B. bei 30 bis 150mm Hg-Überdruck, stehenläßt. Man kann aber auch die Kupfer-Eisen-Masse mehrere Stunden mit dem zu reinigenden Gas stehenlassen.The addition of gold not only significantly lowers the reaction temperature, but a considerable prolongation of the activity of the copper-iron mass is also achieved. It is beneficial the copper-iron mass activated with gold with carbon oxide or gas mixtures containing carbon oxide treat before use. Further activation is achieved through this pretreatment. This pretreatment can be done, for example, by adding carbon oxide over the copper-iron mass leads away or the copper-iron mass for a long time, e.g. B. one or more hours in a carbon dioxide atmosphere, advantageous with low overpressure. e.g. at 30 to 150mm Hg overpressure. But you can also leave the copper-iron mass for several hours with the gas to be cleaned.
Die Kupfer-Eisen-Masse wird im allgemeinen mit 0,1 bis 1,0 Gewichtsprozent Gold versetzt. Man kann jedoch auch größere Mengen Gold zusetzen. Ausgezeichnete Wirkungen erzielt man. wenn man zu einer Kupfer-Eisen-Nitratlösung Goldchlorid hinzufügt und die Metalle mit Soda fällt. Es ist zweckmäßig, die Fällung mit destilliertem Wasser nitratfrei zu waschen und durch Formen und Trocknen bei etwa 200° C in eine gebrauchsfertige Form zu bringen.The copper-iron mass is generally mixed with 0.1 to 1.0 percent by weight of gold. One can however, also add larger amounts of gold. Excellent effects are achieved. if one to gold chloride is added to a copper-iron-nitrate solution and the metals are precipitated with soda. It is appropriate Wash the precipitate free of nitrates with distilled water and mold and dry at about 200 ° C in a ready-to-use form.
Durch das erfindungsgemäße Verfahren ist es möglich, Sauerstoff aus Kohlenoxyd oder kohlenoxydhaltigen Gasen bei hohen Strömungsgeschwindigkeiten und schon bei Temperaturen von 0 bis 40° C, z. B. bei 25° C, bei Normaldruck zu entfernen und den Sauerstoffgehalt bis auf etwa 1 ppm herabzusetzen. Die Behandlung der Gase zur Sauerstoffentfernung kann aber auch bei jedem anderen beliebigen Druck erfolgen.With the method according to the invention it is possible to obtain oxygen from carbon oxides or carbon oxides Gases at high flow rates and even at temperatures from 0 to 40 ° C, e.g. B. at 25 ° C, to remove at normal pressure and reduce the oxygen content to about 1 ppm. The treatment of the gases for the removal of oxygen can, however, also take place at any other pressure take place.
Ein weiterer Vorteil des Verfahrens besteht darin, daß die zu reinigenden Gase auch von Stickstoffoxyd befreit werden.Another advantage of the process is that the gases to be cleaned are also free of nitrogen oxide to be freed.
Verfahren zur EntfernungProcedure for removal
von Sauerstoff aus Kohlenoxydof oxygen from carbon monoxide
oder kohlenoxydhaltigen Gasgemischenor gas mixtures containing carbon oxides
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft,Corporation,
Ludwigshafen/RheinLudwigshafen / Rhine
Dr. Max Schütze, Ludwigshafen/Rhein,
ist als Erfinder genannt wordenDr. Max Schütze, Ludwigshafen / Rhine,
has been named as the inventor
B e i s ρ i e 1 1B e i s ρ i e 1 1
Durch Fällen einer Lösung von Eisennitrat, Kupfernitrat und Goldchlorid mit Soda. Waschen und Tablettieren wird ein Katalysator hergestellt, der 38 %> Eisen, 26°/» Kupfer und 0,5% (JoId enthält.By precipitating a solution of iron nitrate, copper nitrate and gold chloride with soda. Washing and tabletting a catalyst is produced which contains 38% iron, 26% copper and 0.5% (JoId.
Leitet man über einen derartigen Katalysator ein Gasgemisch, das aus etwa 92°/o Wasserstoff, 6% Kohlenoxyd und 2% Stickstoff besteht und 450 ppm Sauerstoff enthält, mit einer Belastung von 30 0001 Gas pro Liter Katalysator in der Stunde, dann geht bei einer Reaktionstemperatur von 40° C der Sauerstoffgehalt auf 1 ppm zurück. Verwendet man dagegen einen unter den gleichen Bedingungen hergestellten Katalysator, der kein Gold enthält, dann wird auch bei 60° C der Sauerstoffgehalt nur auf 30 ppm gesenkt. Der Katalysator ermüdet aber schon nach 30 Minuten.If a gas mixture consisting of about 92% hydrogen, 6% Carbon oxide and 2% nitrogen and contains 450 ppm oxygen, with an exposure of 30,0001 Gas per liter of catalyst per hour, then the oxygen content goes down at a reaction temperature of 40 ° C back to 1 ppm. On the other hand, if you use one made under the same conditions If the catalyst does not contain gold, the oxygen content is only reduced to 30 ppm even at 60 ° C. The catalytic converter fatigues after just 30 minutes.
Man läßt zunächst den im Beispiel 1 beschriebenen Katalysator 2 Stunden lang unter einem Kohlenoxydüberdruck von 60 mm Hg bei 25° C im Reaktionsrohr stehen und schickt dann das zu reinigende Gas, das die gleiche Zusammensetzung wie im Beispiel 1 hat, mit einer Belastung von 30 000 1 Gas pro Liter Katalysator und Stunde bei 25° C über den Katalysator. Der Sauerstoff des Gasgemisches wird auch bei 25° C bis auf 1 ppm entfernt.The catalyst described in Example 1 is first left under a positive pressure of carbon dioxide for 2 hours of 60 mm Hg at 25 ° C in the reaction tube and then sends the gas to be purified, the has the same composition as in Example 1, with a loading of 30,000 liters of gas per liter of catalyst and hour at 25 ° C over the catalyst. The oxygen in the gas mixture is also at 25 ° C removed down to 1 ppm.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1070603B true DE1070603B (en) | 1959-12-10 |
Family
ID=595465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1070603D Pending DE1070603B (en) | Process for removing oxygen from carbon dioxide or gas mixtures containing carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1070603B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3481987A (en) * | 1967-08-14 | 1969-12-02 | Union Oil Co | Removal of oxygen impurity from carbon monoxide |
-
0
- DE DENDAT1070603D patent/DE1070603B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3481987A (en) * | 1967-08-14 | 1969-12-02 | Union Oil Co | Removal of oxygen impurity from carbon monoxide |
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