DE1078550B - Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogen - Google Patents
Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogenInfo
- Publication number
- DE1078550B DE1078550B DEB45205A DEB0045205A DE1078550B DE 1078550 B DE1078550 B DE 1078550B DE B45205 A DEB45205 A DE B45205A DE B0045205 A DEB0045205 A DE B0045205A DE 1078550 B DE1078550 B DE 1078550B
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen
- catalyst
- carbon oxide
- copper
- manganese
- 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 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 27
- 239000001257 hydrogen Substances 0.000 title claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 24
- 229910002090 carbon oxide Inorganic materials 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 14
- 230000003197 catalytic effect Effects 0.000 title claims description 9
- 231100000614 poison Toxicity 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- -1 manganese activated nickel-copper Chemical class 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 206010010774 Constipation Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/045—Purification by catalytic desulfurisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur katalytischen Entfernung von Kontaktgiften, insbesondere Kohlenoxyd, aus Wasserstoff Wasserstoff, der aus dem Wassergasprozeß stammt und mit ammoniakalischer Kupferlauge gewaschen ist, enthält noch Kohlenoxyd sowie etwas Sauerstoff und Schwefel. Für die meisten katalytischen Hydrierverfahren muß der zur Anwendung kommende Wasserstoff aber völlig frei von Kohlenoxyd, Sauerstoff und Schwefel sein, da die Metalle, wie Nickel, Kobalt, Eisen, Palladium oder Kupfer, unter deren katalytischer Einwirkung die Hydrierung durchgeführt wird, durch sie, insbesondere durch Kohlenoxyd, größtenteils inaktiviert werden und bei höherem Kohlenoxydgehalt des Wasserstoffs vollständig vergiftet werden können. Oft sind geringe Kohlenoxydmengen im Wasserstoff der Grund dafür, daß die Lebensdauer der angewendeten Katalysatoren sehr gering ist. Schwach vergiftete Katalysatoren erfordern stets eine höhere Reaktionstemperatur, die sich auf die Ausbeute und die Reinheit der herzustellenden Produkte ungünstig auswirkt. Die chemische Industrie- bringt heute eine Reihe von -Produkten auf den Markt, an deren Reinheit sehr hohe Anforderungen gestellt werden. So darf z. B. ein gutes Äthylhexanol, wie es z. B. für Weichmacher Verwendung findet, mit konzentrierter Schwefelsäure gemischt, sich nicht verfärben. Verwendet man bei der Herstellung des Äthylhexanols für- den Hydrierprozeß kohlenoxydhaltigen Wasserstoff, so tritt bereits im Rohprodukt ein sehr starker Farbzahlanstieg auf. Ähnlich liegen die Verhältnisse bei anderen Alkoholen oder Produkten, an die hohe Reinheitsforderungen gestellt werden, wie z. B. bei Faservorprodukten, Hexamethylendiamin usw.Process for the catalytic removal of contact poisons, in particular Carbon oxide, from hydrogen, hydrogen, which comes from the water gas process and washed with ammoniacal copper liquor, still contains carbon oxide and some Oxygen and sulfur. For most catalytic hydrogenation processes, the used hydrogen but completely free of carbon oxide, oxygen and Be sulfur, since the metals, such as nickel, cobalt, iron, palladium or copper, under whose catalytic action the hydrogenation is carried out, through them, in particular by carbon oxide, are largely inactivated and with a higher carbon oxide content of the hydrogen can be completely poisoned. Often there are small amounts of carbon monoxide in hydrogen the reason for the fact that the life of the catalysts used is very low. Slightly poisoned catalysts always require a higher reaction temperature, which adversely affect the yield and the purity of the products to be manufactured affects. The chemical industry today brings a number of products to the Market, the purity of which is very demanding. So z. B. a good ethylhexanol, as it is e.g. B. is used for plasticizers, with more concentrated Sulfuric acid mixed, does not discolor. Used in manufacturing of ethylhexanol for the hydrogenation process, hydrogen containing carbon dioxide, occurs already in the crude product there is a very strong increase in the color number. The situation is similar with other alcohols or products that have high purity requirements become, such as B. in fiber precursors, hexamethylenediamine, etc.
Größere Mengen Kohlenoxyd werden aus dem Wasserstoff meist mit ammoniakalischen Kupfersalzlösungen ausgewaschen. Eine solche Wäsche vermag das Kohlenoxyd jedoch nur bis auf einen Restgehalt von mindestens 0,01 Volumprozent des Wasserstoffs zu entfernen.Larger amounts of carbon monoxide are usually obtained from the hydrogen with ammoniacal ones Washed out copper salt solutions. Carbon oxide, however, is capable of such washing only up to a residual content of at least 0.01 percent by volume of the hydrogen remove.
Zur -Entfernung dieser Restmengen Kohlenoxyd aus dem Wasserstoff sind vorwiegend Absorptionsverfahren vorgeschlagen worden, die indes technisch keine Bedeutung erlangt haben. Auch katalytischeVerfahren unter Verwendung von Katalysatoren auf Kupferbasis wurden empfohlen, die aber ebenfalls keine restlose Entfernung des Kohlenoxyds ermöglichen.To remove these residual amounts of carbon dioxide from the hydrogen mainly absorption processes have been proposed, which, however, technically none Have gained importance. Also catalytic processes using catalysts based on copper were recommended, but they also do not completely remove the Enable carbon dioxide.
Aus der deutschen Patentschrift 537 433 ist bekannt, Wasserstoff oder wasserstoffhaltige Gasgemische von darin enthaltenem Kohlenoxyd durch katalytische Oxydation des letzteren mittels Luft bei Temperaturen unterhalb 150° C zu befreien, wobei Gemische von Kupfer, Kobalt, Chrom, Eisen, Mangan sowie anderen Schwer- und Edelmetallen und deren verschiedene Oxyde als Katalysatoren benutzt werden. Dabei wirken die in den Katalysatoren enthaltenen Oxyde unmittelbar oxydierend. auf die reduzierenden Gase und beschleunigen die katalytische Vereinigung der reduzierenden Gase mit im Gasgemisch vorhandenem Sauerstoff. Wegen der Gefahr der Knallgasbildung hat dieses Verfahren keinen Eingang in die - Praxis gefunden. -Aus der USA.-Patentschrift -1-589 628 ist -ein Verfahren bekannt, bei dem Kohlenoxyd auf- reduktivem Wege -aus einem wasserstoffhaltigen Gasgemisch durch Umsetzung an einen Eisenkontakt bei Temperaturen von 400 bis 450°-C entfernt wird. In der italienischen Patentschrift 314590 ist vorgeschlagen, Kohlenoxyd aus Wassergas durch Überleiten über- Kontakte zu entfernen, die neben metallischen Komponenten, wie Nickel, Kobalt und Molybdän,-leicht oxydierbare Metalle, wie Eisen und Zink oder ihre Oxyde, und schwer reduzierbare Metalloxyde, wie Calciumoxyd; Magnesiumoxyd, Manganoxyd, enthalten. Trotz der dafür verwendeten Temperatur von 250 bis 500° C läßt sich hiermit eine technisch befriedigende Abtrennung des Kohlenoxyds nicht erreichen: Diese Patentschriften vermitteln keinen Hinweis auf die erfindungsgemäße-Reinigung von Wasserstoff an aus metallischem Nickel, Kupfer und Mangan bestehenden Katalysatoren, zumal, da der Veröffentlichung in der Zeitschrift »Brennstoff-Chemie«, 12, 1931, S. 225 ff., zu entnehmen ist, daß ein Kupferzusatz zu Nickel die Aktivität desselben nicht nur nicht steigert, sondern sogar schädigt.From the German patent 537 433 is known, hydrogen or hydrogen-containing gas mixtures of carbon dioxide contained therein by catalytic To free oxidation of the latter by means of air at temperatures below 150 ° C, whereby mixtures of copper, cobalt, chromium, iron, manganese and other heavy and Precious metals and their various oxides are used as catalysts. Included The oxides contained in the catalytic converters have a direct oxidizing effect. on the reducing gases and accelerate the catalytic association of the reducing Gases with oxygen present in the gas mixture. Because of the risk of oxyhydrogen formation this procedure has not found its way into practice. - From the USA patent -1-589 628 is -a method known in the carbon oxide on-reductive route -aus a hydrogen-containing gas mixture by conversion to an iron contact at temperatures from 400 to 450 ° C is removed. In the Italian patent 314590 is proposed to remove carbon oxide from water gas by passing it over contacts, which, in addition to metallic components such as nickel, cobalt and molybdenum, are easily oxidized Metals, such as iron and zinc or their oxides, and metal oxides that are difficult to reduce, like calcium oxide; Magnesium oxide, manganese oxide, contain. Despite the used for it A technically satisfactory separation can thus be achieved at temperatures of 250 to 500 ° C of the carbon monoxide: These patents do not give any indication on the inventive purification of hydrogen from metallic nickel, copper and manganese existing catalysts, especially since the publication in the journal "Fuel-Chemistry", 12, 1931, p. 225 ff., It can be seen that a copper additive to nickel not only does not increase its activity, but even damages it.
Es wurde gefunden, daß man auf einfache Weise die Kontaktgifte, insbesondere Kohlenoxyd, daneben Sauerstoff; Schwefel und auch Halogen aus dem Wasserstoff quantitativ entfernen kann, wenn man den diese Gifte enthaltenden Wasserstoff über einen mit Mangan aktivierten Nickel-Kupfer-Mischkatalysator leitet.It has been found that in a simple manner the contact poisons, in particular Carbon dioxide, next to it oxygen; Sulfur and also halogen from the hydrogen quantitatively can remove if you have the hydrogen containing these poisons over a with manganese activated nickel-copper mixed catalyst conducts.
Das Gewichtsverhältnis von Nickel, Kupfer und Mangan im Katalysator kann innerhalb weiter Grenzen variiert werden. Als Aktivatoren können außerdem auch andere Metalle, wie z. B. Chrom, verwendet werden. Als besonders geeignet hat sich ein Katalysator erwiesen, in dem das Gewichtsverhältnis 17 Teile Nickel zu 5 Teilen Kupfer zu 0,7 Teilen Mangan beträgt. Besonders hohe Aktivitäten erreicht man, wenn man die Metalle in Form ihrer Nitrate in wäßriger Lösung auf den Träger aufbringt, die Nitrate dann durch Erhitzen in die entsprechenden Oxyde und diese durch Reduktion mit Wasserstoff in die Metalle überführt.The weight ratio of nickel, copper and manganese in the catalyst can be varied within wide limits. Can also be used as activators other metals such as B. chromium, can be used. Has proven to be particularly suitable proved a catalyst in which the weight ratio 17 parts nickel to 5 parts Copper is 0.7 parts manganese. Particularly high activities are achieved when the metals are applied to the support in the form of their nitrates in aqueous solution, the nitrates are then converted into the corresponding oxides by heating and these by reduction converted into the metals with hydrogen.
Je nach der Reaktionstemperatur wird das Kohlenoxyd katalytisch in Methanol oder Methan übergeführt. Die restlose Entfernung des Kohlenoxyds aus dem Wasserstoff erfolgt bereits bei 170° C. Vorteilhaft arbeitet man bei Temperaturen zwischen 220 und 240° C, da bei diesen Temperaturen nicht nur das Kohlenoxyd restlos entfernt wird, sondern auch etwa vorhandenes Ammoniak als Amin gebunden wird, das mit dem Wasser und Methanol in einem Abscheider abgeschieden wird. Sauerstoff und Schwefel werden unter diesen Bedingungen ebenfalls vollständig aus dem Wasserstoff entfernt.Depending on the reaction temperature, the carbon oxide is catalytically in Converted to methanol or methane. The complete removal of the carbon dioxide from the Hydrogen takes place at 170 ° C. It is advantageous to work at temperatures between 220 and 240 ° C, because at these temperatures not only the carbon oxide is completely is removed, but also any ammonia present is bound as an amine, the with the water and methanol is separated in a separator. Oxygen and Under these conditions, sulfur is also completely removed from the hydrogen removed.
Als Träger für den Katalysator kann man alle bekannten Trägermaterialien verwenden. Zweckmäßig verwendet man hierfür Kieselsäurestränge, da sie zum Unterschied von dem zumeist zur Anwendung kommenden Kieselgel keinen Abrieb zeigen, der sich in Form von festem, verbackendem Staub in den Apparaturen und Leitungen absetzt und zu Verstopfungen führt.All known support materials can be used as supports for the catalyst use. For this purpose, silica strands are expediently used, since they differ from each other show no abrasion of the mostly used silica gel settles in the form of solid, caked dust in the equipment and lines and leads to constipation.
Das erfindungsgemäße Verfahren kann ohne weiteres auch bei höheren Drücken, z. B. bei 300 Atm., durchgeführt werden und somit auch auf die Herstellung von gereinigtem Hochdruckwasserstoff Anwendung finden.The method according to the invention can also be used with higher Press, e.g. B. at 300 atm., And thus also on the production of purified high pressure hydrogen find application.
Enthält das zu reinigende Gas bis zu 0,0211/o Kohlenoxyd, so ist eine Umwälzung des Gases zwecks Wärmeabführung nicht nötig. Vielmehr genügt es, den zu reinigenden Wasserstoff drucklos oder bei erhöhtem Druck in einem einzigen Durchgang über den Katalysator zu führen, um Kohlenoxyd, Sauerstoff, Schwefel und Ammoniak restlos zu entfernen. Bei einem Kohlenoxydgehalt des Gases bis 0,0211/a kann der Katalysator mit bis zu 20 000 Nm3/h belastet werden. Bei höheren Kohlenoxydgehalten empfiehlt es sich, das zu reinigende Gas mit einer Gasumlaufpumpe umzuwälzen, um einen Wärmestau am Katalysator zu verhindern.If the gas to be cleaned contains up to 0.0211 / o carbon oxide, it is one Circulation of the gas for the purpose of heat dissipation is not necessary. Rather, it is enough to do that cleaning hydrogen without pressure or at increased pressure in a single pass over the catalyst lead to carbon oxide, oxygen, sulfur and ammonia to be removed completely. With a carbon oxide content of the gas up to 0.0211 / a, the Catalyst can be loaded with up to 20,000 Nm3 / h. At higher carbon monoxide contents it is advisable to circulate the gas to be cleaned with a gas circulation pump to prevent heat build-up on the catalytic converter.
Der erfindungsgemäße Katalysator zeichnet sich durch eine sehr hohe Lebensdauer aus. So können mit 1 kg des Katalysators leicht 4 000 000 Nm3 Wasserstoff vollständig von Kohlenoxyd, Sauerstoff und Ammoniak befreit werden. Auch Halogen, wie z. B. Chlor, das in geringen Mengen im Wasserstoff enthalten sein kann, wird dabei restlos entfernt. Es war nicht ohne weiteres zu erwarten, daß gerade Nickel und Kupfer, die gegen Katalysatorgifte bekanntlich sehr empfindlich sind, sich zur Entfernung von Kohlenoxyd, Ammoniak und Halogen eignen, wenn sie in der erfindungsgemäßen Kombination zur Anwendung kommen, und daß diese Katalysatorgifte auch bei einer sehr hohen Belastung des Katalysators entfernt werden können. Bei einem stündlichen Durchsatz von 10 000 Nm3 Gas hält eine Katalysatorfüllung von 3,5 t rund 3 Jahre.The catalyst according to the invention is characterized by a very high Lifetime. With 1 kg of the catalyst, 4,000,000 Nm3 of hydrogen can easily be produced be completely freed from carbon monoxide, oxygen and ammonia. Also halogen, such as B. Chlorine, which may be contained in hydrogen in small amounts, will completely removed. It was not to be expected without further ado that nickel in particular and copper, which are known to be very sensitive to catalyst poisons Removal of carbon oxide, ammonia and halogen are suitable when used in the invention Combination are used, and that these catalyst poisons also with a very high load on the catalyst can be removed. At an hourly A catalyst filling of 3.5 t lasts around 3 years throughput of 10,000 Nm3 gas.
Der Energieaufwand des Verfahrens ist sehr gering, wenn man mit einem Wärmeaustauscher arbeitet. Beispiel Ein Hochdruckgefäß von 1800 mm Länge und 600 mm lichter Weite wird mit 3 500 kg Nickel-Kupfer-Mangan-Kontakt, dessen Träger aus Kieselsäuresträngen besteht, gefüllt. Das Metallverhältnis in dem Katalysator beträgt 17 Teile Nickel zu 5 Teilen Kupfer zu 0,7 Teilen Mangan. Über den Katalysator werden unter einem Druck von 300 Atm stündlich 8000 Nm3 Wasserstoff geleitet, der 0,018°/o Kohlenoxyd, 0,00311/o Sauerstoff sowie je m3 0,2 mg Schwefel, 20 mg Ammoniak und 3,5 mg Chlor enthält. Um bezüglich des Durchsatzes Spielraum zu haben und um das Ammoniak als Amin zu binden, stellt man die Temperatur etwas überhöht auf 240° C ein. Das den Kontaktofen verlassende gereinigte Gas wird durch einen Hochdruckkühler und einen Abscheider geleitet, in dem die flüssigen Anteile, nämlich ein Gemisch von Wasser, Methanol und basischen Bestandteilen, abgeschieden werden. Das Reingas ist nach einmaligem Durchgang durch den Kontaktofen und Abscheider vollständig frei von Kohlenoxyd, Schwefel, Chlor, Sauerstoff und Ammoniak. Sein Kohlensäuregehalt beträgt 0,0005°/o gegenüber 0,002511/o im Rohgas, sein Wassergehalt 290 mg/m3 gegenüber 650 mg/m3 im Rohgas.The energy expenditure of the procedure is very low when working with a The heat exchanger is working. Example A high pressure vessel 1800 mm long and 600 mm long mm clearance is made with 3,500 kg of nickel-copper-manganese contact, its carrier Silica strands is filled. The metal ratio in the catalyst is 17 parts nickel to 5 parts copper to 0.7 parts manganese. Be over the catalyst 8000 Nm3 of hydrogen per hour passed under a pressure of 300 atm, the 0.018% Carbon oxide, 0.00311 / o oxygen and 0.2 mg sulfur, 20 mg ammonia and Contains 3.5 mg of chlorine. In order to have leeway in terms of throughput and the To bind ammonia as an amine, the temperature is set a little too high to 240 ° C a. The purified gas leaving the contact furnace is passed through a high pressure cooler and passed a separator in which the liquid components, namely a mixture of water, methanol and basic components. The clean gas is completely free after a single pass through the contact furnace and separator of carbon monoxide, sulfur, chlorine, oxygen and ammonia. Its carbonation is 0.0005% compared to 0.002511 / o in the raw gas, its water content compared to 290 mg / m3 650 mg / m3 in the raw gas.
Steigt der Kohlenoxydgehalt im Rohgas auf 0,03111o, so wird mit Hilfe einer Gasumlaufpumpe das Gas umgewälzt, wobei gleichzeitig kontinuierlich Rohgas zugeführt und Reingas abgezogen wird. Bei Verwendung eines Wärmeaustauschers beträgt der Dampfverbrauch bei einem stündlichen Durchsatz von 10 000 Nm3 Gas 180 kg.If the carbon oxide content in the raw gas rises to 0.03111o, then with the help a gas circulation pump circulates the gas, while at the same time continuously raw gas is supplied and clean gas is withdrawn. When using a heat exchanger is the steam consumption at an hourly throughput of 10 000 Nm3 gas 180 kg.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB45205A DE1078550B (en) | 1957-07-04 | 1957-07-04 | Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB45205A DE1078550B (en) | 1957-07-04 | 1957-07-04 | Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1078550B true DE1078550B (en) | 1960-03-31 |
Family
ID=6967540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB45205A Pending DE1078550B (en) | 1957-07-04 | 1957-07-04 | Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1078550B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1589628A (en) * | 1921-03-25 | 1926-06-22 | Lazote Inc | Purification of gases for ammonia synthesis |
| DE537433C (en) * | 1926-02-20 | 1931-11-03 | Bayerische Stickstoff Werke Ak | Removal of carbon oxide from hydrogen or hydrogen-containing gas mixtures |
| DE528915C (en) * | 1926-02-13 | 1931-11-07 | I G Farbenindustrie Akt Ges | Process for the desulphurization of gases and vapors |
-
1957
- 1957-07-04 DE DEB45205A patent/DE1078550B/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1589628A (en) * | 1921-03-25 | 1926-06-22 | Lazote Inc | Purification of gases for ammonia synthesis |
| DE528915C (en) * | 1926-02-13 | 1931-11-07 | I G Farbenindustrie Akt Ges | Process for the desulphurization of gases and vapors |
| DE537433C (en) * | 1926-02-20 | 1931-11-03 | Bayerische Stickstoff Werke Ak | Removal of carbon oxide from hydrogen or hydrogen-containing gas mixtures |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60125103T2 (en) | Recovery of the ammonia synthesis catalyst | |
| DE2928049C2 (en) | ||
| DE1047206B (en) | Process for the production of hydrogenation catalysts for the reduction of organic nitro compounds | |
| DE2952061C2 (en) | ||
| DE608361C (en) | Process for the production of methyl alcohol from carbon oxide | |
| DE1078550B (en) | Process for the catalytic removal of contact poisons, in particular carbon oxide, from hydrogen | |
| DE856294C (en) | Process for the production of ª ‡, ª ‰ -unsaturated carboxylic acids and their derivatives | |
| DE69014628T2 (en) | CATALYST FOR HETEROGENEOUS CATALYSIS, MADE OF AN ALLOY OF TRANSITIONAL METALS. | |
| DE2022818A1 (en) | Process for the production of formaldehyde | |
| CH618619A5 (en) | ||
| EP0322760A1 (en) | Process for the preparation of cobalt catalysts | |
| DE902375C (en) | Process for the production of methanol | |
| DE2738269A1 (en) | PROCESS FOR PRODUCING ACETONE FROM ISOBUTYRALDEHYDE | |
| DE441433C (en) | Process for the production of organic compounds by catalytic gas reactions | |
| AT105591B (en) | Process for the preparation of methanol. | |
| DE1593606B1 (en) | Process for the preparation of cis-cyclodecene by catalytic hydrogenation of trans, cis-1,5-cyclodecadiene | |
| DE1201262B (en) | Process for practically complete removal of oxygen dissolved in water | |
| AT116601B (en) | Process for the preparation of methanol and other oxygen-containing organic compounds. | |
| DE597515C (en) | Process for the preparation of hydrocarbons from gases containing carbon oxides and hydrogen | |
| DE937706C (en) | Process for the production of oxygen-containing products with a high ester content | |
| AT112972B (en) | Process for the production of hydrogen. | |
| EP0079490A1 (en) | Process for the production of formaldehyde | |
| DE1941634C (en) | Process for the preparation of 2 ethylhexanal (1) | |
| DE600677C (en) | Process for the preparation of methyl alcohol by reducing carbon oxide | |
| DE763982C (en) | Process for the catalytic conversion of gas mixtures containing carbon dioxide and hydrogen into hydrocarbons |