DE764047C - Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen - Google Patents

Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen

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Publication number
DE764047C
DE764047C DEST61859D DEST061859D DE764047C DE 764047 C DE764047 C DE 764047C DE ST61859 D DEST61859 D DE ST61859D DE ST061859 D DEST061859 D DE ST061859D DE 764047 C DE764047 C DE 764047C
Authority
DE
Germany
Prior art keywords
carbon dioxide
solid
liquid
production
hydrogen
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
Application number
DEST61859D
Other languages
German (de)
Inventor
Franz Dr Fischer
Helmut Dr Pichler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
STUDIEN und VERWERTUNGS GES M
Original Assignee
STUDIEN und VERWERTUNGS GES M
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by STUDIEN und VERWERTUNGS GES M filed Critical STUDIEN und VERWERTUNGS GES M
Priority to DEST61859D priority Critical patent/DE764047C/en
Application granted granted Critical
Publication of DE764047C publication Critical patent/DE764047C/en
Expired legal-status Critical Current

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Classifications

    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/0445—Preparation; Activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron

Description

Verfahren zur Herstellung fester, flüssiger und leicht verflüssigbarer aliphatischer Kohlenwasserstoffe aus Kohlenoxyd und Wasserstoff enthaltenden Gasen Bei einer mit Hilfe vorn Eisenkontakten zwecks Herstellung von Kohlenwasserstoffen durchgeführten Kohlenoxydhydrierung hat man die zur Anwendung kommenden Eisenkontakte, welche durch Fällung aus geeigneten Eisensalzlösungen gewonnen sind, vorher oberhalb von 200°, vorzugsweise in einem um etwa 240° liegenden Temperaturbereich unter Drücken mit Kohlenoxyd- und Wasserstoff enthaltenden Gasen vorbehandelt, die wesentlich unterhalb des nachfolgenden Synthesedruckes liegen. Die Kontaktvorbehandlung kann beispielsweise bei Atmosphärendruck erfolgen, während die Synthese bei etwa 2 bis 50 atü ausgeführt wird.Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon monoxide and hydrogen In one with the help of iron contacts for the production of hydrocarbons carried out carbohydrate hydrogenation, one has the iron contacts that are used, which are obtained by precipitation from suitable iron salt solutions, previously above of 200 °, preferably in a temperature range lying around 240 ° under pressures pretreated with gases containing carbon dioxide and hydrogen, which are essential are below the subsequent synthesis pressure. Contact pre-treatment can for example take place at atmospheric pressure, while the synthesis at about 2 to 50 atü is executed.

Eine derartige Behandlung verleiht dem Katalysator eine ausreichende Lebensdauer und versetzt ihn außerdem in die Lage, das Synthesegas in besonders wirtschaftlicher Ausbeute in höhere Kohlenwasserstoffe umzuwandeln.Such treatment gives the catalyst a sufficient one Service life and also enables him to use the synthesis gas in particularly to convert them into higher hydrocarbons in an economical yield.

Es wurde gefunden, daß man diese Vorbehandlung nicht nur mit Kohlenoxyd-Wasserstoff-Gemischen, sondern auch nur mit Kohlenoxyd erfolgreich durchführen kann. Bei dieser Arbeitsweise unterbleibt die während der Kontaktvorbehandlung unenvünschte Bildung von Kohlenwasserstoffen. Das den Kontakt verlassende Gas kann unter Umständen nach Herausnahme der von der Formierung (Reduktion und Kohlenstoffeinbau) stammenden Kohlensäure im Kreislauf wieder zur Vorbehandlung Verwendung finden. It has been found that this pretreatment can not only be carried out with carbon-oxide-hydrogen mixtures, but also only with carbon dioxide can perform successfully. at this procedure omits the undesirable during the contact pretreatment Formation of hydrocarbons. The gas leaving the contact can under certain circumstances after removing those from the formation (reduction and carbon incorporation) Carbon dioxide can be used again in the circuit for pretreatment.

Als Katalysatoren werden Eisenfällungskontakte verwendet, die durch Zusätze, wie beispielsweise geringe Älengen an Alkali oder Kupfer, aktiviert werden können. Iron precipitation contacts are used as catalysts, which through Additives, such as small amounts of alkali or copper, are activated can.

Aus den nachfolgenden Ausführungsbeispielen sind nähere Einzelheiten der erfindungsgemäßen Arbeitsweise ersichtlich. Further details are given in the following exemplary embodiments the method of operation according to the invention can be seen.

Ausführungsbeispiel I Eisennitrat, das durch Lösen von I kg Eisenspänen in verdünnter Salpetersäure (d = I,I62) hergestellt worden ist, wurde mit einer verdünnten Lösung von Soda in geringem Überschuß in der Hitze gefällt. Der Niederschlag wurde abfiltriert, bis zur Alkalifreiheit gewaschen, mit o,I25 °lo Kaliumcarbonat, bezogen auf Eisen, alkalisiert, bei 1100 getrocknet, gekörnt und in einen druckfesten Kontaktapparat gefüllt. Embodiment I iron nitrate obtained by dissolving 1 kg of iron filings in dilute nitric acid (d = I, I62) was prepared with a dilute solution of soda precipitated in a slight excess in the heat. The precipitation was filtered off, washed until alkali-free, with 0.125 ° lo potassium carbonate, based on iron, alkalized, dried at 1100, granulated and in a pressure-resistant Contact apparatus filled.

Zur Formierung leitete man bei Atmosphärendruck und 260° 400 1 KohlenoMrd je Stunde über den Kontakt. Zunächst trat stärkere Kohlendioxydbildung auf. Sie klang im Laufe von zwei Tagen allmählich ab und erreichte schließlich einen konstanten Wert von rund 8 0to. For formation, 400 l of coal were passed at atmospheric pressure and 260 ° per hour via the contact. At first there was stronger carbon dioxide formation. she Gradually subsided over the course of two days and finally reached a constant level Value of around 8 0to.

Sobald dieser konstante Wert erreicht war, wurde auf Wassergas, 15 at Druck und 240° umgestellt. Bei einem Durchsatz von 400 1 WVassergas, bezogen auf Atmosphärendruck, je Stunde betrug die Kontraktion 50 Of, bei einer Ausbeute an festen, flüssigen und leicht verflüssigbaren Kohlenwasserstoffen von 130 gINcbm Synthesegas. Im Laufe mehrerer Monate wurde die Temperatur entsprechend dem Absinken der Aktivität des Kontaktes allmählich bis auf 260° erhöht.As soon as this constant value was reached, water gas, 15 at pressure and 240 ° switched. At a throughput of 400 1 W water gas at atmospheric pressure, the contraction was 50% per hour, with one yield of solid, liquid and easily liquefiable hydrocarbons of 130 gINcbm Synthesis gas. Over the course of several months, the temperature became corresponding to the drop the activity of the contact gradually increased up to 260 °.

Ausführungsbeispiel 2 Ein wie bei Ausführungsbeispiel I hergestellter Rontakt wurde mit 4 cbm reinem Kohlenoxyd, bezogen auf 1 kg Eisen, je Stunde bei 2900 und Atmosphärendruck formiert. Der Kohlendioxydgehalt des Endgases hatte nach Durchschreitung des Ataximums nach 6 Stunden einen konstanten Wert von rund I bis 2 0/, C O2 angenommen. Nun wurde auf Synthesegas, das Kohlenoxyd und Wasserstoff im Verhältnis 3: 2 enthielt, 15 at Druck und 240 umgestellt. Die Kontraktion betrug 53 00. Die Ausbeute an festen, flüssigen und leicht verflüssigbaren Kohlenwasserstoffen betrug I50 ggNcbm. Bei allmählicher Steigerung der Synthesetemperatur auf 250 und schließlich 260° blieb die Ausbeute durch viele Monate bei I30 bis 150 glN'Cbm Synthesegas. Embodiment 2 A manufactured as in embodiment I. Contact was made with 4 cbm of pure carbon oxide, based on 1 kg of iron, per hour 2900 and atmospheric pressure formed. The carbon dioxide content of the end gas had decreased Passing through the ataximum after 6 hours a constant value of around I to 2 0 /, C O2 assumed. Now synthesis gas, the carbon oxide and hydrogen were turned on contained in the ratio 3: 2, 15 at pressure and 240 converted. The contraction was 53 00. The yield of solid, liquid and easily liquefiable hydrocarbons was I50 ggNcbm. With a gradual increase in the synthesis temperature to 250 and finally 260 ° the yield remained for many months at 130 to 150 glN'Cbm synthesis gas.

Claims (1)

PATENTANSPRC'CH: Verfahren zur Herstellung fester, flüssiger und leicht verflüssigbarer aliphatischer Kohlenwasserstoffe aus Kohlenoxvd und Wasserstoff enthaltenden Gasen unter erhöhtem Druck von etwa 2 bis 50 at bei höheren, aber unter 320" liegenden Temperaturen über Eisenkatalysatoren, welche durch Fällung aus Eisensalzlösungen hergestellt sind, dadurch gekennzeichnet, daß ein Eisenkontakt verwendet wird, der vor seiner Benutzung mit Kohlenoxid bei Temperaturen oberhalb 200c, aber unterhalb 500°, vorzugsweise in einem zwischen 240 und 325" liegenden Temperaturbereich, unter wesentlich unterhalb des später zu verwendenden Synthesedruckes liegenden Drucken, beispielsweise bei Atmosphärendruck, vorbehandelt wurde. PATENT CLAIM: Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from carbon dioxide and hydrogen containing gases under increased pressure of about 2 to 50 atm at higher, but under 320 "temperatures above iron catalysts, which are obtained by precipitation from iron salt solutions are made, characterized in that an iron contact is used, the before using it with carbon oxide at temperatures above 200c, but below 500 °, preferably in a temperature range between 240 and 325 ", below pressure significantly below the synthesis pressure to be used later, for example at atmospheric pressure, was pretreated.
DEST61859D 1941-05-06 1941-05-06 Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen Expired DE764047C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEST61859D DE764047C (en) 1941-05-06 1941-05-06 Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEST61859D DE764047C (en) 1941-05-06 1941-05-06 Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen

Publications (1)

Publication Number Publication Date
DE764047C true DE764047C (en) 1953-06-22

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ID=7468490

Family Applications (1)

Application Number Title Priority Date Filing Date
DEST61859D Expired DE764047C (en) 1941-05-06 1941-05-06 Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen

Country Status (1)

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DE (1) DE764047C (en)

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