DE907170C - Process for the synthetic production of alcohols from gas mixtures containing carbon oxide and hydrogen - Google Patents

Process for the synthetic production of alcohols from gas mixtures containing carbon oxide and hydrogen

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Publication number
DE907170C
DE907170C DER3272A DER0003272A DE907170C DE 907170 C DE907170 C DE 907170C DE R3272 A DER3272 A DE R3272A DE R0003272 A DER0003272 A DE R0003272A DE 907170 C DE907170 C DE 907170C
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Germany
Prior art keywords
hydrogen
alcohols
gas mixtures
water
mixtures containing
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Expired
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DER3272A
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German (de)
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Dr Karl Buechner
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RUHRCHEMINE AG
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RUHRCHEMINE AG
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Priority to DER3272A priority Critical patent/DE907170C/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Verfahren zur synthetischen Gewinnung von Alkoholen aus Kohlenoxyd und Wasserstoff enthaltenden Gasgemischen Zur Gewinnung von synthetischen Alkoholen aus Kohlenoxyd und Wasserstoff enthaltenden Gasgemischen, insbesondere aus Wassergas, wurde im Patent 902 ¢92 ein Kombinationsverfahren vorgeschlagen, bei dem zunächst ein Teil des Gasgemisches mit Eisenkatalysatoren zu stark sauerstoffhaltigen und olefinischen Syntheseprodukten umgesetzt wird. Diese Syntheseprodukte werden darauf unter hohem Druck mit Wassergas behandelt. Hierbei ergeben sich Reaktionsgemische, die vorwiegend Aldehyde und Alkohole enthalten. Daneben werden geringe oder höhere Mengen von ätherartig gebundenen sauerstoffhaltigen Verbindungen gebildet. Durch katalytische Anlagerung von Wasserstoff lassen sich diese Gemische in Endprodukte überführen, die vorwiegend aus Alkoholen der verschiedensten Molekülgröße bestehen.Process for the synthetic production of alcohols from carbon monoxide and gas mixtures containing hydrogen for the production of synthetic alcohols from gas mixtures containing carbon oxide and hydrogen, in particular from water gas, a combination process was proposed in the patent 902 [92] in which initially part of the gas mixture with iron catalysts to be highly oxygenated and olefinic synthesis products is implemented. These synthesis products are on it treated with water gas under high pressure. This results in reaction mixtures which mainly contain aldehydes and alcohols. In addition, there will be lower or higher Amounts of ether-like bound oxygen-containing compounds are formed. By catalytic addition of hydrogen converts these mixtures into end products transfer, which mainly consist of alcohols of various molecular sizes.

Dieses Verfahren hat den Nachteil, daß die ätherartigen Produkte bisher nicht restlos zur Alkoholbildung ausgenutzt werden konnten. Zum größten Teil bestehen diese ätherartigen Verbindungen aus Acetalen, die sich mit Aldehyden aus im Gemisch vorhandenen oder während der Reaktion entstehenden Alkoholen bilden. Acetale und ähnliche Verbindungen zeigen weder eine Hydroxylzahl noch andere Kennzahlen, so daß ihre Menge analytisch nicht ohne weiteres angegeben werden kann. Ihre Bildung führt zu einer nicht unerheblichen Verminderung der theoretisch möglichen Alkoholausbeute.This method has the disadvantage that the ethereal products so far could not be used completely for alcohol formation. For the most part exist These ethereal compounds are made from acetals, which are mixed with aldehydes form alcohols present or formed during the reaction. Acetals and similar compounds show neither a hydroxyl number nor other indicators, see above that their amount cannot easily be stated analytically. Your education does not lead to one insignificant reduction in theoretical possible alcohol yield.

Es wurde gefunden, daß sich die Ausbeute an Alkoholen erhöhen läßt, wenn man die Hydrierung der aus den Kohlenoxydhydrierungsprodukten durch katalytische Wassergasanlagerung erhaltenen Reaktionsprodukte nicht mit Wasserstoff allein, sondern hydratisierend in Gegenwart von ausreichenden Mengen Wasser durchführt. Hierbei wird der primär durch Acetalaufspaltung neben dem Alkohol entstehende Aldehyd ebenfalls durch Wasserstoff zum Alkohol reduziert, so daß man sowohl den Alkohol der Aldehydkomponente als auch den der Alkoholkomponente als zusätzliche Alkoholmenge erhält.It has been found that the yield of alcohols can be increased if one considers the hydrogenation of the caroxydrogenation products by catalytic Reaction products obtained by the addition of water gas are not obtained with hydrogen alone, but hydrating in the presence of sufficient amounts of water. Here the aldehyde, which is primarily formed by splitting acetal, is also formed in addition to the alcohol reduced by hydrogen to the alcohol, so that both the alcohol and the aldehyde component as well as that of the alcohol component as an additional amount of alcohol.

Die erfindungsgemäß anzuwendende hydratisierende Hydrierung wird zweckmäßig mit Nickel enthaltenden Katalysatoren durchgeführt. Am besten verwendet man Katalysatoren, die aus Nickel und Magnesiumoxyd bestehen und als Trägerstoff Kieselgur enthalten. Durch kurzzeitige Wasserstoffbehandlung bei annähernd 16o bis 18o° werden die in den Reaktionsprodukten vorhandenen Acetale gespalten, wobei die in Freiheit gesetzten Aldehyde zu Alkoholen aufhydriert werden.The hydrating hydrogenation to be used according to the invention is expedient carried out with nickel-containing catalysts. It is best to use catalysts which consist of nickel and magnesium oxide and contain kieselguhr as a carrier. Brief hydrogen treatment at approximately 16o to 18o ° removes the in split the acetals present in the reaction products, with those set free Aldehydes are hydrogenated to alcohols.

Bei der abschließenden hydratisierenden Hydrierung der oxolierten Kohlenoxydhydrierungsprodukte muß eine Wassermenge anwesend sein, welche die von denaufzuspaltenden Ätherbindungen aufzunehmende Wassermenge möglichst übersteigt. Diese Wassermenge wird vor der hydrierenden Behandlung zugesetzt; teilweise kann sie aber auch von einer wäßrigen Katalysatorlösung geliefert werden, die bei der Hochdruck-Wassergas-Anlagerung benutzt wird und deren Wassergehalt sich zu einem geringen Teil in den Formylierungsprodukten löst. Beispiel Durch katalytische Wassergasumsetzung an Eisenkatalysatoren wurden imZweistufenverfahren mit zwischen den Stufen in üblicher Weise eingeschalteter Kohlensäurewäsche und Ölwäsche Kohlenoxydhydrierungsprodukte gewonnen, aus denen man unter Weglassung der gasförmigen Kohlenwasserstoffe (Gasole), dier wäßrigen Produkte und der Paraffinfraktion eine zwischen So bis 36o° siedende Fraktion herausschnitt. Diese Fraktion besaß folgende Kennzahlen: Dichte ..................... = 0,779 Brechungsindex . . . . . . . . n10 = 1,4178 D Hydroxylzahl .. .. .. .. . OHZ =:2i2 Neutralisationszahl ...... NZ = 0,2 Esterzahl................ EZ = 12,3 Carbonylzahl . . . . . . . . . . . COZ = 21 Jodzahl.................. JZ = So Von dieser Fraktion wurden 48oo ccm mit r5oo ccm einer Lösung vermischt, die bei einer Wasserstoffionenkonzentration von pH=5,8/1 13,6 g Co als Co S 04 und 21 g Mg O als Mg S 04 enthielt. Die Mischung wurde go Minuten bei 117 bis 188 kg/qcm und 15o bis 16o° mit Wassergas behandelt, das 41 Volumprozent Kohlenoxyd und 5 i Volumprozent Wasserstoff enthielt. Hierbei ergaben sich 4750 ccm eines Formylierungsproduktes, das folgende Kennzahlen aufwies Dichte.................... = o,812 Brechungsindex . . . . . . . . n ö = 44299 Hydroxylzahl .. .. . . .. . OHZ = Ioi Carbonylzahl . . . . . .. . . . COZ = 51 Neutralisationszahl ...... NZ = o,8 Esterzahl ............... EZ = 14,8 Jodzahl.................. JZ = 2 Die vorstehenden Zahlenwerte zeigen, daß von der Carbonylzahl offenbar annähernd 5o0/9 analytisch nicht nachweisbar sind, denn auf Grund der Jodzahlabnahme von So vor der Oxolierung auf :2 nach der Oxolierung, d. h. um etwa 48 Einheiten, hätte die Carbonylzahl auf etwa den doppelten Wert, d. h. auf annähernd 1o2 ansteigen müssen. Hieraus läßt sich erkennen, daß zwischen den entstandenen Aldehyden und Alkoholen teilweise ätherartige Verbindungen gebildet sein müssen.During the subsequent hydrating hydrogenation of the oxolated carbohydrate hydrogenation products, an amount of water must be present which, if possible, exceeds the amount of water to be absorbed by the ether bonds to be broken down. This amount of water is added before the hydration treatment; but in some cases it can also be supplied by an aqueous catalyst solution which is used in the high-pressure water gas addition and the water content of which dissolves to a small extent in the formylation products. EXAMPLE By catalytic water gas conversion on iron catalysts in a two-stage process with carbonic acid washing and oil washing switched on in the usual way between the stages, carbohydrate hydrogenation products were obtained, from which, leaving out the gaseous hydrocarbons (gasols), the aqueous products and the paraffin fraction, a fraction boiling between 50 ° and 360 ° was cut out. This group had the following indicators: Density ..................... = 0.779 Refractive index. . . . . . . . n10 = 1.4178 D. Hydroxyl number .. .. .. ... OHZ =: 2i2 Neutralization number ...... NZ = 0.2 Ester number ................ EZ = 12.3 Carbonyl number. . . . . . . . . . . COZ = 21 Iodine number .................. JZ = So 48oo ccm of this fraction were mixed with 500 ccm of a solution which, at a hydrogen ion concentration of pH 5.8 / 1, contained 13.6 g of Co as Co S 04 and 21 g of Mg O as Mg S 04. The mixture was treated with water gas containing 41 percent by volume of carbon oxide and 5 percent by volume of hydrogen at 117 to 188 kg / sq. This resulted in 4750 ccm of a formylation product which had the following key figures Density .................... = o, 812 Refractive index. . . . . . . . n ö = 44299 Hydroxyl number .. ... . ... OHZ = Ioi Carbonyl number. . . . . ... . . COZ = 51 Neutralization number ...... NZ = o, 8 Ester number ............... EZ = 14.8 Iodine number .................. JZ = 2 The above numerical values show that approximately 50/9 of the carbonyl number cannot be detected analytically, because due to the decrease in iodine number from So before oxolation to: 2 after oxolation, i.e. by about 48 units, the carbonyl number would have doubled , ie have to rise to approximately 1o2. From this it can be seen that ethereal compounds must be formed between the aldehydes and alcohols formed.

Zur Freimachung dieser Alkoholmengen wurden die bei der katalytischen Wassergasanlagerung (Oxolierung) erhaltenen Produkte mit 400 ccm Wasser vermischt und mit 15o g eines Katalysators versetzt, der auf ioo Teile Ni-Metall i2 Teile Magnesiumoxyd und 6o Teile Kieselgur enthielt. Die Reaktionsmischung wurde sodann 6o Minuten bei 15o kg/qcm und 16o° mit Wasserstoff behandelt.To release these amounts of alcohol, the catalytic Water gas accumulation (oxolation) is mixed with 400 cc of water and 150 g of a catalyst were added containing ioo parts of Ni-Metal i2 parts It contained magnesium oxide and 60 parts of diatomite. The reaction mixture was then Treated with hydrogen for 60 minutes at 150 kg / qcm and 160 °.

Hierbei ergab seich ein Endprodukt, dias folgernde Kennzahlen aufwies: Dichte.. ................... = o,8o8 Brechungsindex ... .. ... nm = 1,4229 Hydroxylzahl . . . . . . . . . OHZ = 317 Carbonylzahl . . . . . . . . . . COZ = 2 Neutralisationszahl ...... NZ = i Esterzahl ............... EZ = IS Jodzahl................. JZ = o Wenn man dieHydrierung in der bisher üblichen Weise ohne ausreichenden Wasserzusatz durchführte, konnte eine Hydroxylzahl von nur 2g6 erreicht werden. Aus der Differenz-zwischen den Hydroxylzahlen 317 und 296 ergibt sich, daß bei der erfindungsgemäßen Arbeitsweise eine Mehrausbeute von mindestens 61/& Alkohole entstand.This resulted in an end product that had the following key figures: Density .. ................... = o, 8o8 Refractive index ... .. ... nm = 1.4229 Hydroxyl number. . . . . . . . . OHZ = 317 Carbonyl number. . . . . . . . . . COZ = 2 Neutralization number ...... NZ = i Ester number ............... EZ = IS Iodine number ................. JZ = o If the hydrogenation was carried out in the usual manner without sufficient addition of water, a hydroxyl number of only 2g6 could be achieved. The difference between the hydroxyl numbers 317 and 296 shows that the procedure according to the invention resulted in a higher yield of at least 61% alcohols.

Claims (3)

PATENTANSPRÜCHE: i. Verfahren zur synthetischen Gewinnung von Alkoholen aus Kohlenoxyd und Wasserstoff enthaltenden Gasgemischen, durch Umsetzung dieser Gasgemische, insbesondere von Wassergas, mit Eisenkatalysatoren, anschließende katalytische Anlagerung von Wassergas an die gewonnenen Kohlenoxydhydrierungsprodukte und abschließende Hydrierung mit Wasserstoff, nach Patent 902 492, dadurch gekennzeichnet, daß die aus den Kohlenoxydhydrierungsprodukten durch katalytische Wassergasanlagerung erhaltenen Reaktionsprodukte in Gegenwart von Wasser hydriert werden. PATENT CLAIMS: i. Process for the synthetic production of alcohols from gas mixtures containing carbon and hydrogen, by reacting these gas mixtures, in particular water gas, with iron catalysts, subsequent catalytic addition of water gas to the obtained carbon dioxide hydrogenation products and final hydrogenation with hydrogen, according to Patent 902 492, characterized in that the reaction products obtained from the carbon dioxide hydrogenation products by catalytic addition of water gas are hydrogenated in the presence of water. 2. Verfahren nach Anspruch i, dadurch gekennzeichnet, daB die hydratisierende Hydrierung unter Verwendung von Nickel enthaltenden Katalysatoren durchgeführt wird. 2. Procedure according to claim i, characterized in that the hydrating hydrogenation under Use of nickel-containing catalysts is carried out. 3. Verfahren nach Ansprüchen i und 2, gekennzeichnet durch die Verwendung eines Nickel, Magnesiumoxyd und Kieselgur enthaltenden Katalysators.3. Procedure according to claims i and 2, characterized by the use of a nickel, magnesium oxide and a catalyst containing kieselguhr.
DER3272A 1950-08-10 1950-08-10 Process for the synthetic production of alcohols from gas mixtures containing carbon oxide and hydrogen Expired DE907170C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE975064C (en) * 1951-02-07 1961-08-10 Exxon Research Engineering Co Process for the production of alcohols

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE975064C (en) * 1951-02-07 1961-08-10 Exxon Research Engineering Co Process for the production of alcohols

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