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WO1996005163A1 - Method of manufacturing acetic acid - Google Patents

Method of manufacturing acetic acid Download PDF

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Publication number
WO1996005163A1
WO1996005163A1 PCT/EP1995/003137 EP9503137W WO9605163A1 WO 1996005163 A1 WO1996005163 A1 WO 1996005163A1 EP 9503137 W EP9503137 W EP 9503137W WO 9605163 A1 WO9605163 A1 WO 9605163A1
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WO
WIPO (PCT)
Prior art keywords
catalysts
activators
metals
acetic acid
contain
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.)
Ceased
Application number
PCT/EP1995/003137
Other languages
German (de)
French (fr)
Inventor
Hans-Joachim Freund
Jörg WAMBACH
Oliver Seiferth
Bernd Dillmann
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.)
Hoechst AG
Original Assignee
Hoechst AG
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
Priority claimed from DE4428566A external-priority patent/DE4428566C1/en
Priority claimed from DE1995120257 external-priority patent/DE19520257A1/en
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AU33430/95A priority Critical patent/AU3343095A/en
Publication of WO1996005163A1 publication Critical patent/WO1996005163A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the invention relates to a process for the production of acetic acid by catalytic conversion of carbon dioxide and methane.
  • Acetic acid is one of the important basic organic chemicals and is used extensively in the chemical industry. The largest proportion of industrially used acetic acid is used for the production of polymers. Substantial amounts are also used as solvents immediately or after esterification with alcohols. Furthermore, acetic acid is the starting material or intermediate for many industrially used reactions.
  • acetic acid is the oxidation of aliphatic hydrocarbons, in particular of n-butane in the liquid phase.
  • Air or oxygen-enriched air serves as the oxidizing agent.
  • the implementation takes place at temperatures of 150 to 200 ° C. and
  • ERS ⁇ ZBL ⁇ (RULE 26) Pressures between 3 and 8 MPa. Which pressures and temperatures are used in the individual case is determined in particular by the type of hydrocarbon used. The reaction can be carried out with or without catalysts.
  • the oxidation of acetaldehyde is also a proven way of producing acetic acids.
  • the oxidizing agent is air, to which oxygen can be added.
  • the reaction proceeds via peracetic acid as an intermediate at temperatures from 50 to 100 ° C and pressures from 0.2 to 10 MPa.
  • the object was therefore to provide a process which is as selective as possible and which, starting from inexpensive raw materials, leads to acetic acid.
  • acetic acid consists in the reaction of carbon dioxide and methane at temperatures from 100 to 600 ° C and pressures from 0.1 to 20 MPa in the presence of catalysts which contain one or more metals from groups VIA, VIIA and VIIIA of the Periodic Table of the Elements.
  • Carbon dioxide has hardly been described as a starting material for the production of acetic acid.
  • Known investigations relate to the implementation of carbon dioxide with water
  • ERS ⁇ ZBLA ⁇ (RULE 26) hydrogen in the presence of catalysts. It leads to a complex reaction mixture, which also contains acetic acid.
  • the reaction of carbon dioxide with methane has so far only been carried out under the influence of silent electrical discharges and also results in a mixture of different oxygen-containing organic compounds, including acetic acid. However, such a reaction path is not suitable for technical use.
  • the new process enables acetic acid to be obtained under technical conditions that are common in chemical syntheses.
  • the raw materials are available in large quantities, carbon dioxide as a by-product of technical processes, methane e.g. in the form of natural gas or as a by-product of oil processing in refineries.
  • Carbon dioxide is used in the commercial form with a Ge of at least 99.7%, preferably at least 99.9% CO2. It essentially contains the constituents of the air, namely nitrogen, oxygen and argon. The methane is also used in a purity of at least 99.5%. If appropriate, catalyst poisons, in particular sulfur compounds, have to be removed beforehand by known processes. The starting materials can be reacted in a molar ratio of 1: 1, but the excess of one of the reaction components does not interfere. Molar ratios of 1: 1.1 to 1: 1.5 are preferred
  • the metals of groups VIA, VIIA and VIIIA of the Periodic Table of the Elements are also referred to below as catalytically active metals - in elemental form or as compounds.
  • Preferred among the metals mentioned are chromium, rhenium,
  • REPLACEMENT BLA ⁇ Iron, nickel, rhodium, ruthenium and palladium and particularly suitable chromium, nickel and rhodium.
  • the catalytically active metals or metal compounds are used alone or as a mixture consisting of two or more metals or metal compounds.
  • the catalysts also contain carriers.
  • Aluminum oxide such as ⁇ - or Hydroxides of aluminum, such as boehmite, silicon dioxide and hydrates of silicon dioxide in their various forms, such as precipitated silica or diatomaceous earth.
  • Aluminum silicates and zirconium dioxide have also proven successful.
  • Preferred carriers are ⁇ - ⁇ 2 ⁇ 3 and silicon dioxide.
  • the performance of the catalysts is improved in many cases by adding activators.
  • Alkali, alkaline earth and lanthanum compounds in particular the hydroxides and oxides of lithium, sodium, potassium, magnesium and calcium as well as anthane oxide, are used with success.
  • the composition of the catalysts can be varied over a wide range with regard to the type and proportion of the components.
  • Catalysts which, based in each case on the catalyst mass, contain 3 to 20% by weight of catalytically active metals and 80 to 95% by weight of carriers have proven successful.
  • the proportion of activators, based on the catalyst mass, is also 1 to 10% by weight.
  • the catalysts preferably contain 5 to 12% by weight of active metals, 85 to 90% by weight of carrier material and 2 to 3% by weight of activators.
  • the heterogeneous catalysts used according to the invention are produced by the processes known for this class of substances, in particular by precipitating the components or by impregnating carriers.
  • Precipitation catalysts are obtained by jointly separating the components, which may also include precursors of the support material, from their solutions with suitable precipitation reagents, such as alkaline compounds, for example the alkali metal carbonates or the hydroxides of the alkali metals and the alkaline earth metals.
  • suitable precipitation reagents such as alkaline compounds, for example the alkali metal carbonates or the hydroxides of the alkali metals and the alkaline earth metals.
  • the carrier substance instead of precipitating the carrier substance together with the other catalyst constituents, it can also be suspended as an insoluble solid in the solution of the metal compounds and the dissolved components precipitated in their presence.
  • the intermediate catalyst product is separated from the solvent or suspension medium, dried, shaped and activated.
  • Impregnation processes are particularly suitable for the production of catalysts for the new process in which the proportion of active metals is small compared to the proportion of the carrier material.
  • the usual procedure is to treat the carrier material with a solution of the active metal or metals.
  • the wearer can be impregnated in one stage or in several stages. If the metal salt solutions act on the support in several stages, solutions of different concentrations and / or solutions of different compositions can be used in the individual stages, that is to say, for example, for the production of catalysts which contain a plurality of active metals and which apply components to the support one after the other. Additional reaction steps can be provided between the individual impregnation stages, for example the active metals can be individually fixed on the support.
  • the catalyst Before the reactants are converted, the catalyst must be converted into the active form. For this purpose, it is treated at temperatures from 200 ° C. to 600 ° C. with hydrogen or with a gas mixture containing hydrogen and also inert substances.
  • the catalytic conversion of methane and carbon dioxide takes place in reactors of conventional design in the temperature range from 100 to 600 ° C., preferably at temperatures between 150 to 300 ° C.
  • the pressures are between 0.1 and 20 MPa, the pressure range from 0.1 to 5 MPa is preferred.
  • reaction product is distilled in a known manner.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention calls for acetic acid to be manufactured by reacting methane with carbon dioxide at temperatures of 100 to 600 DEG C and pressures of 0.1 to 20 MPa in the presence of catalysts containing one or more metals from group VIA, VIIA, or VIIIA of the periodic table of the elements.

Description

Verfahren zur Herstellung von Essigsäure Process for the production of acetic acid

Die Erfindung betrifft ein Verfahren zur Herstellung von Essigsäure durch katalytische Umsetzung von Kohlendioxid und Methan.The invention relates to a process for the production of acetic acid by catalytic conversion of carbon dioxide and methane.

Essigsäure gehört zu den wichtigen organischen Grundchemi¬ kalien und wird in der chemischen Industrie umfangreich an¬ gewendet. Der größte Anteil industriell genutzter Essig¬ säure dient zur Herstellung von Polymeren. Erhebliche Men¬ gen werden auch unmittelbar oder nach Veresterung mit Alko- holen als Lösungsmittel eingesetzt. Weiterhin ist Essig¬ säure für viele technisch genutzte Reaktionen Ausgangsstoff oder Zwischenprodukt.Acetic acid is one of the important basic organic chemicals and is used extensively in the chemical industry. The largest proportion of industrially used acetic acid is used for the production of polymers. Substantial amounts are also used as solvents immediately or after esterification with alcohols. Furthermore, acetic acid is the starting material or intermediate for many industrially used reactions.

Zur Herstellung von Essigsäure sind mehrere industriell ausgeübte Prozesse entwickelt worden. Ein bewährtes Verfah- ren ist die Carbonylierung von Methanol, d.h. die Umsetzung von Methanol mit Kohlen onoxid. Die Reaktion erfolgt in Ge¬ genwart von Katalysatoren auf Basis von Kobalt und Jod bei Drücken von 60 bis 80 MPa und Temperaturen zwischen 200 und 300°C. Eine Variante dieses Verfahrens arbeitet mit Jod/Rhodium-Katalysatoren und erfordert Drücke von ledig¬ lich 2 bis 4 MPa und Temperaturen bis etwa 200°C.Several industrial processes have been developed for the production of acetic acid. A good practice is the carbonylation of methanol, i.e. the implementation of methanol with carbon onoxide. The reaction takes place in the presence of catalysts based on cobalt and iodine at pressures of 60 to 80 MPa and temperatures between 200 and 300 ° C. A variant of this process works with iodine / rhodium catalysts and requires pressures of only 2 to 4 MPa and temperatures up to about 200 ° C.

Eine andere Arbeitsweise zur Gewinnung von Essigsäure ist die Oxidation aliphatischer Kohlenwasserstoffe, insbeson¬ dere von n-Butan in flüssiger Phase. Als Oxidationsmittel dient Luft oder mit Sauerstoff angereicherte Luft. Die Um¬ setzung läuft bei Temperaturen von 150 bis 200°C undAnother procedure for the production of acetic acid is the oxidation of aliphatic hydrocarbons, in particular of n-butane in the liquid phase. Air or oxygen-enriched air serves as the oxidizing agent. The implementation takes place at temperatures of 150 to 200 ° C. and

ERSÄΓZBLÄΓΓ (REGEL 26) Drücken zwischen 3 und 8 MPa ab. Welche Drücke und Tempera¬ turen im Einzelfall angewandt werden, wird insbesondere durch die Art des eingesetzten Kohlenwasserstoffes be¬ stimmt. Die Reaktion kann mit oder ohne Katalysatoren durchgeführt werden.ERSÄΓZBLÄΓΓ (RULE 26) Pressures between 3 and 8 MPa. Which pressures and temperatures are used in the individual case is determined in particular by the type of hydrocarbon used. The reaction can be carried out with or without catalysts.

Neben der Oxidation von Kohlenwasserstoffen ist auch die Oxidation von Acetaldehyd ein bewährter Weg zur Herstellung von Essigsäuren. Oxidationsmittel ist wiederum Luft, der Sauerstoff zugesetzt werden kann. Die Reaktion verläuft über Peressigsäure als Zwischenstufe bei Temperaturen von 50 bis 100°C und Drücken von 0,2 bis 10 MPa.In addition to the oxidation of hydrocarbons, the oxidation of acetaldehyde is also a proven way of producing acetic acids. The oxidizing agent is air, to which oxygen can be added. The reaction proceeds via peracetic acid as an intermediate at temperatures from 50 to 100 ° C and pressures from 0.2 to 10 MPa.

Die bekannten Verfahren erfordern den Einsatz eigens herge¬ stellter Ausgangsstoffe wie Methanol und Acetaldehyd oder sie arbeiten nur wenig selektiv mit der Folge, daß sich der Synthese aufwendige Trennschritte anschließen müssen.The known processes require the use of specially prepared starting materials such as methanol and acetaldehyde or they work only a little selectively, with the result that the synthesis has to be followed by complex separation steps.

Es bestand daher die Aufgabe, einen möglichst selektiven Prozeß bereitzustellen, der, von kostengünstigen Rohstoffen ausgehend, zu Essigsäure führt.The object was therefore to provide a process which is as selective as possible and which, starting from inexpensive raw materials, leads to acetic acid.

Die vorstehend beschriebene Aufgabe wird gelöst durch ein Verfahren zur Herstellung von Essigsäure. Es besteht in der Umsetzung von Kohlendioxid und Methan bei Temperaturen von 100 bis 600°C und Drücken von 0,1 bis 20 MPa in Gegenwart von Katalysatoren, die ein Metall oder mehrere Metalle der Gruppen VIA, VIIA und VIIIA des Periodensystems der Elemente enthalten.The object described above is achieved by a process for the production of acetic acid. It consists in the reaction of carbon dioxide and methane at temperatures from 100 to 600 ° C and pressures from 0.1 to 20 MPa in the presence of catalysts which contain one or more metals from groups VIA, VIIA and VIIIA of the Periodic Table of the Elements.

Kohlendioxid ist als Ausgangsstoff für die Herstellung von Essigsäure bisher kaum beschrieben worden. Bekannte Unter¬ suchungen betreffen die Umsetzung von Kohlendioxid mit Was-Carbon dioxide has hardly been described as a starting material for the production of acetic acid. Known investigations relate to the implementation of carbon dioxide with water

ERSÄΓZBLAΠ (REGEL 26) serstoff in Gegenwart von Katalysatoren. Sie führt zu einem komplex zusammengesetztem Reaktionsgemisch, in dem auch Es¬ sigsäure enthalten ist. Die Umsetzung von Kohlendioxid mit Methan wurde bisher nur unter der Einwirkung stiller elek- trischer Entladungen durchgeführt und ergibt ebenfalls ein Gemisch unterschiedlicher sauerstoffhaltiger organischer Verbindungen, darunter Essigsäure. Für die technische Nut¬ zung ist ein solcher Reaktionsweg jedoch nicht geeignet.ERSÄΓZBLAΠ (RULE 26) hydrogen in the presence of catalysts. It leads to a complex reaction mixture, which also contains acetic acid. The reaction of carbon dioxide with methane has so far only been carried out under the influence of silent electrical discharges and also results in a mixture of different oxygen-containing organic compounds, including acetic acid. However, such a reaction path is not suitable for technical use.

Das neue Verfahren ermöglicht es, Essigsäure unter techni- sehen Bedingungen zu gewinnen, die bei chemischen Synthesen üblich sind. Die Ausgangsstoffe stehen in großer Menge zur Verfügung, Kohlendioxid als Nebenprodukt technischer Pro¬ zesse, Methan z.B. in Form von Erdgas oder als Nebenprodukt der Erdölaufarbeitung in Raffinerien.The new process enables acetic acid to be obtained under technical conditions that are common in chemical syntheses. The raw materials are available in large quantities, carbon dioxide as a by-product of technical processes, methane e.g. in the form of natural gas or as a by-product of oil processing in refineries.

Kohlendioxid wird in der handelsüblichen Form mit einem Ge¬ halt von mindestens 99,7 %, bevorzugt mindestens 99,9 % CO2 eingesetzt. Als Verunreinigungen enthält es im wesentlichen die Bestandteile der Luft, nämlich Stickstoff, Sauerstoff und Argon. Auch das Methan wird in einer Reinheit von min- destens 99,5 % verwendet. Gegebenenfalls sind zuvor Kataly¬ satorgifte, insbesondere Schwefelverbindungen, nach bekann¬ ten Verfahren zu entfernen. Die Umsetzung der Ausgangs¬ stoffe kann im Molverhältnis 1 : 1 erfolgen, jedoch stört der Überschuß einer der Reaktionskomponenten nicht. Bevor- zugt wählt man Molverhältnisse von 1 : 1,1 bis 1 : 1,5Carbon dioxide is used in the commercial form with a Ge of at least 99.7%, preferably at least 99.9% CO2. It essentially contains the constituents of the air, namely nitrogen, oxygen and argon. The methane is also used in a purity of at least 99.5%. If appropriate, catalyst poisons, in particular sulfur compounds, have to be removed beforehand by known processes. The starting materials can be reacted in a molar ratio of 1: 1, but the excess of one of the reaction components does not interfere. Molar ratios of 1: 1.1 to 1: 1.5 are preferred

Als Katalysatoren finden die Metalle der Gruppen VIA, VIIA und VIIIA des Periodensystems der Elemente (nach IUPAC) im folgenden auch als katalytisch aktive Metalle bezeichnet - in elementarer Form oder als Verbindungen Anwendung. Un- ter den genannten Metallen bevorzugt sind Chrom, Rhenium,The metals of groups VIA, VIIA and VIIIA of the Periodic Table of the Elements (according to IUPAC) are also referred to below as catalytically active metals - in elemental form or as compounds. Preferred among the metals mentioned are chromium, rhenium,

ERSATZBLAΓΓ (REGEL 26) Eisen, Nickel, Rhodium, Ruthenium und Palladium und beson¬ ders geeignet Chrom, Nickel und Rhodium. Die katalytisch aktiven Metalle oder Metallverbindungen werden allein oder auch als Mischung, die aus zwei oder mehr Metallen oder Metallverbindungen bestehen, eingesetzt.REPLACEMENT BLAΓΓ (RULE 26) Iron, nickel, rhodium, ruthenium and palladium and particularly suitable chromium, nickel and rhodium. The catalytically active metals or metal compounds are used alone or as a mixture consisting of two or more metals or metal compounds.

Neben den katalytisch aktiven Metallen enthalten die Kata¬ lysatoren weiterhin Trägerstoffe. Geeignet sind Aluminium¬ oxid, wie α- oder

Figure imgf000006_0001
ι Hydroxide des Aluminiums, wie Böhmit, Silicumdioxid und Hydrate des Siliciumdioxids in ihren verschiedenen Erscheinungsformen, wie gefällte Kie¬ selsäure oder Kieselgur. Bewährt haben sich ferner Alumini¬ umsilikate und Zirkondioxid. Bevorzugt als Träger werden ^-^2^3 und Siliciumdioxid.In addition to the catalytically active metals, the catalysts also contain carriers. Aluminum oxide such as α- or
Figure imgf000006_0001
Hydroxides of aluminum, such as boehmite, silicon dioxide and hydrates of silicon dioxide in their various forms, such as precipitated silica or diatomaceous earth. Aluminum silicates and zirconium dioxide have also proven successful. Preferred carriers are ^ - ^ 2 ^ 3 and silicon dioxide.

Die Leistungsfähigkeit der Katalysatoren wird in vielen Fällen durch Zusatz von Aktivatoren verbessert. Mit Erfolg finden Alkali-, Erdalkali- und Lanthanverbindungen, insbe¬ sondere die Hydroxide und Oxide von Lithium, Natrium, Kalium, Magnesium und Calcium sowie Anthanoxid Anwendung.The performance of the catalysts is improved in many cases by adding activators. Alkali, alkaline earth and lanthanum compounds, in particular the hydroxides and oxides of lithium, sodium, potassium, magnesium and calcium as well as anthane oxide, are used with success.

Die Zusammensetzung der Katalysatoren kann sowohl hinsicht- lieh Art als auch Anteil der Komponenten in weiten Berei¬ chen variiert werden. Bewährt haben sich Katalysatoren, die, jeweils bezogen auf die Katalysatormasse, 3 bis 20 Gew.-% katalytisch aktive Metalle und 80 bis 95 Gew.-% Trägerstoffe enthalten. Der Anteil der Aktivatoren beträgt ebenfalls, bezogen auf die Katalysatormasse, 1 bis 10 Gew.- %. Vorzugsweise enthalten die Katalysatoren 5 bis 12 Gew.-% aktive Metalle, 85 bis 90 Gew.-% Trägermaterial und 2 bis 3 Gew.-% Aktivatoren.The composition of the catalysts can be varied over a wide range with regard to the type and proportion of the components. Catalysts which, based in each case on the catalyst mass, contain 3 to 20% by weight of catalytically active metals and 80 to 95% by weight of carriers have proven successful. The proportion of activators, based on the catalyst mass, is also 1 to 10% by weight. The catalysts preferably contain 5 to 12% by weight of active metals, 85 to 90% by weight of carrier material and 2 to 3% by weight of activators.

ERSÄTZB π (REGEL 26) Die erfindungsgemäß eingesetzten, heterogenen Katalysatoren werden nach den für diese Stoffklasse bekannten Verfahren, insbesondere durch Fällen der Komponenten oder durch Trän¬ ken von Trägerstoffen hergestellt. Fällungskatalysatoren erhält man durch gemeinsame Abscheidung der Komponenten, zu denen auch Vorstufen des Trägermaterials gehören können, aus ihren Lösungen mit geeigneten Fällungsreagenzien, wie alkalisch reagierenden Verbindungen, z.B. den Alkalicarbo- naten oder den Hydroxiden der Alkali- und der Erdalkalime- talle. Statt die Trägersubstanz gemeinsam mit den übrigen Katalysatorbestandteilen auszufällen, kann man sie auch als nichtlöslichen Feststoff in der Lösung der Metallverbindun¬ gen suspendieren und die Ausfällung der gelösten Komponen¬ ten in ihrer Gegenwart vornehmen. Das Katalysatorvorprodukt wird vom Lösungs- bzw. Suspensionsmittel abgetrennt, ge¬ trocknet, geformt und aktiviert. Tränkungsverfahren eignen sich insbesondere zur Herstellung von Katalysatoren für das neue Verfahren, in denen der Anteil der aktiven Metalle, verglichen mit dem Anteil des Trägermaterials, gering ist. Die übliche Arbeitsweise besteht darin, das Trägermaterial mit einer Lösung des aktiven Metalls oder der aktiven Me¬ talle zu behandeln. Die Tränkung des Trägers kann in einer Stufe oder in mehreren Stufen erfolgen. Bei mehrstufiger Einwirkung der Metallsalzlösungen auf den Träger kann man in den einzelnen Stufen Lösungen unterschiedlicher Konzen¬ tration und/oder Lösungen unterschiedlicher Zusammensetzung anwenden, also z.B. zur Herstellung von Katalysatoren, die mehrere aktive Metalle enthalten, die Komponenten nachein¬ ander auf den Träger aufbringen. Zwischen den einzelnen Tränkungsstufen können noch zusätzliche Reaktionsschritte vorgesehen werden, z.B. können die aktiven Metalle auf dem Träger individuell fixiert werden.REPLACEMENT π (RULE 26) The heterogeneous catalysts used according to the invention are produced by the processes known for this class of substances, in particular by precipitating the components or by impregnating carriers. Precipitation catalysts are obtained by jointly separating the components, which may also include precursors of the support material, from their solutions with suitable precipitation reagents, such as alkaline compounds, for example the alkali metal carbonates or the hydroxides of the alkali metals and the alkaline earth metals. Instead of precipitating the carrier substance together with the other catalyst constituents, it can also be suspended as an insoluble solid in the solution of the metal compounds and the dissolved components precipitated in their presence. The intermediate catalyst product is separated from the solvent or suspension medium, dried, shaped and activated. Impregnation processes are particularly suitable for the production of catalysts for the new process in which the proportion of active metals is small compared to the proportion of the carrier material. The usual procedure is to treat the carrier material with a solution of the active metal or metals. The wearer can be impregnated in one stage or in several stages. If the metal salt solutions act on the support in several stages, solutions of different concentrations and / or solutions of different compositions can be used in the individual stages, that is to say, for example, for the production of catalysts which contain a plurality of active metals and which apply components to the support one after the other. Additional reaction steps can be provided between the individual impregnation stages, for example the active metals can be individually fixed on the support.

ERSATZBLÄΓT(REGEL26) Vor der Umsetzung der Reaktanten muß der Katalysator in die aktive Form überführt werden. Hierzu wird er bei Temperatu¬ ren von 200°C bis 600°C mit Wasserstoff oder mit einem Wasserstoff und daneben Inerte enthaltenden Gasgemisch be- handelt.SPARE BLADE (RULE 26) Before the reactants are converted, the catalyst must be converted into the active form. For this purpose, it is treated at temperatures from 200 ° C. to 600 ° C. with hydrogen or with a gas mixture containing hydrogen and also inert substances.

Die katalytische Umsetzung von Methan und Kohlendioxid er¬ folgt in Reaktoren herkömmlicher Bauart im Temperaturbe¬ reich von 100 bis 600°C, vorzugsweise bei Temperaturen zwi¬ schen 150 bis 300°C. Die Drücke liegen zwischen 0,1 und 20 MPa, bevorzugt wird der Druckbereich von 0,1 bis 5 MPa.The catalytic conversion of methane and carbon dioxide takes place in reactors of conventional design in the temperature range from 100 to 600 ° C., preferably at temperatures between 150 to 300 ° C. The pressures are between 0.1 and 20 MPa, the pressure range from 0.1 to 5 MPa is preferred.

Bewährt hat es sich, die Reaktion in beheizten Rohrreakto¬ ren an festangeordneten Katalysatoren vorzunehmen. Hierbei empfiehlt es sich, die Ausgangsstoffe lediglich zum Teil umzusetzen und das Restgas, nach Abtrennung der Produkte und gegebenenfalls nach Ergänzung der Reaktanten, in die Reaktionszone zurückzuführen. Für die technische Durchfüh¬ rung der Reaktion völlig ausreichende Umsätze erhält man bei Einhaltung von Raumgeschwindigkeiten im Bereich von 500 bis 5000 1 Gas je 1 Katalysator und Stunde. Die unter die- sen Bedingungen erzielbare Selektivität hinsichtlich Essig¬ säure beträgt zwischen 70 und 95 %, bezogen auf eingesetz¬ tes Methan.It has proven useful to carry out the reaction in heated tubular reactors on fixed-bed catalysts. It is advisable here to only partially convert the starting materials and to return the residual gas to the reaction zone after the products have been separated off and, if appropriate, after the reactants have been added. For the technical implementation of the reaction, completely sufficient conversions are obtained with space velocities in the range from 500 to 5000 liters of gas per 1 catalyst and hour. The selectivity with respect to acetic acid which can be achieved under these conditions is between 70 and 95%, based on the methane used.

Zu Abtrennung der Essigsäure wird das Reaktionsprodukt in bekannter Weise destilliert. To separate the acetic acid, the reaction product is distilled in a known manner.

Claims

Patentansprüche claims 1.) Verfahren zur Herstellung von Essigsäure, dadurch ge¬ kennzeichnet, daß man Kohlendioxid und Methan bei Temperatu¬ ren von 100 bis 600°C und Drücken von 0,1 bis 20 MPa in Ge- genwart von Katalysatoren umsetzt, die ein Metall oder meh¬ rere Metalle der Gruppen VIA, VIIA und VIIIA des Periodensy¬ stems der Elemente (katalytisch aktive Metalle) enthalten.1.) Process for the production of acetic acid, characterized in that carbon dioxide and methane are reacted at temperatures from 100 to 600 ° C. and pressures from 0.1 to 20 MPa in the presence of catalysts which are a metal or contain several metals from groups VIA, VIIA and VIIIA of the periodic table of the elements (catalytically active metals). 2.) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Katalysatoren Chrom, Rhenium, Eisen, Nickel, Rhodium, Ruthenium oder Palladium allein oder als Mischung aus zwei oder mehreren dieser Metalle enthalten.2.) Process according to claim 1, characterized in that the catalysts contain chromium, rhenium, iron, nickel, rhodium, ruthenium or palladium alone or as a mixture of two or more of these metals. 3.) Verfahren nach Anspruch 1 oder 2, dadurch gekennzeich¬ net, daß die Katalysatoren Chrom, Nickel und/oder Rhodium enthalten.3.) Process according to claim 1 or 2, characterized gekennzeich¬ net that the catalysts contain chromium, nickel and / or rhodium. 4.) Verfahren nach einem oder mehreren der Ansprüche 1 bis4.) Method according to one or more of claims 1 to 3, dadurch gekennzeichnet, daß die Katalysatoren Trägerstoffe enthalten.3, characterized in that the catalysts contain carriers. 5.) Verfahren nach einem oder mehreren der Ansprüche 1 bis5.) Method according to one or more of claims 1 to 4, dadurch gekennzeichnet, daß als Trägerstoffe Aluminium- oxid, Aluminiumhydroxid, Siliciumdioxid oder Hydrate des Si- liciumdioxids verwendet werden.4, characterized in that aluminum oxide, aluminum hydroxide, silicon dioxide or hydrates of silicon dioxide are used as carriers. 6.) Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß als Trägerstoff oder Siliciumdioxid verwendet wird.
Figure imgf000009_0001
6.) Method according to claim 5, characterized in that is used as a carrier or silicon dioxide.
Figure imgf000009_0001
 7. ) Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Katalysatoren Aktivatoren enthalten. 7.) Process according to one or more of claims 1 to 6, characterized in that the catalysts contain activators. 8. ) Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß als Aktivatoren Alkali-, Erd¬ alkali- oder Lanthanverbindungen verwendet weden.8.) Method according to one or more of claims 1 to 7, characterized in that alkali, Erd¬ alkali or lanthanum compounds are used as activators. 9.) Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß 5 als Aktivatoren die Hydroxide oder Oxide von Lithium, Na¬ trium, Kalium, Magnesium oder Calcium oder Lanthanoxid verwendet werden.9.) Method according to claim 8, characterized in that 5 the hydroxides or oxides of lithium, sodium, potassium, potassium, magnesium or calcium or lanthanum oxide are used as activators. 10.) Verfahren nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Katalysatoren (bezogen auf 10 die Katalysatormasse) 3 bis 20 Gew.-% katalytisch aktive Me¬ talle, 80 bis 95 Gew.-% Trägerstoffe sowie 1 bis 10 Gew.-% Aktivatoren enthalten.10.) Method according to one or more of claims 1 to 9, characterized in that the catalysts (based on 10, the catalyst mass) 3 to 20 wt .-% catalytically active metals, 80 to 95 wt .-% carriers and 1st contain up to 10 wt .-% activators. 11.) Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß die Katalysatoren 5 bis 12 Gew.-% katalytisch aktive Metalle, 15 85 bis 90 Gew.-% Trägermaterial und 2 bis 3 Gew.-% Aktivato¬ ren enthalten.11.) Method according to claim 10, characterized in that the catalysts contain 5 to 12 wt .-% catalytically active metals, 15 85 to 90 wt .-% carrier material and 2 to 3 wt .-% activators. 12. ) Verfahren nach einem oder mehreren der Ansprüche 1 bis12.) Method according to one or more of claims 1 to 11, dadurch gekennzeichnet, daß das Molverhältnis von Kohlen¬ dioxid und Methan 1 : 1,1 bis 1 : 1,5 beträgt.11, characterized in that the molar ratio of carbon dioxide and methane is 1: 1.1 to 1: 1.5. 20 13.) Verfahren nach einem oder mehreren der Ansprüche 1 bis20 13.) Method according to one or more of claims 1 to 12, dadurch gekennzeichnet, daß die Umsetzung bei Temperatu¬ ren von 150 bis 300°C erfolgt.12, characterized in that the reaction takes place at temperatures from 150 to 300 ° C. 14. ) Verfahren nach einem oder mehreren der Ansprüche 1 bis14.) Method according to one or more of claims 1 to 13, dadurch gekennzeichnet, daß die Umsetzung bei Drücken von 25 0,1 bis 5 MPa erfolgt.13, characterized in that the reaction takes place at pressures of 25 0.1 to 5 MPa. ERSATZBLÄΓT (REGEL 25) SPARE BLADE (RULE 25)
PCT/EP1995/003137 1994-08-12 1995-08-08 Method of manufacturing acetic acid Ceased WO1996005163A1 (en)

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DE4428566A DE4428566C1 (en) 1994-08-12 1994-08-12 Acetic acid prodn.
DE1995120257 DE19520257A1 (en) 1995-06-02 1995-06-02 Cost-effective prodn. of acetic acid with high selectivity
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103330C (en) * 2000-09-30 2003-03-19 太原理工大学 Process for synthesizing acetic acid in heterogeneous catalysis system
US6960682B2 (en) 2003-07-24 2005-11-01 The Regents Of The University Of California Process for production of acetyl anhydrides and optionally acetic acid from methane and carbon dioxide
US7009074B2 (en) 2004-07-28 2006-03-07 The Regents Of The University Of California Process for direct oxidation of methane to acetic acid
KR101838612B1 (en) * 2016-04-11 2018-03-14 인하대학교 산학협력단 Continuous manufacturing methods of acetic acid from CH4 and CO2 using fixed-bed reactor
WO2021250493A1 (en) * 2020-06-09 2021-12-16 Nova Chemicals (International) S.A. Forming acetic acid by the selective oxidation of methane
CN114832839A (en) * 2022-05-31 2022-08-02 南京工业大学 Iron-based solid super acidic catalyst synthesized by persulfate in assistance, preparation and application thereof

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Publication number Priority date Publication date Assignee Title
GB226248A (en) * 1923-06-22 1924-12-22 Henry Dreyfus Improvements relating to the manufacture of acetic acid, acetaldehyde or acetone or mixtures containing the same
CH139179A (en) * 1926-05-12 1930-04-15 Casale Sacchi Maria Process for the production of liquid mixtures of aliphatic saturated oxygen-containing compounds by catalytic conversion of gaseous hydrocarbons with oxides of carbon under the application of pressure.
FR768584A (en) * 1933-03-23 1934-08-08 Manufacturing process for aliphatic acids
US4016185A (en) * 1975-12-11 1977-04-05 Chevron Research Company Production of carboxylic acids from paraffins and carbon dioxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB226248A (en) * 1923-06-22 1924-12-22 Henry Dreyfus Improvements relating to the manufacture of acetic acid, acetaldehyde or acetone or mixtures containing the same
CH139179A (en) * 1926-05-12 1930-04-15 Casale Sacchi Maria Process for the production of liquid mixtures of aliphatic saturated oxygen-containing compounds by catalytic conversion of gaseous hydrocarbons with oxides of carbon under the application of pressure.
FR768584A (en) * 1933-03-23 1934-08-08 Manufacturing process for aliphatic acids
US4016185A (en) * 1975-12-11 1977-04-05 Chevron Research Company Production of carboxylic acids from paraffins and carbon dioxide

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1103330C (en) * 2000-09-30 2003-03-19 太原理工大学 Process for synthesizing acetic acid in heterogeneous catalysis system
US6960682B2 (en) 2003-07-24 2005-11-01 The Regents Of The University Of California Process for production of acetyl anhydrides and optionally acetic acid from methane and carbon dioxide
US7009074B2 (en) 2004-07-28 2006-03-07 The Regents Of The University Of California Process for direct oxidation of methane to acetic acid
KR101838612B1 (en) * 2016-04-11 2018-03-14 인하대학교 산학협력단 Continuous manufacturing methods of acetic acid from CH4 and CO2 using fixed-bed reactor
WO2021250493A1 (en) * 2020-06-09 2021-12-16 Nova Chemicals (International) S.A. Forming acetic acid by the selective oxidation of methane
CN114832839A (en) * 2022-05-31 2022-08-02 南京工业大学 Iron-based solid super acidic catalyst synthesized by persulfate in assistance, preparation and application thereof
CN114832839B (en) * 2022-05-31 2023-09-26 南京工业大学 Persulfate-assisted synthesis of iron-based solid superacid catalyst and its preparation and application

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