DE3439643A1 - Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst - Google Patents

Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst

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Publication number
DE3439643A1
DE3439643A1 DE19843439643 DE3439643A DE3439643A1 DE 3439643 A1 DE3439643 A1 DE 3439643A1 DE 19843439643 DE19843439643 DE 19843439643 DE 3439643 A DE3439643 A DE 3439643A DE 3439643 A1 DE3439643 A1 DE 3439643A1
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DE
Germany
Prior art keywords
catalyst
hydrogen
chromium
formaldehyde
absence
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.)
Withdrawn
Application number
DE19843439643
Other languages
German (de)
Inventor
Erich Dr. 8600 Bamberg Hums
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Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to DE19843439643 priority Critical patent/DE3439643A1/en
Publication of DE3439643A1 publication Critical patent/DE3439643A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

A process is proposed for reacting formaldehyde to give water, carbon monoxide and hydrocarbons. The catalyst system is a true surface compound in the form of a combination of reducible chromium(VI) species and sparingly reducible metal oxide (for example silicon dioxide, Al2O3, ceramic compositions). The hydrogen which is fed in is used as hydrogenating agent for carbon monoxide and carbon dioxide. In addition to the hydrogenation of the carbon oxides, the presence of hydrogen causes constant regeneration of the catalyst. This is why traces of oxygen in the reaction gas do not constitute a catalyst poison, since the catalyst is constantly converted into its reduced form under the operating conditions.

Description

Bezeichnung: Verfahren zur Umsetzung von FormaldehydName: Process for converting formaldehyde

in Anwesenheit und Abwesenheit von Wasserstoff mit einem Festbett-Katalysator. in the presence and absence of hydrogen with a fixed bed catalyst.

Um die intermediäre Bildung von Formaldehyd bei der Umsetzung von Kohlenmonoxid mit Wasserstoff an Fischer-Tropsch-Katalysatoren wird seit vielen Jahren spekuliert. Im Rahmen grundlegender Untersuchungen an reduzierbaren Oberflächen-Chrom-Verbindungen konnte der Nachweis für ein Formaldehyd-Intermediat erbracht werden. In der Zeitschrift "Industrial and Engineering Chemistry" ist von mir dieser Effekt erstmals publiziert worden.To the intermediate formation of formaldehyde in the implementation of Carbon monoxide with hydrogen on Fischer-Tropsch catalysts has been used for many Years of speculation. As part of fundamental investigations into reducible surface chromium compounds proof of a formaldehyde intermediate could be provided. In the magazine I published this effect for the first time in "Industrial and Engineering Chemistry" been.

Als Katalysatoren eignen sich grundsätzlich alle Oberflächen-Chrom(VI)-Verbindungen auf entsprechenden Trägermaterialien, die durch Reduktionsmittel, wie CO, H2 (natürlich auch Formaldehyd).sind oder aufgrund ihrer Präperation bereits als reduzierte Oberflächen-Verbindungen eingesetzt werden. Die Trägermaterialien sind erfahrungsgemäß bei ca. 3 Gewichts-%iger Chrom-Dotierung abgesättigt. Ihr Dotierungsgrad richtet sich nach der OH-Population des jeweils eingesetzten Trägers. Als Trägermaterialien eignen sich schwer reduzierbare Metalloxide von Aluminium, Silicium oder Mischungen daraus, keramische Massen, die eine OH-gruppenreiche Oberfläche besitzen.In principle, all surface chromium (VI) compounds on appropriate support materials that are or are due to reducing agents such as CO, H2 (of course also formaldehyde) are suitable as catalysts can already be used as reduced surface compounds due to their preparation. Experience has shown that the carrier materials are saturated at approx. 3% by weight chromium doping. Their degree of doping depends on the OH population of the particular carrier used. Suitable carrier materials are metal oxides of aluminum, silicon or mixtures thereof which are difficult to reduc, ceramic masses which have a surface rich in OH groups.

Die Lage des Gleichgewichts bei der Umsetzung von Formaldehyd zu den Reaktionsprodukten Methan, Wasser, Kohlenmonoxid liegt zu 100 % auf der Seite der Produkte. Der Prozeß der Formaldehyd-"Zersetzung" ist in Anwesenheit von Wasserstoff katalytisch. Die Umsetzung von reduziertem Oberflächen-Chrom(VI) auf Träger Merck 7733 mit Formaldehyd führte bei T = 300 "C zu den Produkten Methan, Wasser Kohlenmonoxid, Kohlendioxid. Die Ausbeute an Methan ließ sich durch Wasserstoff-Einspeisung in den Reaktionsraum auf Kosten der gebildeten Kohlenoxide steigern.The position of equilibrium in the conversion of formaldehyde to the Reaction products methane, water and carbon monoxide are 100% on the side of the Products. The process of formaldehyde "decomposition" is in the presence of hydrogen catalytic. The implementation of reduced surface chromium (VI) on support Merck 7733 with formaldehyde led at T = 300 "C to the products methane, water carbon monoxide, Carbon dioxide. The yield of methane could be by feeding hydrogen into increase the reaction space at the expense of the carbon oxides formed.

Darstellungsbeispiele für Oberflächen-Chrom(VI)-Verbindungen auf Silicagel-Trägern bekannter Kenngrößen 1. 100 g Silicagel wurden durch 30-minütiges Kochen mit 400 ml destilliertem Wasser hydroxiliert. Nach Filtration wurde das Produkt gut getrocknet.Representation examples for surface chromium (VI) compounds on silica gel carriers Known parameters 1. 100 g of silica gel were boiled for 30 minutes with 400 ml of distilled water hydroxylated. After filtration, the product was dried well.

2. Die Chromdotierung erfolgte mit wässriger Chrom(VI)-Säure.2. The chromium was doped with aqueous chromium (VI) acid.

Zur Darstellung von Silicagel-Katalysatoren mit beispielsweise 0,3 % Gesamtchrom wurde 1 g Cr03 in 200 ml destilliertem Wasser gelöst und 100 g Silicagel aus 1. eingerührt. Nach ca. For the preparation of silica gel catalysts with, for example, 0.3 % Total chromium, 1 g of Cr03 was dissolved in 200 ml of distilled water and 100 g of silica gel stirred in from 1.. After approx.

15 min wurde das Produkt abgenutscht. Alternativ dazu wurde der Dotierungsschritt der Gele durch Zutropfen einer Chromsäure Maßlösung zu der gerührten, trockenen Silicagel-Masse vorgenommen. The product was suction filtered for 15 minutes. Alternatively, the doping step was used of the gels by adding dropwise a chromic acid standard solution to the stirred, dry one Silica gel mass made.

3. Die Trocknung erfolgte 15 Std. bei ca. 120 "C/Wasserstrahlpumpenvakuum. Das rieselfähige Produkt wurde im Sauerstoffstrom im Laufe von 8 Std. auf 800 OC aufgeheizt. Diese Temperatur von 800 "C wurde ca. 30 min konstant gehalten. Dann wurde im Sauerstoffstrom auf Raumtemperatur abgekühlt.3. Drying took place for 15 hours at approx. 120 ° C. / water jet pump vacuum. The free-flowing product was in a stream of oxygen over the course of 8 hours to 800 OC heated up. This temperature of 800 ° C. was kept constant for about 30 minutes. Then was cooled to room temperature in a stream of oxygen.

Claims (5)

patentansprüche.patent claims. Das Das Verfahren zur Umsetzung von Formaldehyd ist dadurch gekennzeichnet, daß es an einem Festbett-Katalysator erfolgt, der eine Kombination aus reduzierbarer Chrom(VI)-Verbindung und schwer reduzierbarem Metalloxid darstellt, die unter den Betriebsbedingungen eine reduzierte Chrom-Oberflächenverbindung darstellt.The process for converting formaldehyde is characterized by that it takes place on a fixed bed catalyst, which is a combination of reducible Chromium (VI) compound and difficult to reducible metal oxide, which are under the Operating conditions represents a reduced chromium surface bond. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Kombination aus Träger und Chromkomponente einen Chromgehalt von 3 Gewichtsprozent nicht überschreitet. 2. The method according to claim 1, characterized in that the combination from carrier and chromium component does not exceed a chromium content of 3 percent by weight. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß der Katalysator in seiner oxidierten oder in einer reduzierten Form eingesetzt werden kann. 3. The method according to claim 1 and 2, characterized in that the Catalyst can be used in its oxidized or in a reduced form can. 4. Verfahren nach Anspruch 1, 2 und 3, dadurch gekennzeichnet, daß der Katalysator Formaldehyd in Anwesenheit und Abwesenheit von Wasserstoff umsetzt. 4. The method according to claim 1, 2 and 3, characterized in that the catalyst converts formaldehyde in the presence and absence of hydrogen. 5. Verfahren nach Ansprch 1, 2, 3 und 4, dadurch gekennzeichnet, daß die Umsetzungstemperatur variabel ist, vorzugsweise bei Normaldruck oberhalb 200 ° C liegt, ansonsten bereits darunter. 5. The method according to claim 1, 2, 3 and 4, characterized in that that the reaction temperature is variable, preferably at normal pressure above 200 ° C, otherwise already below.
DE19843439643 1984-10-30 1984-10-30 Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst Withdrawn DE3439643A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19843439643 DE3439643A1 (en) 1984-10-30 1984-10-30 Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19843439643 DE3439643A1 (en) 1984-10-30 1984-10-30 Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst

Publications (1)

Publication Number Publication Date
DE3439643A1 true DE3439643A1 (en) 1986-04-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
DE19843439643 Withdrawn DE3439643A1 (en) 1984-10-30 1984-10-30 Process for reacting formaldehyde in the presence and absence of hydrogen using a fixed-bed catalyst

Country Status (1)

Country Link
DE (1) DE3439643A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5606107A (en) * 1995-06-07 1997-02-25 Monsanto Company Formic acid and formaldehyde destruction in waste streams

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5606107A (en) * 1995-06-07 1997-02-25 Monsanto Company Formic acid and formaldehyde destruction in waste streams

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