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EP0000055B1 - Preparation of silica containing hydrogenation catalysts and their use in hydrogenation - Google Patents

Preparation of silica containing hydrogenation catalysts and their use in hydrogenation Download PDF

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Publication number
EP0000055B1
EP0000055B1 EP78100097A EP78100097A EP0000055B1 EP 0000055 B1 EP0000055 B1 EP 0000055B1 EP 78100097 A EP78100097 A EP 78100097A EP 78100097 A EP78100097 A EP 78100097A EP 0000055 B1 EP0000055 B1 EP 0000055B1
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Prior art keywords
hydrogenation
catalyst
solution
nickel
copper
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German (de)
French (fr)
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EP0000055A1 (en
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Wolfgang Dr. Schroeder
Wolfgang Dr. Franzischka
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BASF SE
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BASF SE
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/75Cobalt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica

Definitions

  • a nickel-alumina catalyst with an amorphous structure is obtained during the precipitation.
  • catalysts from common precipitation of copper, nickel and / or cobalt with silica with a metal content between about 40 and 80% by weight, based on the total weight, i.e. the shaped, dried, tempered and reduced solid show a clear activity maximum. The maximum is pronounced at around 60 to 70%, with certain fluctuations depending on the type of metal being observed.
  • the subject of the invention is therefore a process for the preparation of hydrogenation catalysts which contain copper, nickel or cobalt on a silica support, which is characterized in that aqueous solutions of salts of copper, nickel and / or cobalt with alkali silicate solutions with a ratio of Me 2 0 to Sio 2 over 1 (where Me means sodium or potassium) in such amounts that the mixture has a pH of 6 to 8 and the metal content of copper, nickel and / or cobalt in the finished catalyst is about 40 to 80% by weight % and the precipitation that occurs during the mixture is obtained in the usual way, molded, dried and treated with reducing agents.
  • the catalysts are manufactured according to a principle that is the same for all metals.
  • a chlorine and sulfur free compound is preferred as the metal salt, e.g. Nitrate, acetate or formate.
  • a preferred approximately 1 to 3 molar aqueous solution is prepared therefrom.
  • alkali silicate solution can be used as the starting material for the preparation of the catalysts.
  • This water glass can have different alkali oxide / Si0 2 ratios. exhibit; the molar ratio Me 2 0 / Si0 2 can for example be between 0.25 to 1.4.
  • the compounds are not stoichiometrically composed, molar ratios of 1 (which corresponds to the metasilicate) are generally present.
  • alkali-rich silicates can be produced, the tendency to hydrolytically cleave in aqueous solution increases with increasing alkali content, so that compounds which are stable for a relatively long time are hardly definable here.
  • Si0 2 -rich silicates contain polymeric silica anions, as is known for ordinary water glass (cf. Hollemann-Wiberg, textbook of inorganic chemistry).
  • the alkali hydroxide excess is understood to be the amount of alkali hydroxide by which the (arithmetical) molar ratio Me 2 0: Sio 2 is shifted into the range above 1.
  • the resulting solution contains silicate ions and an excess of alkali.
  • the concentration of silications is not critical.
  • the alkali silicate and the metal salt solution are combined in amounts which give the desired ratio, taking into account the concentration, preferably at an elevated temperature (for example at 60 to 90 ° C.).
  • a pH in the resulting mixture is -Value from 6 to 8, preferably maintained at 7.
  • the amount of alkali hydroxide required for this is determined in each case in a preliminary test.
  • the precipitate is washed free of alkali and nitrate and then separated from the wash water.
  • the precipitation is dried under mild conditions. To either vacuum drying at 100 to 120 ° C or spray drying at 100 to 150 ° C is used.
  • Spray drying supplies the dried catalyst precursor in a particle size suitable for hydrogenation in the suspension process.
  • the products from both drying methods are suitable for forming into tablets or other bodies suitable for hydrogenation in a fixed bed.
  • the two solutions were fed in a 1: 1 ratio to a kettle equipped with an effective stirrer.
  • a temperature of 80 to 90 ° C. was maintained in the stirred tank by external heating and by preheating the solutions.
  • the pH value of 7 was maintained by regulating the feed quantity of solution 1 in the mother liquor.
  • the dry matter now had a pastel blue color. After subsequent temperature treatment at 300 ° C., the dry mass had a purely green color, and the X-ray analysis showed an amorphous state.
  • Part of this dry matter was mechanically brought to a grain size of 60 to 100 ⁇ , which is suitable for carrying out suspension catalytic tests.
  • Another part was pressed into cylindrical tablets with the main dimensions 3 x 3 mm and then annealed at 350 ° C. In this form, the catalyst precursor is suitable for investigations in a fixed bed.
  • the copper concentration in the reduced state was 62% by weight. According to this general preparation procedure, further catalysts were produced, the composition of which can be seen from the following examples.
  • Example 1 The powder from Example 1 prepared for suspension catalysis was heated to 120 ° C. in an indirectly heated fluidized bed in a stream of nitrogen. After adding hydrogen in an amount of 1 to 2% by volume of nitrogen, the reduction of the copper oxide content in the catalyst precursor begins. The water formed was condensed and measured. When the water separation ceased, the temperature was increased until 180 ° C. was finally reached. The calculated amount of water was calculated. Now the nitrogen flow was shut off and the fluidized bed was fed with pure hydrogen.
  • the catalyst was suspended in a mixture of methyl esters of C 4 - to C a -dicarboxylic acids, so that 5% by weight of catalyst was present in the suspension. This suspension was transferred to a heated autoclave for hydrogenation. After removing the atmospheric oxygen, the hydrogenation conditions were set: 230 ° C. and 250 bar. The progress of the hydrogenation reaction was followed by the consumption of hydrogen and by the determination of the ester number on occasionally taken samples.
  • the original ester mixture had an ester number of 700, after 12 hours an ester number of 60 was found in the hydrogenation mixture.
  • Ni (N0 3 ) 2. 6H 2 0 nickel nitrate (Ni (N0 3 ) 2. 6H 2 0) was dissolved in water, so that a 1 molar solution was formed.
  • the water glass described in Example 1 was used to prepare solution 2, in an amount such that 0.5 mol of SiO 2 was present in 1 mol of the nickel dissolved in solution 1. 112 g of potassium water glass were therefore used for 1 l of solution 1. This does not contain enough K 2 0 to bind the nitrate ions, so that KOH had to be added to the water glass, namely 1.66 mol KOH per liter of solution 1.
  • the dried precipitation was annealed at 550 ° C. Part of this mass was mechanically brought to a grain size of 60 to 100 ⁇ , which is suitable for carrying out suspension catalytic tests. Another part was pressed into cylindrical tablets with a height of 3 mm and a diameter of 5 mm. In this form, the catalyst precursor is suitable for investigations in a fixed bed.
  • Example 12 prepared for suspension catalysis was gradually heated up to 570 ° C. in an indirectly heated fluidized bed with circulated hydrogen and thereby reduced.
  • the catalyst was slurried in a technical, crude butynediol solution, so that a suspension with 5% by weight of catalyst was formed.
  • the crude butynediol solution had the following composition according to gas chromatographic analysis:
  • the catalyst suspension was transferred to a high pressure bubble column.
  • the suspension was gassed with hydrogen at 90 bar and 40 to 50 ° C.
  • the flow rate of the hydrogen in the (thought empty) bubble acid was 2 cm / sec.
  • Samples were taken from the bubble column and analyzed at intervals of 10 minutes.
  • C C multiple bonds are then no longer detectable. This end of hydrogenation was reached after 45 minutes.
  • the catalysts obtained from Examples 8 to 11 were reduced in particle sizes from 60 to 100 ⁇ m in the indirectly heated fluidized bed at temperatures up to a maximum of 550 ° C. in a stream of hydrogen. They were then slurried in toluene and mixed with adipic acid dinitrile in the high pressure bubble acid. The mixture then consisted of 76% by weight of toluene, 19% by weight of adiponitrile and 5% by weight of catalyst. It was then hydrogenated at 90 bar, 100 ° C., the flow rate of the hydrogen based on the (empty) bubble column was 2 cm / sec. The progress of the hydrogenation reaction, which mainly produces hexamethylenediamine, was followed by the increase in the amine number over time. The results are summarized in Table 3.
  • Example 12 a catalyst with the formula composition CuO. Co0 - Si0 2 produced, which was deformed into tablets with a height of 5 mm and a diameter of 5 mm. In the reduced state, the catalyst thus contained 67% by weight of active metals.
  • a thermostable pressure-resistant reactor contained 500 ml of this catalyst. Hydrogen was passed through the catalyst bed from top to bottom, in an amount corresponding to 100 NI per hour at the reactor outlet. A pressure of 200 bar and a temperature of 75 ° C. were set in the reactor. A mixture of benzonitrile and ammonia was then run in continuously in an hourly amount of 1.2 l, 2 volumes of ammonia (liquid) being used for 1 volume of benzonitrile.
  • reaction mixture drawn off consisted of 98% by weight of benzylamine, 0.05% by weight of benzonitrile and less than 2% of by-products or impurities.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Es ist bekannt, Hydrierkatalysatoren mit feiner Verteilung der wirksamen Stoffe in Aluminiumoxid dadurch herzustellen, daß man die hydrierend wirkenden Stoffe aus einer Lösung zusammen mit gelösten Aluminiumsalzen mit Hilfe einer Alkalicarbonatlösung ausfällt und für die Fällung die Kristallstruktur des Mannaseits, in einem anderen Verfahren die Kristallstruktur des Takovits anstrebt (vgl. DE-C 20 24 282, DE-A- 24 45 303).It is known to produce hydrogenation catalysts with a fine distribution of the active substances in aluminum oxide by precipitating the hydrogenating substances from a solution together with dissolved aluminum salts with the aid of an alkali metal carbonate solution and for the precipitation the crystal structure of the manna side, in another process the crystal structure of the Takovits strives (see. DE-C 20 24 282, DE-A-24 45 303).

In einem anderen Fall wird bei der Fällung ein Nickel-Aluminiumoxid-Katalysator mit amorpher Struktur erhalten.In another case, a nickel-alumina catalyst with an amorphous structure is obtained during the precipitation.

In Katalysatorsystemen, die Kieselsäure als Träger bzw. chemisch indifferentes Verteilungsmedium anstelle von Aluminiumoxid enthalten, sucht man die feine Verteilung der wirksamen Stoffe bisher dadurch zu erreichen, daß man entweder einen porösen Träger mit einer Lösung der Stoffe tränkt oder den Träger in feinteiliger Form suspendiert und die Stoffe durch Fällung aufbringt. Methoden zur gemeinsamen Fällung von Aktivkomponente und Inertmaterial sind ebenfalls beschrieben worden.In catalyst systems which contain silica as a carrier or chemically indifferent distribution medium instead of aluminum oxide, attempts have been made to achieve the fine distribution of the active substances by either impregnating a porous carrier with a solution of the substances or suspending the carrier in finely divided form and the substances are deposited by precipitation. Methods for the co-precipitation of active component and inert material have also been described.

Ein solches Verfahren, bei dem Kupfer- und Nickelkationen zusammen mit Silikationen auf einem Träger, bevorzugt ebenfalls Kieselsäure durch Fällung mittels Ammoniumbicarbonat niedergeschlagen werden, ist aus der DE-A 26 20 554 bekannt. Die danach hergestellten Katalysatoren müssen jedoch sorgfältig von Alkalimetallionen freigehalten werden, wodurch sie sonst vergiftet werden und bestehen hinsichtlich ihrer wirksamen Metalle anscheinend überwiegend aus Nickel, wobei der Gesamtgehalt an Metallen relativ niedrig ist.Such a process, in which copper and nickel cations are deposited together with silications on a support, preferably also silica, by precipitation using ammonium bicarbonate is known from DE-A 26 20 554. However, the catalysts produced after this must be carefully kept free from alkali metal ions, as a result of which they are poisoned and, in terms of their active metals, apparently consist predominantly of nickel, the total content of metals being relatively low.

Es wurde nun gefunden, daß Katalysatoren aus gemeinsamen Fällungen von Kupfer, Nickel und/oder Kobalt mit Kieselsäure bei einem Metallgehalt zwischen etwa 40 und 80 Gew.%, bezogen auf das Gesamtgewicht, d.h. den geformten, getrockneten, getemperten und reduzierten Feststoff ein deutliches Aktivitätsmaximum zeigen. Ausgeprägt ist das Maximum bei etwa 60 bis 70%, wobei gewisse Schwankungen je nach Art des Metalls beobachtet wurden.It has now been found that catalysts from common precipitation of copper, nickel and / or cobalt with silica with a metal content between about 40 and 80% by weight, based on the total weight, i.e. the shaped, dried, tempered and reduced solid show a clear activity maximum. The maximum is pronounced at around 60 to 70%, with certain fluctuations depending on the type of metal being observed.

Erfindungsgegenstand ist daher ein Verfahren zur Herstellung von Hydrierkatalysatoren, die Kupfer, Nickel oder Kobalt auf einem Kieselsäure-Träger enthalten, das dadurch gekennzeichnet ist, daß man wäßrige Lösungen von Salzen des Kupfers, Nickels und/oder Kobalts mit Alkalisilikatlösungen mit einem Verhältnis von Me20 zu Sio2 über 1 (wobei Me Natrium oder Kalium bedeutet) in solchen Mengen vermischt, daß die Mischung einen pH-Wert von 6 bis 8 aufweist und der Metallgehalt an Kupfer, Nickel und/oder Kobalt im fertigen Katalysator etwa 40 bis 80 Gewichts% beträgt und die bei der Mischung ausfallenden Niederschläge in üblicher Weise gewinnt, formt, trocknet und mit reduzierenden Mitteln behandelt.The subject of the invention is therefore a process for the preparation of hydrogenation catalysts which contain copper, nickel or cobalt on a silica support, which is characterized in that aqueous solutions of salts of copper, nickel and / or cobalt with alkali silicate solutions with a ratio of Me 2 0 to Sio 2 over 1 (where Me means sodium or potassium) in such amounts that the mixture has a pH of 6 to 8 and the metal content of copper, nickel and / or cobalt in the finished catalyst is about 40 to 80% by weight % and the precipitation that occurs during the mixture is obtained in the usual way, molded, dried and treated with reducing agents.

Im einzelnen wurden die Aktivitätsmaxima bei folgenden Metallkonzentrationen gefunden

  • für Kupfer 50 bis 80, insbesondere 60 bis 65 Gew.%,
  • für Nickel 50 bis 80, insbesondere 65 bis 70 Gew.%,
  • für Kobalt 55 bis 75, insbesondere 65 Gew.%.
The activity maxima were found at the following metal concentrations
  • for copper 50 to 80, in particular 60 to 65% by weight,
  • for nickel 50 to 80, in particular 65 to 70 wt.%,
  • for cobalt 55 to 75, in particular 65% by weight.

Die Katalysatoren werden nach einem für alle Metalle übereinstimmenden Prinzip hergestellt. Als Metallsalz wird eine chlor- und schwefelfreie Verbindung bevorzugt, z.B. Nitrat, Acetat oder Formiat. Hieraus wird eine bevorzugte etwa 1- bis 3-molare wäßrige Lösung hergestellt.The catalysts are manufactured according to a principle that is the same for all metals. A chlorine and sulfur free compound is preferred as the metal salt, e.g. Nitrate, acetate or formate. A preferred approximately 1 to 3 molar aqueous solution is prepared therefrom.

Als Ausgangsmaterial zur Herstellung der Katalysatoren kann man handelsübliches Wasserglas (Alkalisilikatlösung) verwenden. Dieses Wasserglas kann unterschiedliche Alkalioxid/Si02 Verhältnisse. aufweisen; das Molverhältnis Me20/Si02 kann z.B. zwischen 0,25 bis 1,4 liegen. Es handelt sich also im allgemeinen nicht um stöchiometrisch zusammengesetzte Verbindungen, wobei in der Regel Molverhältnisse um 1 (was dem Metasilikat entspricht) vorliegen. Alkalireichere Silikate lassen sich zwar herstellen, mit zunehmendem Alkaligehalt steigt jedoch die Neigung, in wäßriger Lösung hydrolytisch zu spalten, so daß hier kaum definierbare, längere Zeit stabile Verbindungen vorliegen. Si02-reichere Silikate enthalten polymere Kieselsäureanionen, wie dies für das gewöhnliche Wasserglas bekannt ist (vgl. Hollemann-Wiberg, Lehrbuch der anorg. Chemie).Commercial water glass (alkali silicate solution) can be used as the starting material for the preparation of the catalysts. This water glass can have different alkali oxide / Si0 2 ratios. exhibit; the molar ratio Me 2 0 / Si0 2 can for example be between 0.25 to 1.4. In general, the compounds are not stoichiometrically composed, molar ratios of 1 (which corresponds to the metasilicate) are generally present. Although alkali-rich silicates can be produced, the tendency to hydrolytically cleave in aqueous solution increases with increasing alkali content, so that compounds which are stable for a relatively long time are hardly definable here. Si0 2 -rich silicates contain polymeric silica anions, as is known for ordinary water glass (cf. Hollemann-Wiberg, textbook of inorganic chemistry).

Es konnte festgestellt werden, daß man für die Zwecke der Erfindung am besten von solchen stabilen Polysilikat-Anionen ausgeht. Demzufolge verwendet man als Ausgangsmaterial ein Wasserglas mit einem Molverhältnis Me,0 : Si02, das z.B. zwischen 0,5 und 1 liegt, dem man Alkalihydroxid zusetzt (Me = Na, K). Als Alkalihydroxid-Überschuß wird die Menge Alkalihydroxid verstanden, durch die das (rechnerische) Molverhältnis Me20 : Sio2 in den Bereich über 1 verschoben wird. Die so entstehende Lösung enthält also Silikationen und einen Überschuß Alkali. Die Konzentration an Silikationen ist nicht kritisch.It was found that such stable polysilicate anions are best used for the purposes of the invention. Accordingly, the starting material used is a water glass with a molar ratio of Me, 0: Si0 2 , which is, for example, between 0.5 and 1, to which alkali metal hydroxide is added (Me = Na, K). The alkali hydroxide excess is understood to be the amount of alkali hydroxide by which the (arithmetical) molar ratio Me 2 0: Sio 2 is shifted into the range above 1. The resulting solution contains silicate ions and an excess of alkali. The concentration of silications is not critical.

Die Alkalisilikat- und die Metallsalz-Lösung werden in Mengen, die unter Berücksichtigung der Konzentration das gewünschte Verhältnis ergeben, bevorzugt bei erhöhter Temperatur (z.B. bei 60 bis 90°C vereinigt. Während der Zusammenführung der beiden Lösungen wird in dem sich ergebenden Gemisch ein pH-Wert von 6 bis 8, bevorzugt um 7, aufrecht erhalten. Die hierzu notwendige Alkalihydroxidmenge wird jeweils in einem Vorversuch ermittelt.The alkali silicate and the metal salt solution are combined in amounts which give the desired ratio, taking into account the concentration, preferably at an elevated temperature (for example at 60 to 90 ° C.). During the combination of the two solutions, a pH in the resulting mixture is -Value from 6 to 8, preferably maintained at 7. The amount of alkali hydroxide required for this is determined in each case in a preliminary test.

Nach der Fällung wird der Niederschlag alkali- und nitratfrei gewaschen und dann vom Waschwasser abgetrennt.After the precipitation, the precipitate is washed free of alkali and nitrate and then separated from the wash water.

Die Trocknung des Niederschlags wird bei schonenden Bedingungen durchgeführt. Dazu verwendet man entweder eine Vakuumtrocknung bei 100 bis 120°C oder eine SprühtrocKnung bei 100 bis 150°C.The precipitation is dried under mild conditions. To either vacuum drying at 100 to 120 ° C or spray drying at 100 to 150 ° C is used.

Sprühtrocknung liefert den getrockneten Katalysatorvorläufer in einer für die Hydrierung im Suspensionsverfahren geeigneten Korngröße. Die Produkte aus beiden Trocknungsmethoden sind zur Verformung zu Tabletten oder anderen für die Hydrierung im Festbett geeigneten Körper geeignet.Spray drying supplies the dried catalyst precursor in a particle size suitable for hydrogenation in the suspension process. The products from both drying methods are suitable for forming into tablets or other bodies suitable for hydrogenation in a fixed bed.

Beispiel 1example 1

Zur Bereitung einer Lösung 1 wurde Kupfer-(II)-Nitrat-Hydrat (Cu(N03)2 3H20) in Wasser zu einer 1-molaren Lösung gelöst.To prepare a solution 1, copper (II) nitrate hydrate (Cu (N0 3 ) 2 3H 2 0) was dissolved in water to give a 1-molar solution.

Zur Bereitung der Lösung 2 wurde handelsübliches Kaliwasserglas mit 4,45 Mol Si02 pro Kilogramm und 1,52 Mol K20 pro Kilogramm verwendet, und zwar in einer Menge, daß auf 1 Mol des in Lösung 1 gelösten Kupfers 0,67 Mol Si02 entfielen. Auf 1 I der Lösung 1 wurden also 150 gi Kaliwasserglas verwendet. Dieses enthält nichf genügend K20 zur Bindung der Nitrarionen, so daß dem Wasserglas KOH zugesetzt werden mußte, und zwar 1,544 Mol KOH pro Liter Lösung 1. Für 1 l Lösung 1 enthielt die Lösung 2 als Fälläquivalent also 0,67 Mol Si02 und 1 Mol K20 (= 2 Mol KOH). Die Lösung 2 wurde schließlich auf das der Lösung 1 entsprechende Volumen gebracht, um die Fällung bequem vornehmen zu können.To prepare solution 2, commercially available potassium water glass with 4.45 mol Si0 2 per kilogram and 1.52 mol K 2 0 per kilogram was used, in an amount such that 0.67 mol Si0 per 1 mol of the copper dissolved in solution 1 2 accounted for. 150 gi of potassium water glass were therefore used in 1 l of solution 1. This does not contain enough K 2 0 to bind the nitrarions, so that KOH had to be added to the water glass, namely 1.544 mol KOH per liter of solution 1. For 1 l of solution 1, solution 2 contained 0.67 mol of SiO 2 and 1 mol K 2 0 (= 2 mol KOH). Solution 2 was finally brought to the volume corresponding to solution 1 in order to be able to carry out the precipitation conveniently.

Die beiden Lösungen wurden im Verhältnis 1:1 einem Kessel zugeführt, der mit einem wirkungsvollen Rührer ausgestattet war. Im Rührkessel wurde durch äußere Beheizung und durch Vorwärmen der Lösungen eine Temperatur von 80 bis 90°C aufrecht erhalten. Während des Zusammengebens der Lösungen wurde durch Regulierung der Zulaufmenge der Lösung 1 in der Mutterlauge die Einhaltung eines pH-Wertes von 7 sichergestellt.The two solutions were fed in a 1: 1 ratio to a kettle equipped with an effective stirrer. A temperature of 80 to 90 ° C. was maintained in the stirred tank by external heating and by preheating the solutions. While the solutions were being combined, the pH value of 7 was maintained by regulating the feed quantity of solution 1 in the mother liquor.

Nach beendeter Fällung wurde der rein blaue Niederschlag von der Mutterlauge abgetrennt und dann mit kaltem Wasser gewaschen bis im Waschwasser kein Nitrat mehr nachweisbar war.After the precipitation had ended, the purely blue precipitate was separated from the mother liquor and then washed with cold water until nitrate was no longer detectable in the wash water.

Nach mechanischer Abtrennung des Niederschlags vom Waschwasser wurde in einer Vakuum-Trockenkammer bei Lufttemperaturen um 120°C getrocknet.After mechanical separation of the precipitate from the wash water, drying was carried out in a vacuum drying chamber at air temperatures around 120 ° C.

Die Trockenmasse hatte nun eine pastellblaue Farbe. Nach anschließender Temperaturbehandlung bei 300°C hatte die Trokkenmasse eine rein grüne Farbe, die Röntgenanalyse ergab einen amorphen Zustand. Ein Teil dieser Trockenmasse wurde mechanisch auf eine Körnung von 60 bis 100µ gebracht, die zur Durchführung von suspensionskatalytischen Untersuchungen geeignet ist. Ein anderer Teil wurde zu zylinderförmigen Tabletten mit den Hauptmaßen 3 x 3 mm verpreßt und anschließend bei 350°C getempert. In dieser Form ist der Katalysatorvorläufer für Untersuchungen im Festbett geeignet.The dry matter now had a pastel blue color. After subsequent temperature treatment at 300 ° C., the dry mass had a purely green color, and the X-ray analysis showed an amorphous state. Part of this dry matter was mechanically brought to a grain size of 60 to 100µ, which is suitable for carrying out suspension catalytic tests. Another part was pressed into cylindrical tablets with the main dimensions 3 x 3 mm and then annealed at 350 ° C. In this form, the catalyst precursor is suitable for investigations in a fixed bed.

Die Kupferkonzentration im reduzierten Zustand betrug 62 Gew.%. Nach dieser allgemeinen Herstellvorschrift wurden weitere Katalysatoren hergestellt, deren Zusammensetzung aus folgenden Beispielen ersichtlich ist.

Figure imgb0001
The copper concentration in the reduced state was 62% by weight. According to this general preparation procedure, further catalysts were produced, the composition of which can be seen from the following examples.
Figure imgb0001

Anwendungsbeispiel 1Application example 1

Das zur Suspensionskatalyse vorbereitete Pulver aus Beispiel 1 wurde in einer indirekt beheizten Wirbelschicht im Stickstoffstrom auf 120°C aufgeheizi. Nach Zumischung von Wasserstoff in einer Menge von 1 bis 2 Vol% des Stickstoffs beginnt die Reduktion des Kupferoxidanteils im Katalysatorvorläufer. Das dabei gebildete Wasser wurde kondensiert und gemessen. Beim Nachlassen der Wasserabscheidung wurde die Temperatur erhöht, bis schließlich 180°C erreicht waren. Dabei wurde die rechnerisch zu erwartende Wassermenge gebildet. Nunmehr wurde Stickstoffstrom abgesperrt und die Wirbelschicht mit reinem Wasserstoff beschickt.The powder from Example 1 prepared for suspension catalysis was heated to 120 ° C. in an indirectly heated fluidized bed in a stream of nitrogen. After adding hydrogen in an amount of 1 to 2% by volume of nitrogen, the reduction of the copper oxide content in the catalyst precursor begins. The water formed was condensed and measured. When the water separation ceased, the temperature was increased until 180 ° C. was finally reached. The calculated amount of water was calculated. Now the nitrogen flow was shut off and the fluidized bed was fed with pure hydrogen.

Nach dem Abkühlen unter Wasserstoff wurde der Katalysator in einem Gemisch von Methylestern von C4- bis Ca-Dicarbonsäuren suspendiert, so daß in der Suspension 5 Gew.% Katalysator vorhanden waren. Diese Suspension wurde zur Hydrierung in einen beheizbaren Rührautoklaven überführt. Nach Entfernen des Luftsauerstoffs wurden die Hydrierbedingungen eingestellt: 230°C und 250 bar. Das Fortschreiten der Hydrierreaktion wurden durch den Wasserstoffverbrauch und durch die Bestimmung der Esterzahl an gelegentlich entnommenen Probe verfolgt.After cooling under hydrogen, the catalyst was suspended in a mixture of methyl esters of C 4 - to C a -dicarboxylic acids, so that 5% by weight of catalyst was present in the suspension. This suspension was transferred to a heated autoclave for hydrogenation. After removing the atmospheric oxygen, the hydrogenation conditions were set: 230 ° C. and 250 bar. The progress of the hydrogenation reaction was followed by the consumption of hydrogen and by the determination of the ester number on occasionally taken samples.

Das ursprüngliche Estergemisch hatte eine Esterzahl von 700, nach 12 Stunden wurde im Hydriergemisch eine Esterzahl von 60 gefunden.The original ester mixture had an ester number of 700, after 12 hours an ester number of 60 was found in the hydrogenation mixture.

Vergleichsversuch 1Comparative experiment 1

Es wurde verfahren wie im Anwendungsbeispiel 1, jedoch mit dem Unterschied, daß als Katalysator ein Kupfer-Chromoxid-Katalysator nach ADKINS verwendet wurde, wie er z.B. von der Firma Girdler-Südchemie unter der Handelsbezeichnung G-13 vertrieben wird.The procedure was as in Application Example 1, but with the difference that a copper-chromium oxide catalyst according to ADKINS was used as the catalyst, as described e.g. is marketed by Girdler-Südchemie under the trade name G-13.

Nach 12 Stunden Hydrierzeit bei den im Anwendungsbeispiel 1 genannten Bedingungen wurde eine Esterzahl von 480 gefunden.After 12 hours of hydrogenation under the conditions mentioned in Application Example 1, an ester number of 480 was found.

Anwendungsbeispiel 2Example of use 2

Es wurde verfahren wie vorstehend beschrieben, jedoch der Katalysator gemäß Beispiel 2 verwendet. Nach 12 Stunden Hydrierzeit wurde eine Esterzahl von 200 gefunden.The procedure was as described above, but the catalyst according to Example 2 was used. After 12 hours of hydrogenation, an ester number of 200 was found.

Anwendungsbeispiel 3Example of use 3

Es wurde verfahren wie im Anwendungsbeispiel 1, jedoch mit dem Unterschied, daß der Katalysator gemäß Beispiel 3 verwendet wurde. Nach der Hydrierzeit von 12 Stunden wurde eine Esterzahl von 100 gefunden.The procedure was as in Application Example 1, but with the difference that the catalyst according to Example 3 was used. After the hydrogenation time of 12 hours, an ester number of 100 was found.

Die vorstehenden Anwendungsbeispiele zeigen einmal den Fortschritt gegenüber dem Stand der Technik und zum anderen den besonderen Vorteil des Katalysators nach Beispiel 1 gegenüber kupferreicheren und -ärmeren, d.h. das Vorhandensein eines Maximums der katalytischen Wirkung.The above application examples show on the one hand the progress compared to the prior art and on the other hand the special advantage of the catalyst according to Example 1 over copper-poorer and poorer, i.e. the presence of a maximum of catalytic activity.

Beispiel 12Example 12

Zur Bereitung der Lösung 1 wurde Nickelnitrat (Ni(N03)2 . 6H20) in Wasser gelöst, so daß eine 1 - molare Losung entstand.To prepare solution 1, nickel nitrate (Ni (N0 3 ) 2. 6H 2 0) was dissolved in water, so that a 1 molar solution was formed.

Zur Bereitung der Lösung 2 wurde das im Beispiel 1 beschriebene Wasserglas verwendet, und zwar in einer Menge, daß auf 1 Mol des in der Lösung 1 gelösten Nickels 0,5 Mol Si02 entfielen. Für 1 I der Lösung 1 wurden also 112 g Kaliwasserglas verwendet. Dieses enthält nicht genügend K20 zur Bindung der Nitrationen, so daß dem Wasserglas KOH zugesetzt werden mußte, und zwar 1,66 Mol KOH pro Liter Lösung 1. Für 1 I Lösung enthielt die Lösung 2 als Fälläquivalent also 0,50 Mol Si02 und 1 Mol K20 (= 2 Mol KOH). Aus der vorstehenden Angabe ergibt sich für den fertigen Katalysator ein Gehalt von 66% Nickel.The water glass described in Example 1 was used to prepare solution 2, in an amount such that 0.5 mol of SiO 2 was present in 1 mol of the nickel dissolved in solution 1. 112 g of potassium water glass were therefore used for 1 l of solution 1. This does not contain enough K 2 0 to bind the nitrate ions, so that KOH had to be added to the water glass, namely 1.66 mol KOH per liter of solution 1. For 1 liter of solution, solution 2 contained 0.50 mol of Si0 2 as the precipitation equivalent and 1 mole of K 2 0 (= 2 moles of KOH). From the above information, the finished catalyst has a nickel content of 66%.

Die Fällung wurde in der im Beispiel 1 beschriebenen Art und Weise hergestellt und behandelt.The precipitation was prepared and treated in the manner described in Example 1.

Die getrocknete Fällung wurde bei 550°C getempert. Ein Teil dieser Masse wurde mechanisch auf eine Körnung von 60 bis 100µ gebracht, die zur Durchführung von suspensionskatalytischen Untersuchungen geeignet ist. Ein anderer Teil wurde zu zylindrischen Tabletten mit 3 mm Höhe und 5 mm Durchmesser verpreßt. In dieser Form ist der Katalysatorvorläufer für Untersuchungen im Festbett geeignet.The dried precipitation was annealed at 550 ° C. Part of this mass was mechanically brought to a grain size of 60 to 100µ, which is suitable for carrying out suspension catalytic tests. Another part was pressed into cylindrical tablets with a height of 3 mm and a diameter of 5 mm. In this form, the catalyst precursor is suitable for investigations in a fixed bed.

Anwendungsbeispiel 4Example of use 4

Das zur Suspensionskatalyse vorbereitete Pulver aus Beispiel 12 wurde in einer indirekt beheizten Wirbelschicht mit umgewälztem Wasserstoff stufenweise bis auf 570°C erhitzt und dadurch reduziert.The powder from Example 12 prepared for suspension catalysis was gradually heated up to 570 ° C. in an indirectly heated fluidized bed with circulated hydrogen and thereby reduced.

Nach dem Abkühlen wurde der Katalysatore in einer technischen, rohen Butindiol-Lösung aufgeschlämmt, so daß eine Suspension mit 5 Gew.% Katalysator entstand. Die rohe Butindiollösung hatte nach gaschromatographischer Analyse folgende Zusammensetzung:

Figure imgb0002
After cooling, the catalyst was slurried in a technical, crude butynediol solution, so that a suspension with 5% by weight of catalyst was formed. The crude butynediol solution had the following composition according to gas chromatographic analysis:
Figure imgb0002

Die Katalysatorsuspension wurde in eine Hochdruck-Blasensäule überführt. Bei 90 bar und 40 bis 50°C wurde die Suspension mit Wasserstoff begast. Die Strömungsgeschwindigkeit des Wasserstoffs in der (leer gedachten) Blasensäure betrug 2 cm/sec. In Zeitabständen von 10 Minuten wurden aus der Blasensäule Proben entnommen und analysiert. Als Ende der Hydrierreaktion wurde das Unterschreiten der Konzentration an intermediär entstandenem Hydroxybutyraldehyd von 0,5%, bezogen auf die wasserfreie Lösung, definiert; C=C-Mehrfachbindungen sind dann nicht mehr nachweisbar. Dieses Hydrier-Ende wurde jeweils nach 45 Minuten erreicht.The catalyst suspension was transferred to a high pressure bubble column. The suspension was gassed with hydrogen at 90 bar and 40 to 50 ° C. The flow rate of the hydrogen in the (thought empty) bubble acid was 2 cm / sec. Samples were taken from the bubble column and analyzed at intervals of 10 minutes. At the end of the hydrogenation reaction, the drop below the concentration of intermediate hydroxybutyraldehyde of 0.5% based on the anhydrous solution was defined; C = C multiple bonds are then no longer detectable. This end of hydrogenation was reached after 45 minutes.

Vergleichsversuch zum Anwendungsbeispiel 4Comparative experiment for application example 4

Verwendet man als Katalysator Raney-Nickel und verfährt im übrigen wie vorstehend beschrieben, so wird das Hydrier-Ende erst nach 130 Minuten erreicht.If Raney nickel is used as the catalyst and the procedure is otherwise as described above, the end of hydrogenation is only reached after 130 minutes.

Anwendungsbeispiele 5 bis 7Application examples 5 to 7

Verfährt man wie vorstehend beschrieben, verwendet jedoch Katalysatoren, die gemäß Beispiel 4 bis 6 erhalten wurden, so findet man die nachstehend zusammengestellten Ergebnisse.

Figure imgb0003
If the procedure is as described above, but catalysts obtained according to Examples 4 to 6 are used, the results summarized below are found.
Figure imgb0003

Die vorstehenden Anwendungsbeispiele zeigen einmal den Fortschritt gegenüber dem Stande der Technik und zum anderen den besonderen Vorteil des Katalysators nach Beispiel 5 gegenüber nickelärmeren und -reicheren Katalysatoren.The above application examples show on the one hand the progress compared to the prior art and on the other hand the special advantage of the catalyst according to Example 5 over catalysts which are poorer and richer in nickel.

Anwendungsbeispiele 8 bis 11Application examples 8 to 11

Die aus den Beispielen 8 bis 11 erhaltenen Katalysatoren wurden in Korngrößen von 60 bis 100µ in der indirekt beheizten Wirbelschicht bei Temperaturen bis maximal 550°C im Wasserstoffstrom reduziert. Sie wurden dann in Toluol aufgeschlämmt und in der Hochdruckblasensäure mit Adipinsäurerdinitril vermischt. Die Mischung bestand danach aus 76 Gew.% Toluol, 19 Gew.% Adipinsäuredinitril und 5 Gew.% Katalysator. Es wurde dann hydriert bei 90 bar, 100°C, die Strömungsgeschwindigkeit des Wasserstoffs bezogen auf die (leer gedachte) Blasensäule betrug 2 cm/sec. Das Fortschreiten der Hydrierreaktion, bei der hauptsächlich Hexamethylendiamin entsteht, wurde durch die zeitliche Zunahme der Aminzahl verfolgt. Die Ergebnisse sind in der Tabelle 3 zusammengestellt.

Figure imgb0004
The catalysts obtained from Examples 8 to 11 were reduced in particle sizes from 60 to 100 μm in the indirectly heated fluidized bed at temperatures up to a maximum of 550 ° C. in a stream of hydrogen. They were then slurried in toluene and mixed with adipic acid dinitrile in the high pressure bubble acid. The mixture then consisted of 76% by weight of toluene, 19% by weight of adiponitrile and 5% by weight of catalyst. It was then hydrogenated at 90 bar, 100 ° C., the flow rate of the hydrogen based on the (empty) bubble column was 2 cm / sec. The progress of the hydrogenation reaction, which mainly produces hexamethylenediamine, was followed by the increase in the amine number over time. The results are summarized in Table 3.
Figure imgb0004

Die vorstehenden Anwendungsbeispiele zeigen einmal den Fortschritt gegenüber dem Stand der Technik und zum anderen den besonderen Vorteil des Katalysators nach Beispiel 9 gegenüber kobaltreicheren und -ärmeren Katalysatoren.The above application examples show on the one hand the progress compared to the prior art and on the other hand the special advantage of the catalyst according to Example 9 over catalysts which are richer and poorer in cobalt.

Anwendungsbeispiel 12Example of use 12

Nach der allgemeinen Vorschrift des Beispiels 12 wurde ein Katalysator mit der formelmäßigen Zusammensetzung CuO. Co0 - Si02 hergestellt, der zu Tabletten mit 5 mm Höhe und 5 mm Durchmesser verformt wurde. Im reduzierten Zustand enthielt der Katalysator also 67 Gew.% aktive Metalle. Eine thermostatierbarer druckbeständiger Reaktor enthielt 500 ml dieses Katalysators. Durch die Katalysatorschüttung wurde von oben nach unten Wasserstoff geleitet, und zwar in einer Menge, die 100 NI je Stunde am Reaktorausgang entsprach. Dabei wurde im Reaktor ein Druck von 200 bar und eine Temperatur von 75°C eingestellt. Sodann ließ man kontinuierlich ein Gemisch aus Benzonitril und Ammoniak in einer stündlichen Menge von 1,2 I zulaufen, wobei auf 1 Volumenteil Benzonitril 2 Volumenteile Ammoniak (flüssig) verwendet wurden.According to the general procedure of Example 12, a catalyst with the formula composition CuO. Co0 - Si0 2 produced, which was deformed into tablets with a height of 5 mm and a diameter of 5 mm. In the reduced state, the catalyst thus contained 67% by weight of active metals. A thermostable pressure-resistant reactor contained 500 ml of this catalyst. Hydrogen was passed through the catalyst bed from top to bottom, in an amount corresponding to 100 NI per hour at the reactor outlet. A pressure of 200 bar and a temperature of 75 ° C. were set in the reactor. A mixture of benzonitrile and ammonia was then run in continuously in an hourly amount of 1.2 l, 2 volumes of ammonia (liquid) being used for 1 volume of benzonitrile.

Das abgezogene Reaktionsgemisch bestand nach dem Entfernen des überschüssigen Ammoniaks aus 98 Gew.% Benzylamin, 0,05 Gew.% Benzonitril und weniger als 2% Nebenprodukten oder Verunreinigungen.After the excess ammonia had been removed, the reaction mixture drawn off consisted of 98% by weight of benzylamine, 0.05% by weight of benzonitrile and less than 2% of by-products or impurities.

Claims (4)

1. A process for the production of a hydrogenation catalyst which contains copper, nickel and/or cobalt on a silica carrier, characterized in that an aqueous solution of a salt of copper, nickel and/or cobalt is mixed with an alkali metal silicate solution having a ratio of Me20 to Sio2 of more than 1 : 1 (Me denoting potassium or sodium) in such an amount that the mixture has a pH of 6 to 8 and the content of copper, nickel and/or cobalt in the finished catalyst is about 40 to 80% by weight, and, using conventional methods, the precipitate formed on mixing is isolated, moulded, dried and treated with a reducing agent.
2. A process for the production of a catalyst as claimed in claim 1, characterized in that the aqueous salt solution used is from about 1 to 3 molar
3. A process as claimed in claim 2, characterized in that the mixing temperature, i.e. the precipitation temperature, is from 60° to 90°C.
4. Use of a catalyst obtained according to any of claims 1 to 3 for hydrogenation.
EP78100097A 1977-06-14 1978-06-06 Preparation of silica containing hydrogenation catalysts and their use in hydrogenation Expired EP0000055B1 (en)

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DE2726710 1977-06-14
DE19772726710 DE2726710A1 (en) 1977-06-14 1977-06-14 PRODUCTION OF SILICATE HYDROGEN CATALYSTS

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CA1140910A (en) * 1979-01-02 1983-02-08 James L. Carter Supported cobalt-silica coprecipitated hydrogenation catalyst
US4439544A (en) * 1979-01-02 1984-03-27 Exxon Research And Engineering Co. Support cobalt-silica coprecipitated hydrogenation catalyst
DE3503587A1 (en) * 1985-02-02 1986-08-07 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING A CATALYST CONTAINING COPPER AND SILICON OXIDE

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