EP3515595A1

EP3515595A1 - Method for providing a catalytically active fixed bed for hydrogenating organic compounds

Info

Publication number: EP3515595A1
Application number: EP17771718.8A
Authority: EP
Inventors: Tobias Maximilian MERKEL; Michael Schreiber; Irene DE WISPELAERE; Rolf Pinkos
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-09-23
Filing date: 2017-09-14
Publication date: 2019-07-31
Also published as: US20200016583A1; SG11201901571RA; JP2019531184A; CN109789401A; WO2018054755A1; KR20190059273A

Abstract

The invention relates to a method for providing a catalytically active fixed bed for hydrogenating organic compounds. A fixed bed which contains monolithic molded bodies as catalyzer carriers or which consists of monolithic molded bodies is introduced into a reactor, and the fixed bed is then brought into contact with at least one catalyst or a precursor thereof. The catalyst-loaded fixed beds obtained in this manner are especially suitable for hydrogenating organic compounds in the presence of CO, wherein the conversion rate is at least 90%. The invention is characterized in that none of the introduced catalyst or only a small content of the introduced catalyst is released into the reaction medium.

Description

Process for providing a catalytically active fixed bed for the hydrogenation of organic compounds

BACKGROUND OF THE INVENTION

The present invention relates to a process for providing a catalytically active fixed bed for the hydrogenation of organic compounds, in which a fixed bed is introduced into a reactor containing monolithic moldings as catalyst support or consists of monolithic moldings and the fixed bed is subsequently treated with at least one catalyst or a precursor thereof brings in contact. The thus obtained, loaded with a catalyst fixed beds are particularly suitable for the hydrogenation of organic compounds in the presence of CO, wherein the conversion is at least 90%. They are characterized by the fact that no or only a very small proportion of the introduced catalyst is released into the reaction medium.

STATE OF THE ART

It is basically known to carry out hydrogenation reactions in the presence of carbon monoxide (CO). The CO can on the one hand be added to the hydrogen used for the hydrogenation and / or originate from the starting materials or their intermediates, by-products or products. If catalysts are used for hydrogenation which contain CO-sensitive active components, it is known as a countermeasure to carry out the hydrogenation at a high hydrogen pressure and / or a low catalyst load. Otherwise, the implementation may be incomplete, so that z. B. an after-reaction in at least one other reactor is absolutely necessary. It can also lead to the increased formation of by-products. Disadvantages associated with the use of high hydrogen pressures are the formation of methane by hydrogenation of CO and thus an increased consumption of hydrogen and increased investment costs.

The US 6,262,317 (DE 196 41 707 A1) describes the hydrogenation of 1, 4-butynediol with hydrogen in the liquid continuous phase in the presence of a heterogeneous hydrogenation catalyst at temperatures of 20 to 300 ° C, a pressure of 1 to 200 bar and values of liquid-side volume-related mass transfer coefficient kl_a of 0.1 s ^_1 to 1 s ^_1 . The reaction can be carried out either in the presence of a catalyst suspended in the reaction medium or in a fixed-bed reactor operated in cocurrent in a cyclic gas mode. It is quite generally described that one can provide fixed bed reactors by using packs as commonly available. cherweise be used in bubble columns, coated directly with catalytically active substances. Further details can not be found here. In the exemplary embodiments, suspension catalysts or reactor fillers based on Raschig rings with a diameter of 5 mm were used.

For the hydrogenation in fixed bed mode, a ratio of supplied gas flow to the reactor leaving the gas stream from 0.99: 1 to 0.4: 1 is described, ie at least 60% of the gas supplied are still present at the end of the reactor. In suspension mode, good hydrogenation results are described in Example 1 at a loading of about 0.4 kg of butynediol / liter of reaction space xh. If the load is increased to about 0.7 (Example 2), then the Butandiolausbeute goes back and the proportion of undesirable by-products, such as 2-methylbutanediol, butanol and propanol increases. The problem with the hydrogenations in suspension is the handling of the suspended catalyst, which must remain in the reactor, so that a filter system for retaining the catalyst is absolutely necessary. Such filters tend to occupy with catalyst particles, so that they must either be periodically cleaned consuming, or the travel time is correspondingly short, before the passage through the filter is uneconomical. Also in Examples 5 and 6 using supported catalysts, a filter was still used to keep the particles of catalyst bed in the reactor. The load corresponded to about 0.25 kg of butynediol / liter of reaction space x h. The total amount of by-products 2-methylbutanediol, butanol and propanol is relatively high at 6%. The implementation of the process described in US Pat. No. 6,262,317 is technically complicated for the reasons mentioned. In addition, in the fixed-bed mode of operation, it is necessary to provide a gaseous cycle stream since at least 60% of the gas supplied to the reactor exits again at the reactor end. In such a cycle gas method, however, the risk is particularly high that aufpegeln unwanted components in the gas stream; This is especially true for CO. DE 199 629 07 A1 describes a process for the preparation of Cio-C ₃ o-alkenes by partial hydrogenation of alkynes on fixed-bed supported catalysts, wherein CO is added to the hydrogenation gas. The hydrogenation-active metal used is exclusively palladium. As suitable starting materials, in particular dehydrolinalool, hydrodehydrolinalool, 1-ethynyl-2,6,6-trimethyl-cyclohexanol, 17-ethynylandrost-5-en-3β, 17β-diol, 3,7,1 1, 15-tetramethyl 1-hexadecino-3-ol (dehydroisophytol), 3,7,1-trimethyl-6-dodecen-1-yn-3-ol (dehydrodihydronerolidol), 4-methyl-4-hydroxy-2-decyne,

1,1-diethoxy-2-octyne and bis (tetrahydro-2-pyranyloxy) -2-butyne. EP 0 754 664 A2 describes a process for the preparation of alkenes by partial hydrogenation of alkynes on fixed-bed supported catalysts, wherein CO is added to the hydrogenation gas. In turn, only palladium is used as hydrogenation-active metal. As a suitable starting material is in addition to a large variety of other 1, 4-butynediol called. In the embodiments, however, only the selective hydrogenation of 2-dehydrolinalool to 2-linalool is described.

DE 43 33 293 A1 describes partially hydrogenating 1,4-butynediol to 1, 4-butenediol at 60 ° C. on a structured Pd catalyst 1, 4-butynediol. Nothing is said about CO formation or its content. Also, not the amount of hydrogen is used, which was used for hydrogenation, but only the pressure (15 bar). Thus, it can be assumed that the hydrogenation was not operated continuously, but the reactant was circulated only in trickle mode without significant hydrogen supply.

Known types of catalysts for hydrogenation reactions are precipitation, carrier or Raney metal catalysts. Raney metal catalysts have found wide commercial use, especially for the hydrogenation of mono- or polyunsaturated organic compounds. Typically, Raney catalysts are alloys containing at least one catalytically active metal and at least one alkali-soluble (leachable) alloy component. Typical catalytically active metals include Ni, Fe, Co, Cu, Cr, Pt, Ag, Au and Pd, and typical leachable alloy components are e.g. B. Al, Zn and Si. Such Raney metal catalysts and processes for their preparation are, for. For example, in US Pat. No. 1,628,190, US Pat. No. 1,915,473 and US Pat. No. 5,563,587. Prior to their use in heterogeneously catalyzed chemical reactions, especially in a hydrogenation reaction, Raney metal alloys generally require activation.

Conventional methods of activating Raney metal catalysts include grinding the alloy into a fine powder if it is not already powdered by the prior art. For activation, the powder is subjected to treatment with an aqueous liquor, wherein the leachable metal is partially removed from the alloy and the highly active non-leachable metal remains. The powders thus activated are pyrophoric and are usually stored under water or organic solvents in order to avoid contact with oxygen and the associated deactivation of the Raney metal catalysts.

According to a known process for activating suspended Raney nickel catalysts, a nickel-aluminum alloy containing 15 to 20% by weight sodium is used. treated umhydroxid solution at temperatures of 100 ° C or higher. In US 2,948,687 it is described to prepare a Raney nickel molybdenum catalyst from a milled Ni-Mo-Al alloy having particle sizes in the range of 80 mesh (about 0.177 mm) or finer by first placing the alloy at 50 ° C treated with 20 wt .-% NaOH solution and the temperature to 100 to 1 15 ° C raises.

A significant disadvantage of powdered Raney metal catalysts is the need to separate them from the reaction medium of the catalyzed reaction by expensive sedimentation and / or filtration processes.

It is known to use Raney metal catalysts in the form of larger particles. Thus, US Pat. No. 3,448,060 describes the preparation of structured Raney metal catalysts, wherein in a first embodiment an inert carrier material is coated with an aqueous suspension of a pulverulent nickel-aluminum alloy and freshly precipitated aluminum hydroxide. The resulting structure is dried, heated and contacted with water, releasing hydrogen. Subsequently, the structure is hardened. Optionally, leaching with an alkali hydroxide solution is provided. In a second embodiment, an aqueous suspension of a powdered nickel-aluminum alloy and freshly precipitated

Aluminum hydroxide subjected to a molding without the use of a support material. The structure thus obtained is activated analogously to the first embodiment.

Other suitable for use in fixed bed catalysts Raney metal catalysts may have hollow bodies or spheres or otherwise supported. Such catalysts are z. In EP 0 842 699, EP 1 068 900, US 6,747,180,

US 2,895,819 and US 2009/0018366.

No. 2,950,260 describes a process for activating a catalyst from a granular nickel-aluminum alloy by treatment with an aqueous alkali solution. Typical particle sizes of this granular alloy range from 1 to 14 mesh (about 20 to 1.4 mm). It has been found that contacting a Raney metal alloy, such as a Ni-Al alloy, with an aqueous liquor results in an exothermic reaction to produce larger amounts of hydrogen. The following reaction equations are intended to illustrate, by way of example, possible reactions which take place when a Ni-Al alloy is brought into contact with an aqueous alkali metal hydroxide, such as NaOH:

2 NaOH + 2 Al + 2 H ₂ 0 - 2 NaAI0 ₂ + 3 H ₂ 2 Al + 6 H ₂ O - 2 Al (OH) ₃ + 3 H ₂

The object of US Pat. No. 2,950,260 is to provide an activated granular hydrogenation catalyst of a Ni-Al alloy with improved activity and service life. For this purpose, the activation is carried out with a 0.5 to 5 wt .-% strength NaOH or KOH, wherein the temperature is maintained by cooling to below 35 ° C and the contact time is chosen so that not more than 1, 5 parts H2 mole per mole equivalent Leach are liberated. In contrast to a powdery, suspended catalyst, in the treatment of granular Raney metal catalysts a significantly lower proportion of aluminum is dissolved out of the structure. This is in a range of only 5 to 30 wt .-%, based on the amount of aluminum originally present. Catalyst particles having a porous activated nickel surface and an unchanged metal core are obtained. A disadvantage of the catalysts thus obtained, in which only the outermost layer of the particles is catalytically active, is their sensitivity to mechanical stress or abrasion, which can lead to a rapid deactivation of the catalyst. The teaching of US Pat. No. 2,950,260 is restricted to granular shaped catalyst bodies which fundamentally differ from larger structured shaped bodies. Moreover, this document also does not teach that the catalysts may contain promoter elements in addition to nickel and aluminum.

It is known to subject hydrogenation catalysts, such as Raney metal catalysts, a doping with at least one promoter element in order, for. B. to achieve an improvement in the yield, selectivity and / or activity in the hydrogenation. Thus, as a rule, products of improved quality can be obtained. Such dopants are disclosed in US 2,953,604, US 2,953,605, US 2,967,893, US Pat.

US 2,950,326, US 4,885,410 and US 4,153,578. The use of promoter elements serves, for example, unwanted side reactions such. B. isomerization reactions to avoid. Promoter elements are also suitable to modify the activity of the hydrogenation catalyst to z. B. in the hydrogenation of starting materials with several hydrogenatable groups to achieve either a targeted partial hydrogenation of a particular group or more specific groups or a complete hydrogenation of all hydrogenatable groups. So z. For example, it is known to use a copper-modified nickel or palladium catalyst for the partial hydrogenation of 1,4-butynediol to 1,4-butenediol (see, for example, US Pat.

GB 832 141). In principle, the activity and / or the selectivity of a catalyst can thus be increased or decreased by doping with at least one promoter metal become. Such doping should not adversely affect the other properties of the doped catalyst as far as possible.

For the modification of shaped catalyst bodies by doping, the following four methods are known in principle:

The promoter elements are already present in the alloy for producing the shaped catalyst bodies (method 1),

the shaped catalyst bodies are brought into contact with a dopant during activation (method 2),

the shaped catalyst bodies are brought into contact after activation with a dopant (Method 3),

the catalyst bodies are brought into contact with a dopant in the hydrogenation feed stream during hydrogenation, or a dopant is otherwise introduced into the reactor during hydrogenation (Method 4).

The above-mentioned method 1, in which at least one promoter element is already contained in the alloy for the preparation of the shaped catalyst body is z. B. in the already mentioned US 2,948,687 described. Thereafter, a finely ground nickel-aluminum-molybdenum alloy is used for Katalysatorher- position to produce a molybdenum-containing Raney nickel catalyst.

The above methods 2 and 3 are z. Example in US 2010/01741 16 A1

(= US 8,889.91 1) described. Thereafter, a doped catalyst is prepared from a Ni / Al alloy which is modified during and / or after its activation with at least one promoter metal. In this case, the catalyst can optionally be subjected to a first doping before activation. The promoter element used for doping by absorption on the surface of the catalyst during and / or after activation is selected from Mg, Ca, Ba, Ti, Zr, Ce, Nb, Cr, Mo, W, Mn, Re, Fe, Co, Ir, Ni, Cu, Ag, Au, Bi, Rh and Ru. If the catalyst precursor is already subjected to doping before activation, then the promoter element is selected from Ti, Ce, V, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Pd, Pt and Bi ,

The above method 3 is also described in GB 2104794. This document relates to Raney nickel catalysts for the reduction of organic compounds, especially the reduction of carbonyl compounds and the preparation of 1,4-butanediol from 1,4-butynediol. To prepare these catalysts, a Raney nickel catalyst is subjected to a doping with a molybdenum compound, which may be solid, as a dispersion or as a solution. Other promoter elements, such as Cu, Cr, Co, W, Zr, Pt or Pd may be additionally used. In a specific embodiment, an already activated commercially available undoped Raney nickel catalyst is suspended in water together with ammonium molybdate and the suspension is stirred until a sufficient amount of molybdenum has been taken up. In this document only particulate Raney nickel catalysts are used for doping, especially the use of structured shaped bodies is not described. There is also no indication as to how the catalysts can be introduced into a reactor in the form of a structured catalyst fixed bed and how the catalyst fixed bed introduced into the reactor can then be activated and doped.

The above method 4 is z. As described in US 2,967,893 or US 2,950,326. Thereafter, copper in the form of copper salts is added to a nickel catalyst for the hydrogenation of 1,4-butynediol in the aqueous.

According to EP 2 486 976 A1, supported activated Raney metal catalysts are subsequently doped with an aqueous metal salt solution. Specifically, as the carrier, the usual bulk materials are used, such. B. SiO 2 -coated glass body with a diameter of about 3 mm. It is not described to carry out the doping and optionally already the activation on a stationary fixed catalyst bed of structured catalyst bodies in a reactor. Thus, with the process described in this document, it is impossible to provide a fixed catalyst bed which has a gradient in the concentration of promoter elements in the direction of flow of the reaction medium of the reaction to be catalyzed.

EP 2 764 916 A1 describes a process for producing foam-shaped shaped catalyst bodies which are suitable for hydrogenations, in which: a metal foam molding is provided which contains at least one first metal, which is selected, for example, from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au and Pd, on the surface of the metal foam molded body applies at least a second leachable component or alloyable component into a leachable component, for example, selected from Al, Zn and Si, and c) by alloying of the metal foam molding obtained in step b)

at least forms an alloy on a part of the surface, and d) subjecting the foam-like alloy obtained in step c) to a treatment with an agent capable of leaching the leachable components of the alloy.

This document teaches that for step d) a 1 to 10 molar, d. H. Use 4 to 40% by weight aqueous NaOH. The temperature in step d) is 20 to 98 ° C and the treatment time is 1 to 15 minutes. It is quite generally mentioned that the foam-like shaped bodies according to the invention can also be formed in situ in a chemical reactor, although any concrete details are missing. EP 2 764 916 A1 further teaches that promoter elements can be used in the preparation of foam-like shaped catalyst bodies. The doping can be carried out together with the application of the leachable component on the surface of the previously prepared metal foam molding. The doping can also take place in a separate step following the activation.

EP 2 764 916 A1 does not contain the slightest information on the dimension of the chemical reactors for the use of the foam-shaped moldings, the type, amount and dimensioning of the moldings introduced into the reactor and for introducing the moldings into the reactor. In particular, there is no indication as to how a fixed catalyst bed actually located in a chemical reactor can first be activated and then doped.

The present invention has for its object to provide an improved method for providing catalytically active fixed beds, which overcomes as many of the aforementioned disadvantages.

It has been found that catalytically active fixed beds for the hydrogenation of organic compounds can be produced particularly advantageously by introducing into a reactor a fixed bed containing monolithic shaped bodies as catalyst support or consisting of monolithic shaped bodies and then the fixed bed containing at least one catalyst or a precursor thereof brings in contact. Surprisingly, it has been found that the fixed catalyst beds thus obtained are characterized in that no or only very small proportions of the catalyst are liberated into the reaction medium of the reaction to be catalyzed. As a rule, based on the total weight of the liquid reaction medium, less than 1000 ppm by weight of catalyst are free in the liquid phase. This is surprising because, in addition to the slurry of the catalyst or its precursor in the carrier pack in the Usually no further active measures are carried out to effect a physical or chemical attachment of the catalyst to the carrier.

It has furthermore been found that unsaturated organic compounds can be hydrogenated to saturated compounds in an advantageous manner if monolithic fixed-bed catalysts are used for the hydrogenation and the CO content in the gas phase within the reactor is in a range of 0.1 to 10 000 volume percent. ppm is, with the conversion is at least 90%. SUMMARY OF THE INVENTION

The invention relates to a process for providing a catalytically active fixed bed which contains monolithic shaped bodies as catalyst support or consists of monolithic shaped bodies which are loaded with a catalyst containing at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir, in which one introduces into a reactor a fixed bed containing monolithic moldings or consists of monolithic moldings, the fixed bed with a suspension of the at least one catalyst or the precursor thereof is contacted in a liquid medium and the suspension of the at least one catalyst or precursor thereof is at least partially carried in a liquid recycle stream, the catalyst or precursor containing at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir, with one with the catalyst or precursor e loaded fixed bed is optionally subjected to the obtained in step b) loaded fixed bed activation, optionally subjected to the obtained in step b) loaded fixed bed or the activated fixed bed obtained in step c) a treatment with a washing medium which is selected from water, C 1 -C 4 -alkanols and mixtures thereof, e) optionally bringing the fixed bed obtained after activation in step c) or after the treatment in step d) into contact with a dopant, which has at least one element that is different from the metal used to load the fixed bed.

EMBODIMENTS OF THE INVENTION

1 . A process for providing a catalytically active fixed bed containing monolithic shaped bodies as catalyst support or consisting of monolithic shaped bodies loaded with a catalyst containing at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt , Ag, Au, Pd, Mn, Re, Ru, Rh and Ir, in which a) introducing into a reactor a fixed bed containing monolithic moldings or consists of monolithic moldings, b) the fixed bed with a suspension of the at least one catalyst or the precursor thereof is contacted in a liquid medium and the suspension of the at least one catalyst or precursor thereof is at least partially carried in a liquid recycle stream, the catalyst or precursor containing at least one metal selected from Ni, Fe , Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir to give a packed bed loaded with the catalyst or precursor c) optionally activating the loaded fixed bed obtained in step b), d) optionally subjecting the loaded fixed bed obtained in step b) or the activated fixed bed obtained in step c) to a treatment with a washing medium which is selected under water, Ci-C4-alkanols and

Mixtures thereof, e) optionally contacting the fixed bed obtained after activation in step c) or after the treatment in step d) with a dopant having at least one element other than the metal used to load the fixed bed. Method according to one of the preceding embodiments, wherein the reactor has an internal volume in the range of 0.1 to 100 m ³ , preferably from 0.5 to 80 m ³ .

Method according to one of the preceding embodiments, wherein the monolithic shaped bodies, based on the entire shaped body, a smallest dimension in a direction of at least 0.3 cm, preferably at least 1 cm, more preferably at least 2 cm, in particular at least 3 cm, especially at least 5 cm.

Method according to one of the preceding embodiments, wherein in step b) the fixed bed is contacted with a suspension of the at least one catalyst or precursor thereof in a liquid medium, the catalyst or precursor containing at least one metal selected from Ni , Co, Cu, Re, Ru, Pt and Pd, preferably selected from Ni, Co, Cu, Re and Ru.

Process according to one of the preceding embodiments, wherein in step b) at least 90% by weight of the at least one catalyst or the precursor thereof, based on the total weight of the catalyst or the precursor thereof, has a particle size in the range from 0.1 to 200 μηη, preferably in the range of 1 to 100 μηη, in particular in the range of 5 to 50 μηη having.

Method according to one of the preceding embodiments, wherein the bulk density of the catalyst used in step b) or the precursor thereof at least 0.8 g / mL, preferably at least 1 g / mL, in particular at least 1, 5 g / mL.

Method according to one of the preceding embodiments, wherein the bulk density of the catalyst used in step b) or the precursor thereof is at most 10 g / mL.

A process according to any one of the preceding embodiments, wherein the catalyst or precursor thereof is selected from precipitation catalysts, supported catalysts and Raney metal catalysts and the precursors thereof. 9. The method according to any one of the preceding embodiments, wherein the monolithic moldings are in the form of a foam.

10. The method according to any one of embodiments 1 to 9, wherein bringing in step b) the fixed bed with an active catalyst in contact.

1 1. The process of embodiment 12 wherein the active catalyst is selected from catalysts that have been subjected to activation with a reducing gas, preferably hydrogen, and Raney metal catalysts.

12. The method according to any one of embodiments 1 to 9, wherein in step b) bringing the fixed bed with a catalyst precursor in contact containing at least one metal in oxidic form and the obtained in step b) loaded fixed bed in step c) for activating a Treatment with a reducing gas, preferably hydrogen, undergoes.

13. The method according to any one of embodiments 1 to 9, wherein in step b) the fixed bed is brought into contact with an alloy containing at least one first metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag , Au and Pd, and containing at least one second component which is selected from Al, Zn and Si, and subjected to the loaded fixed bed obtained in step b) in step c) for activating a treatment with an aqueous base. 14. The method according to one of the preceding embodiments, wherein the fixed bed at any section in the normal plane to the flow direction through the fixed bed, based on the total area of the section, at most 5%, preferably at most 1%, in particular at most 0.1% free area, which is not part of the moldings.

15. The method according to any one of the preceding embodiments, wherein the fixed bed contains moldings having channels and wherein at any cut in the normal plane to the flow direction through the fixed bed at least 90% of the channels, more preferably at least 98% of the channels, an area of at most 3 mm ² .

16. The method according to any one of the preceding embodiments, wherein the fixed bed to at least 90% length in the flow direction through the fixed bed to at least 95% of the reactor cross section, preferably at least 98% of the reactor Gate cross section, in particular at least 99% of the reactor cross section, filled with monolithic moldings. Method according to one of the preceding claims, wherein the catalytically active fixed bed after step b) or after step c) or after step d) or after step e) in a further step f) is reacted with a hydrogenatable organic compound and hydrogen in at least one reactor and during step f) the CO content in the gas phase within the reactor is in a range of 0.1 to 10,000 ppm by volume. Method according to one of the preceding embodiments, wherein the hydrogenatable organic compound in step f) is selected from compounds which have at least one carbon-carbon double bond, carbon-nitrogen double bond, carbon-oxygen double bond, carbon-carbon triple bond, carbon Nitrogen triple bond or nitrogen

Having oxygen double bond.

Method according to one of the embodiments 17 or 18, wherein the hydrogenatable organic compound is selected from 1, 4-butynediol, 1, 4-butenediol,

4-hydroxybutyraldehyde, hydroxypivalic acid, hydroxypivalaldehyde,

n-butyraldehyde, iso-butyraldehyde, n-valeraldehyde, iso-valeraldehyde, 2-ethylhex-2-enal, 2-ethylhexanal, the isomeric nonanals, 1, 5,9-cyclododecatriene, benzene, furan, furfural, phthalic acid esters, acetophenone and alkyl-substituted acetophenones.

Method according to one of the embodiments 17 to 19, wherein step f) is carried out continuously.

A process according to any of embodiments 17 to 20, wherein the conversion at step f) is at least 90 mol%, preferably at least 95 mol%, in particular at least 99 mol%, especially at least 99.5 mol%, based on the total molar amount hydrogenatable compounds in the starting material used in step f).

Method according to one of embodiments 17 to 21, wherein during step f) the CO content in the gas phase within the reactor is in a range from 0.15 to 5000 ppm by volume, in particular in a range from 0.2 to 1000 by volume. ppm, is. 23. The method according to any one of embodiments 17 to 22, wherein the reactor in the flow direction of the reaction medium through the catalytically active fixed bed has a gradient with respect to the CO concentration. 24. Method according to one of embodiments 17 to 23, wherein the CO content at the outlet of the reaction medium from the catalytically active fixed bed is higher by at least 5 mol%, preferably by at least 25 mol%, in particular by at least 75 mol%, as the CO content when entering the reaction medium in the catalytically active fixed bed.

25. The process according to any one of embodiments 17 to 24, wherein the flow rate of the liquid reaction mixture through the reactor containing the catalytically active fixed bed is at least 30 m / h, preferably at least 50 m / h, in particular at least 80 m / h.

26. The method according to any one of embodiments 17 to 25, wherein the flow rate of the liquid reaction mixture through the reactor containing the catalytically active fixed bed at most 1000 m / h, preferably at most

500 m / h, in particular at most 400 m / h.

27. The method according to any one of embodiments 17 to 26, wherein the reaction mixture in step f) is at least partially guided in a liquid circulation stream.

Method according to one of embodiments 17 to 27, wherein the ratio of circulating stream outgoing reaction mixture to freshly supplied reactant stream in a range from 1: 1 to 1000: 1, preferably from 2: 1 to 500: 1, in particular from 5: 1 up to 200: 1.

A method according to any one of embodiments 17 to 28, wherein a discharge is taken from the reactor and subjected to a gas / liquid separation, whereby a hydrogen-containing gas phase and a product-containing liquid phase are obtained. 30. The method according to any one of embodiments 17 to 29, wherein the absolute pressure during step f) in a range of 1 to 330 bar, preferably in a range of 5 to 100 bar, in particular in a range of 10 to 60 bar, is located. 31. Method according to one of embodiments 17 to 30, wherein the temperature during step f) in a range of 60 to 300 ° C, more preferably from 70 to 220 ° C, in particular from 80 to 200 ° C, is located. 32. The method according to any one of embodiments 17 to 31, wherein the catalytically active fixed bed during step f) has a temperature gradient.

33. The process according to any of embodiments 17 to 32, wherein the liquid stream leaving the reactor has less than 1000 ppm by weight, based on the total weight of the liquid stream, of undissolved solids.

DESCRIPTION OF THE INVENTION

In the context of the invention, a fixed bed is understood to be a device incorporated in a reactor in the sense of a packing, through which the reaction mixture of a reaction to be catalyzed can be flowed through. The fixed bed serves to fix a catalyst. For this purpose, first of all a fixed bed containing monolithic shaped bodies as catalyst support or consisting of monolithic shaped bodies is introduced into a reactor (= step a)). The introduction of the fixed bed in the reactor is carried out by fixed installation of the shaped catalyst body. The fixed bed has a plurality of channels, which can be traversed by a liquid medium. This also applies to the reaction mixture of the hydrogenation reaction (= step f)) after loading of the fixed bed with the catalyst. After introducing the fixed bed into the reactor, the fixed bed can be brought into contact either with an already active catalyst or with a precursor of the catalyst (= step b)). This results in a loaded with the catalyst or the precursor fixed bed. If an already active catalyst is introduced into the fixed bed, a subsequent activation (= step c)) can generally be dispensed with. If a catalyst precursor is introduced into the fixed bed, this precursor can be converted into the active catalyst by subsequent activation in step c). A fixed bed containing an active catalyst is called a catalytically active fixed bed.

Introducing a fixed bed into a reactor (step a))

The introduction of the fixed bed in the reactor, as mentioned above, by fixed installation of the monolithic moldings. To produce a suitable fixed bed, the monolithic shaped bodies can be installed side by side and / or one above the other in the interior of the reactor. Method for installing packages, such. B. of moldings are known in principle to the person skilled in the art. Thus, for example, one or more layers of a foam-like catalyst support can be introduced into the reactor. Monoliths, each consisting of a ceramic block, can be stacked next to and above each other in the interior of the reactor. It is essential to the invention that the reaction mixture of the hydrogenation reaction (step f)) flows exclusively or substantially through the moldings loaded with the active catalyst and not past them. In order to ensure a bypass-free flow as possible, the monolithic molded bodies can be sealed against each other and / or to the inner wall of the reactor by means of suitable devices. These include z. As sealing rings, sealing mats, etc., which consist of a material inert under the conditions of treatment and reaction.

Preferably, the monolithic shaped bodies are incorporated into the reactor in one or more substantially horizontal layers with channels which allow the fixed bed to flow in the direction of flow. In this case, the fixed bed allows such a flow both in the loading of the catalyst or a precursor thereof, as well as in the activation, washing, doping and use for hydrogenation. The installation preferably takes place in such a way that the fixed bed fills the reactor cross-section as completely as possible. If desired, the fixed bed may also contain other internals, such as power distributors, devices for feeding gaseous or liquid reactants, measuring elements, in particular for a temperature measurement, or inert packings.

For the hydrogenation by the process according to the invention are in principle pressure-resistant reactors, as they are usually used for exothermic, heterogeneous reactions with the introduction of a gaseous and a liquid starting material. These include the commonly used reactors for gas-liquid reactions, such as. B. tube reactors, tube bundle reactors and gas circulation reactors. A special embodiment of the tube reactors are shaft reactors. Such reactors are known in principle to the person skilled in the art. In particular, a cylindrical reactor with a vertical longitudinal axis is used, which has at the bottom or top of the reactor one or more inlet devices for feeding a reactant mixture which contains at least one gaseous and at least one liquid component. Partial streams of the gaseous and / or the liquid educt may, if desired, additionally be fed to the reactor via at least one further feed device. The reaction mixture of the hydrogenation (step f)) is usually present in the reactor in the form of a two-phase mixture having a liquid and a gaseous phase. It is also possible that in addition to the gas phase two liquid phase sen, z. B. if further components in the hydrogenation (step f)) are present.

The processes according to the invention are particularly suitable for hydrogenations which are to be carried out on an industrial scale. The reactor then preferably has an internal volume in the range from 0.1 to 100 m ³ , preferably from 0.5 to 80 m ³ . The term internal volume refers to the volume including the fixed catalyst beds present in the reactor and optionally further existing internals. Of course, the technical advantages associated with the process according to the invention are also already apparent in reactors with a smaller internal volume.

In the process according to the invention "monolithic" shaped bodies are used as catalyst supports. Monolithic shaped bodies in the sense of the invention are structured shaped bodies which are suitable for producing immobilized, structured fixed beds. In contrast to particulate catalysts and catalyst supports can be made of monolithic moldings fixed beds, which are substantially continuous and seamless. This corresponds to the definition of monolithic in the sense of "consisting of one piece". The monolithic moldings according to the invention are distinguished, in contrast to catalyst beds, for. B. from pellets, often by a higher ratio of axial flow (longitudinal flow) over radial flow (cross-flow) from. Monolithic shaped bodies accordingly have channels in the flow direction of the reaction medium of the hydrogenation reaction (step f)). Particulate catalysts usually have the catalytically active sites on an external surface. Fixed beds of monolithic moldings have a plurality of channels, wherein the catalytically active sites are usually at least partially disposed on the surface of the channel walls. The reaction mixture of the hydrogenation reaction (step f)) can flow through the channels of the catalytically active fixed bed in the flow direction through the reactor. Thus, a much stronger contacting of the reaction mixture with the catalytically active sites usually takes place than with catalyst beds of particulate moldings.

The monolithic shaped bodies used in accordance with the invention are not shaped bodies of individual catalyst bodies having a greatest length extension in any direction of less than 1 cm. Such non-monolithic shaped bodies lead to fixed beds in the form of conventional catalyst beds. The monolithic shaped bodies used according to the invention have a regular planar or spatial structure and thus differ from carriers in particle form, which are used as loose heaps. The monolithic shaped bodies used according to the invention have, based on the entire shaped body, a smallest dimension in a direction of preferably at least 1 cm, particularly preferably at least 2 cm, very particularly preferably at least 3 cm, in particular at least 5 cm. The maximum value for the largest dimension in one direction is in principle not critical and usually results from the production process of the moldings. So z. For example, shaped bodies in the form of foams may be plate-shaped structures having a thickness in the range of millimeters to centimeters, a width in the range of a few centimeters to several hundred centimeters and a length (as the largest dimension in one direction) of up to several Meters.

In contrast to bulk solids, the monolithic shaped bodies used according to the invention can preferably be connected in a form-fitting manner to form larger units or consist of units which are larger than bulk solids.

The monolithic shaped bodies used according to the invention generally also differ from particulate catalysts or their supports in that they are present in substantially fewer parts. Thus, according to the invention, a fixed bed in the form of a single molded body can be used. In general, however, several moldings are used to produce a fixed bed. The monolithic shaped bodies used according to the invention generally have extensive three-dimensional structures. The moldings used according to the invention are usually traversed by continuous channels. The continuous channels may have any geometry, for example, they may be in a honeycomb structure. Suitable shaped bodies can also be produced by deforming flat carrier structures, for example by rolling up or buckling the planar structures into three-dimensional structures. Starting from flat substrates, the outer shape of the molded bodies can be easily adapted to given reactor geometries.

The monolithic shaped bodies used in accordance with the invention are characterized in that fixed beds can be produced from them in which a controlled flow through the packed bed is possible. A movement of the moldings under the conditions of the catalyzed reaction, for. B. a juxtaposition of the shaped body is avoided. Due to the ordered structure of the moldings and the resulting fixed bed, improved possibilities for the fluidically optimum operation of the packed bed result. The monolithic shaped bodies used in the process according to the invention are preferably in the form of a foam, mesh, woven fabric, knitted fabric, knitted fabric or monoliths different therefrom. The term monolithic shaped bodies in the context of the invention also includes structures which are known as "honeycomb catalysts".

In a specific embodiment, the shaped bodies are in the form of a foam. The shaped bodies can have any suitable external shapes, for example cubic, cuboidal, cylindrical, etc. Suitable fabrics can be produced with different types of weave, such as smooth fabrics, body fabrics, weft fabrics, five-shaft atlas fabrics or other special weave fabrics. Also suitable are wire mesh made of weavable metal wires, such as iron, spring steel, brass, phosphor bronze, pure nickel, monel, aluminum, silver, nickel silver (copper-nickel-zinc alloy), nickel, chrome nickel, chrome steel, stainless, acid-resistant and highly heat-resistant Chromium nickel steels and titanium. The same applies to knitted and knitted fabrics. Also, woven, knitted or knitted fabrics of inorganic materials such as AI2O3 and / or S1O2 may be used. Also suitable are woven, knitted or knitted fabrics made of plastics, such as polyamides, polyesters, polyolefins (such as polyethylene, polypropylene), polytetrafluoroethylene, etc. The abovementioned fabrics, knits or knitted fabrics but also other flat structured catalyst supports can be formed into larger spatial monoliths become. It is also possible not to build monoliths from laminar supports, but to produce them directly without intermediate stages, for example the ceramic monoliths with flow channels known to those skilled in the art.

Suitable are moldings, as described for example in EP-A-0 068 862,

EP-A-0 198 435, EP-A 201 614 and EP-A 448 884 are described.

Thus, EP 0 068 862 describes a monolithic shaped body comprising alternating layers of smooth and corrugated sheets in the form of a roll having channels and wherein the smooth sheets contain woven, knitted or knitted textile materials and the corrugated sheets contain a net material.

EP-A-0 198 435 describes a process for the preparation of catalysts in which the active components and the promoters are applied to support materials by vapor deposition in an ultra-high vacuum. The carrier materials used are reticulated or tissue-like carrier materials which, taken in isolation, are also suitable for the process according to the invention. The catalyst webs are for installation assembled into "catalyst packages" in the reactor and the shape of the catalyst packages adapted to the flow conditions in the reactor.

EP-A-0 201 614 describes a reactor for heterogeneously catalyzed chemical reactions, comprising at least one packing element consisting of corrugated plates arranged parallel to the main flow axis of the reactor, whose corrugation is inclined obliquely to the main flow axis and oppositely directed to adjacent plates, wherein between adjacent corrugated plates at least one band-shaped catalyst body is arranged.

Particularly preferably, the monolithic shaped bodies are in the form of a foam. In principle, polymer foams or metal foams having different morphological properties with regard to channel sizes and shapes, layer thicknesses, areal densities, geometric surfaces, porosities, etc. are suitable, whereby passages with at least two openings are meant by channels (and no dead ends). The preparation can be done in a conventional manner. For example, a foam of an organic polymer may be coated by contacting at least one metal and then the polymer removed, e.g. Example by pyrolysis or dissolution in a suitable solvent, wherein a metal foam is obtained.

For coating with at least one metal or precursor thereof, the organic polymer foam may be contacted with a solution or suspension containing the metal. This can be z. B. done by the inventive method. So z. B. a polyurethane foam coated with the first metal and then the polyurethane foam are pyrolyzed. A suitable for the production of moldings in the form of a foam polymer foam preferably has a pore size in the range of 100 to 5000 μηη, more preferably from 450 to 4000 μηη and in particular from 450 to 3000 μηη. A suitable polymer foam preferably has a layer thickness of 5 to 60 mm, particularly preferably 10 to 30 mm. A suitable polymer foam preferably has a density of

300 to 1200 kg / m ³ . The specific surface area is preferably in a range of 100 to 20000 m ² / m ³ , particularly preferably 1000 to 6000 m ² / m ³ . The porosity is preferably in a range of 0.50 to 0.95.

Alternatively, to provide a catalytically active fixed bed according to the invention, a monolithic shaped body in the form of a metal foam based on at least a first metal as a catalyst support in a reactor are introduced and then by the novel process with a suspension of at least one catalyst or a precursor thereof Be brought in contact. The catalyst or precursor contains at least one second metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir. The first and the second metal may in principle be the same or different. Contacting the packed bed with the catalyst or a precursor thereof (step b))

Preferably, the catalysts contain at least one element selected from Ni, Co, Cu, Re, Ru, Pt and Pd. More preferably, the catalysts contain at least one element selected from Ni, Co, Cu, Re and Ru.

In a specific embodiment, the catalysts contain Ni.

In a further specific embodiment, the catalytically active catalysts contain no Pd. This is understood to mean that no palladium is actively added to produce the catalytically active shaped bodies, neither as a catalytically active metal nor as a promoter element, nor to provide the shaped bodies which serve as the carrier material. Preferably, the monolithic moldings loaded with the catalyst or precursor obtained in step b) contain at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir, in an amount of at least 1% by weight, particularly preferably at least 2% by weight, in particular at least 5% by weight, based on the total weight of the monolithic shaped bodies loaded with the catalyst or the precursor.

Preferably, the monolithic moldings loaded with the catalyst or precursor obtained in step b) contain at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir, in an amount of at most 95% by weight, based on the total weight of the monolithic shaped bodies loaded with the catalyst or the precursor.

Preferably, the catalyst or precursor is contacted with the fixed bed in a liquid medium. Preferred liquid media are selected from water, water-miscible organic solvents, and mixtures thereof. Particularly preferred liquid media are selected from water, C 1 -C 4 -alkanols and mixtures thereof. Suitable C 1 -C 4 -alkanols are methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Specifically, the liquid medium contains water or consists of water. The fixed bed is contacted in step b) with a suspension of the catalyst or precursor thereof in a liquid medium. Preferably, the catalyst or precursor is in powder form.

Preferably, in step b), the fixed bed containing at least 0.1 wt .-%, preferably at least 1 wt .-%, more preferably at least 5 wt .-% igen suspension of the catalyst or the precursor thereof in a liquid - brought into contact with the medium.

Preferably, in step b) the contacting of the fixed bed with the catalyst or the precursor takes place at a temperature in the range from 10 to 100 ° C., particularly preferably from 20 to 80 ° C.

Preferably, in step b) the contacting of the fixed bed with the catalyst or the precursor takes place at a pressure in the range from 0.5 bar to 2 bar, particularly preferably 0.8 bar to 1.2 bar, in particular at ambient pressure. The contacting of the fixed bed with at least one catalyst or a precursor thereof takes place in principle by passing the catalyst or the precursor through the fixed bed in a liquid medium.

The catalyst or the precursor thereof is conducted in step b) at least partially in a liquid circulation stream. Suitable for this purpose are in principle all hydrogenation reactors with liquid circulation, as described below.

The contacting of the fixed bed with at least one catalyst or a precursor thereof can be done in a sump or trickle mode. Preference is given to the sumping method, wherein the catalyst or the precursor thereof is fed to the sump side of the fixed catalyst bed and is discharged on the head side after passing through the fixed catalyst bed.

If the contacting of the fixed bed with at least one catalyst or a precursor thereof in step b) is carried out in the upflow mode, the fixed bed provided according to the invention is preferably also operated in the subsequent hydrogenation in the upflow mode. If the contacting of the fixed bed with at least one catalyst or a precursor thereof in step b) takes place in trickle mode, then the fixed bed provided according to the invention is preferably also operated in the subsequent hydrogenation in trickle mode.

In a first embodiment, in step b), the contacting of the fixed bed with at least one catalyst or a precursor thereof takes place in trickle mode. Then, in a vertically oriented reactor, the catalyst or the precursor thereof is fed into the top of the reactor, passed from top to bottom through the fixed bed, taken below the fixed bed a discharge and returned head side into the reactor. The discharged stream can be subjected to a workup, z. B. by removal of a portion of the catalyst or precursor abgeschrier- secured liquid medium or by feeding fresh catalyst or precursor. In a second embodiment, in step b) the contacting of the fixed bed with at least one catalyst or a precursor thereof takes place in the upflow mode. Then, in a vertically oriented reactor, the catalyst or the precursor thereof is fed into the reactor on the swamp side, guided from below upwards through the fixed bed, a discharge taken above the fixed bed and returned to the reactor on the swamp side. The discharged stream can be subjected to a workup, z. Example, by separating a portion of the catalyst or precursor depleted liquid medium or by feeding fresh catalyst or precursor.

In general, the desired amount of the catalyst or its precursor suspended in a liquid medium is introduced into the reactor until the catalyst or its precursor is retained in the monolith. In this case, for example, the suspension is circulated via the reactor, wherein it may be the case that the suspension is only gradually absorbed by the monolith. In this Umpumpstrom can also be gradually metered additional catalyst or its precursor. During the slurrying gas can already be introduced into the reactor. The duration of sludging is usually between 0.5 and 24 hours. The process of slurrying can be repeated even after commissioning of the fixed catalyst bed, z. B. after a malfunction in which the catalyst was partially set free again by the catalyst is simply pumped in a circle until it is back in the monolith. Subsequently, the hydrogenation can be resumed.

Without wishing to be bound by theory, one can imagine the loading of the fixed bed by the method according to the invention, such as the interaction between a filter pack and a solid to be filtered off. In this case, depending on the pore size and the surface of the reactor, the solid can at least partially se be introduced into the fixed bed and is retained due to various mechanisms, such as particle inertia, diffusion effects, electrostatics or locking effects in a fixed bed. The following properties of the catalyst or the precursor are of critical importance.

Preferably, in step b), at least 90% by weight of the at least one catalyst or precursor thereof, based on the total weight of the catalyst or precursor thereof, has a particle size in the range 0.1 to 200 μm, preferably in the range 1 to 100 μηη, in particular in the range of 5 to 50 μηη on.

Particularly preferably, in step b) at least 95 wt .-% of the at least one catalyst or the precursor thereof, based on the total weight of the catalyst or the precursor thereof, a particle size in the range of 0.1 to 200 μηη, in particular in the range of 1 to 100 μηη, especially in the range of 5 to 50 μηη on.

The bulk density of the catalyst used in step b) or the precursor thereof is preferably at least 0.8 g / mL, more preferably at least 1 g / mL, especially at least 1.5 g / mL. It has been found that if the bulk density is too low, too little catalyst remains in the fixed bed. The result is that the space-time yields when using the catalytically active fixed bed for hydrogenation are too low, whereby the process is economically disadvantaged. An example of catalysts or precursors with too low bulk density are those based on activated charcoal as carrier material, since this usually has a bulk density of less than 0.8 g / mL.

Preferably, the bulk density of the catalyst used in step b) or the precursor thereof is at most 10 g / mL.

Bulk density psch (also referred to as bulk density) is the density (i.e., mass per volume) of a mixture of a granular solid (bulk material) and a continuous fluid that fills the voids between the particles. In the present case, the fluid is air. Thus, the bulk density psch is defined analogously to the density of gases, liquids and solids as the ratio of the mass m of the bed to the occupied bulk volume. Methods for determining the bulk density are known in the art and based on the weighing of the bulk material, which occupies a predetermined bulk volume.

It is undesirable that catalytically active fixed beds during the hydrogenation (step f)) larger amounts of solids, especially of catalytically active particles, to the Release reaction medium. This requires on the one hand measures for catalyst retention, so that it is not discharged with the recycle stream and / or the removed product from the reactor. This leads to an economic disadvantage. The catalytically active fixed beds obtained by the process according to the invention are characterized in that only a very small proportion of the introduced catalyst is released into the reaction medium. During the hydrogenation (step f)), the liquid stream leaving the reactor preferably contains less than 1000 ppm by weight, more preferably less than 500 ppm by weight, in particular less than 100 ppm by weight, based on the total weight of the liquid stream , undissolved solids. The determination of the amount of solids dissolved out of the catalytically active fixed bed can be carried out, for example, by gravimetry or elemental analysis, by determining the content of the catalytically active metal component in the total amount of liquid flow leaving the reactor. Preferably, the catalyst or precursor thereof is selected from precipitation catalysts, supported catalysts and Raney metal catalysts and the precursors thereof.

In a first variant, the fixed bed is brought into contact with an already active catalyst in step b).

Preferably, the active catalyst is then selected from catalysts which have been subjected to activation with a reducing gas, preferably hydrogen, and Raney metal catalysts.

Particularly preferred active catalysts which can be subjected to the activation of a treatment with a reducing gas are known in principle to the person skilled in the art. These include z. As the usual activated catalysts containing a metal, for. As Cu, Ni or Co, on an inert carrier. Virtually all support materials of the prior art, as are advantageously used in the preparation of supported catalysts, can be used as the inert support material for the catalysts. The support materials are preferably selected so that the catalysts have the aforementioned preferred particle sizes and / or bulk densities. Suitable carriers are, for example, ZrO.sub.2, TIO.sub.2, SIO.sub.2 (quartz), porcelain, magnesium oxide, tin dioxide, silicon carbide, rutile, Al.sub.2O.sub.3 (alumina), aluminum silicate, steatite

(Magnesium silicate), zirconium silicate, cersilicate or mixtures of these support materials. Preferred support materials are zirconia, titania, alumina and silica. As the silica support material can silica materials of different origin and production, for. B. pyrogenic silicic acids or wet-chemically prepared silicas, such as silica gels, aerogels or precipitated silicas.

In a second variant, the fixed bed is contacted in step b) with a catalyst precursor containing at least one metal in oxidic form, and subjected to the loaded fixed bed obtained in step b) in step c) to activate a treatment with a reducing Gas, preferably hydrogen. Suitable metals in oxidic form are, for. As the oxides of Cu, Re, Ni, Co or Ru. In a third variant, in step b), the fixed bed is brought into contact with an alloy containing at least one first metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au and Pd, and the at least contains a second component which is selected from Al, Zn and Si, and subjects the loaded fixed bed obtained in step b) in step c) to activate a treatment with an aqueous base.

Activation (step c))

Optionally, the loaded fixed bed obtained in step b) is subjected to activation.

In the first variant mentioned above in step b), the fixed bed is brought into contact with an already active catalyst. According to this variant can be dispensed with activation of the loaded fixed bed in the rule.

In the second variant mentioned above in step b), the fixed bed is subjected to the activation of a treatment with a reducing gas, preferably hydrogen. Such methods for activating catalyst precursors are known to the person skilled in the art. Preferably, a two-phase mixture is used for activation, which contains a gaseous phase which consists essentially of hydrogen, and which contains a liquid phase. Suitable liquids are water, alcohols, hydrocarbons or mixtures thereof.

In the third variant mentioned above in step b), the fixed bed is subjected to the activation of a treatment with an aqueous base.

Preference is given to alloys in which the first metal contains Ni or consists of Ni. Preference is furthermore given to alloys in which the second component contains Al or AI consists. A specific embodiment is alloys containing nickel and aluminum.

The moldings used for activation preferably have from 60 to 95% by weight, particularly preferably from 70 to 80% by weight, of a first metal selected from Ni, Fe, Co, Cu, Cr, based on the total weight. Pt, Ag, Au and Pd.

Preferably, the moldings used for activation based on the total weight of 5 to 40 wt .-%, particularly preferably 20 to 30 wt .-%, of a second component which is selected from Al, Zn and Si.

Preferably, the moldings used for activation based on the total weight of 60 to 95 wt .-%, particularly preferably 70 to 80 wt .-%, Ni. Preferably, the moldings used for activation based on the total weight of 5 to 40 wt .-%, particularly preferably 20 to 30 wt .-%, AI on.

Preferably, from the moldings, the activation removes from 30 to 70% by weight, particularly preferably from 40 to 60% by weight, of the second component, based on the original weight of the second component.

Preferably, the moldings used for activation contain Ni and Al and is removed by the activation 30 to 70 wt .-%, particularly preferably 40 to 60 wt .-%, of Al, based on the original weight.

The determination of the dissolved out of the moldings amount of the second component, for. As aluminum, for example, can be done by elemental analysis by determining the content of the second component in the total amount of discharged laden aqueous base and the washing medium. Alternatively, the determination of the dissolved out of the catalyst moldings amount of the second component can be determined by the amount of hydrogen formed during the activation. In the case in which aluminum is used, in each case 3 mol of hydrogen are produced by dissolving 2 mol of aluminum.

During activation, the fixed bed is subjected to a treatment with an aqueous base as a treatment medium, wherein the second (leachable) component of the shaped body is at least partially dissolved and removed from the moldings. The treatment with the aqueous base is exothermic, so that the fixed bed warmed up as a result of activation. The heating of the fixed bed is dependent on the concentration of the aqueous base used. If no heat is removed from the reactor by active cooling, but instead is transferred to the treatment medium, so that an adiabatic procedure is effectively implemented, then during activation a temperature gradient develops in the fixed bed, the temperature increasing in the current direction of the aqueous base. However, even if heat is removed from the reactor by active cooling, a temperature gradient forms in the fixed bed during activation. The activation of the fixed catalyst bed can be carried out in a sump or trickle mode. Preference is given to the upflow method, wherein the fresh aqueous base is fed to the marsh side of the fixed catalyst bed and is discharged at the top end after passing through the fixed catalyst bed. After passing through the fixed catalyst bed, a loaded aqueous base is obtained. The loaded aqueous base has a lower base concentration than the aqueous base before passing through the fixed catalyst bed and is enriched in the reaction products formed during activation and at least partially soluble in the base. These reaction products include, for. Example, when using aluminum as the second (leachable) component alkali aluminates, aluminum hydroxide hydrates, hydrogen, etc. (see, for example, US 2,950,260).

The statement that the fixed catalyst bed has a temperature gradient during the activation is understood in the context of the invention as meaning that over a longer period of the total activation the fixed catalyst bed has this temperature gradient. The fixed catalyst bed preferably has a temperature gradient until at least 50% by weight, preferably at least 70% by weight, in particular at least 90% by weight, of the amount of aluminum to be removed has been removed from the shaped catalyst bodies. Unless during the activation the strength of the aqueous base used is increased and / or the temperature of the fixed catalyst bed is increased by less cooling than at the beginning of activation or external heating, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed become progressively lower in the course of activation and can then also assume the value of zero towards the end of the activation.

Preferably, the temperature difference between the coldest point of the catalyst fixed bed and the warmest point of the fixed catalyst bed is kept at a maximum of 50 K. To determine the temperature difference in the course of the fixed catalyst bed can this be provided with conventional measuring devices for temperature measurement. For determining the temperature difference between the warmest point of the fixed catalyst bed and the coldest point of the fixed catalyst bed, it is generally sufficient for a non-actively cooled reactor to determine the temperature difference between the most upstream location of the fixed catalyst bed and the most downstream location of the fixed catalyst bed , In an actively cooled reactor, it may be useful to provide at least one additional temperature sensor in the flow direction between the most upstream location of the fixed catalyst bed and the most downstream location of the fixed catalyst bed (eg, 1, 2, or 3 more temperature sensors).

Preferably, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed is maintained at a maximum of 40 K, preferably at a maximum of 25 K.

Preferably, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed at the beginning of activation in a range of 0.1 to 50 K, preferably in a range of 0.5 to 40 K, in particular in a range of 1 to 25K, kept. It is possible initially to initially introduce an aqueous medium without base and then to add fresh base until the desired concentration has been reached. In this case, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed at the beginning of the activation means the time at which the desired base concentration at the reactor inlet is reached for the first time.

The control of the size of the temperature gradient in the fixed catalyst bed can be carried out in a non-actively cooled reactor by selecting the amount and concentration of the supplied aqueous base according to the heat capacity of the medium used for activation. In order to control the size of the temperature gradient in the fixed catalyst bed in an actively cooled reactor, heat is also removed from the medium used for activation by heat exchange. Such removal of heat can be done by cooling the medium used for activation in the reactor used and / or, if present, the liquid circulation stream.

The monolithic shaped bodies are preferably subjected to the activation of a treatment with a maximum of 3.5% by weight aqueous base. Particularly preferred is the use of a maximum of 3.0 wt .-% aqueous base. Preference is given to Shaped body for activating a treatment with a 0.1 to 3.5 wt .-% aqueous base, more preferably a 0.5 to 3.5 wt .-% aqueous base subjected. The concentration specification refers to the aqueous base prior to its contact with the shaped catalyst bodies. If, for activation, the aqueous base is brought into contact only once with the shaped catalyst bodies, the concentration information relates to the fresh aqueous base. If, for activation, the aqueous base is passed at least partly in a liquid circulation stream, then the laden base obtained after the activation can be added before it is used again to activate the fresh base moldings. The previously indicated concentration values apply analogously.

By maintaining the above-mentioned concentrations for the aqueous base, moldings of Raney metal catalysts having high activity and very good stability are obtained. This applies in particular to the activation of fixed beds for hydrogenation reactions on an industrial scale. Surprisingly, an excessively high temperature increase and the uncontrolled formation of hydrogen in the activation of the catalysts are effectively avoided with the given concentration ranges of the base. This advantage has a special effect on reactors on an industrial scale.

In a preferred embodiment, the aqueous base used for activation is at least partially conducted in a liquid circulation stream. In a first embodiment, the reactor is operated with the catalyst to be activated in the upflow mode. Then, in a vertically oriented reactor, the aqueous base is fed to the sump side of the reactor, passed from bottom to top through the fixed catalyst bed, taken above the fixed catalyst bed a discharge and returned to the sump side in the reactor. The discharged stream is preferably a workup, z. B. by separation of hydrogen and / or the discharge of a portion of the loaded aqueous base. In a second embodiment, the reactor is operated in trickle mode with the catalyst to be activated. Then, in a vertically oriented reactor, the aqueous base is fed into the top of the reactor, passed from top to bottom through the fixed catalyst bed, removed below the fixed catalyst bed and discharged back into the reactor at the top. In this case, the discharged current is preferably in turn a workup, z. B. by separation of hydrogen and / or the discharge of a portion of the loaded aqueous base. Preferably, the activation takes place in a vertical reactor in the upflow mode (ie with an upward flow through the fixed catalyst bed). Such driving is beneficial if due to hydrogen formation during activation Even a small gas load is generated, as this can be easily dissipated overhead.

In a preferred embodiment, fresh aqueous base is added to the fixed bed in addition to the base carried in the liquid recycle stream. The supply of fresh base can be done in the liquid recycle stream or separately in the reactor. In this case, the fresh aqueous base may also be concentrated higher than 3.5 wt .-%, provided that after mixing with the recycled aqueous base, the base concentration is not higher than 3.5 wt .-%.

The ratio of aqueous base passed in the circulation stream to freshly supplied aqueous base is preferably in a range from 1: 1 to 1000: 1, more preferably from 2: 1 to 500: 1, in particular from 5: 1 to 200: 1. The feed rate of the aqueous base (if the aqueous base used for the activation is not conducted in a liquid circulation stream) is preferably at most 5 L / min per liter of fixed bed, preferably at most 1.5 L / min per liter of fixed bed, more preferably at most 1 L / min per liter of fixed bed, based on the total volume of the fixed bed.

The aqueous base used for activation is preferably conducted at least partially in a liquid circulation stream and the feed rate of the freshly fed aqueous base is at most 5 L / min per liter of fixed bed, preferably at most 1.5 L / min per liter of fixed bed, more preferably at most 1 L / min per liter of fixed bed, based on the total volume of the fixed bed.

Preferably, the feed rate of the aqueous base (when the aqueous base used for activation is not carried in a liquid recycle stream) is in the range of 0.05 to 5 L / min per liter of fixed bed, more preferably in the range of 0.1 to 1 , 5 L / min per liter of fixed bed, in particular in a range of 0.1 to 1 L / min per liter of fixed bed, based on the total volume of the fixed bed.

Preferably, the aqueous base used for activation is at least partially conducted in a liquid circulation stream and the feed rate of the freshly supplied aqueous base is in a range of 0.05 to 5 L / min per liter of fixed bed, more preferably in a range of 0.1 to 1, 5 L / min per liter of fixed bed, in particular in a range of 0.1 to 1 L / min per liter of fixed bed, based on the total volume of the fixed bed. This control of the feed rate of the fresh aqueous base is an effective way to maintain the temperature gradient resulting in the fixed bed within the desired range of values. The flow rate of the aqueous base through the reactor containing the fixed bed is preferably at least 0.5 m / h, more preferably at least 3 m / h, especially at least 5 m / h, especially at least 10 m / h.

In order to avoid a mechanical load and abrasion of the newly formed porous catalyst metal, it may be useful not to choose the flow rate too high. The flow rate of the aqueous base through the reactor containing the fixed bed is preferably at most 100 m / h, more preferably at most 50 m / h, especially at most 40 m / h. The above-mentioned flow rates can be achieved particularly well if at least some of the aqueous base is conducted in a liquid circulation stream.

The base used to activate the fixed bed is selected from alkali metal hydroxides, alkaline earth metal hydroxides and mixtures thereof. Preferably, the base is selected from NaOH, KOH and mixtures thereof. Specifically, NaOH is used as the base. The base is used for activation in the form of an aqueous solution.

The procedure described above makes it possible to effectively minimize a detachment of the catalytically active metal, such as nickel, during the activation. A suitable measure of the effectiveness of the activation and the stability of the obtained Raney metal catalyst is the metal content in the loaded aqueous base. When using a liquid recycle stream, the metal content in the recycle stream is a convenient measure of the effectiveness of the activation and the stability of the resulting Raney metal catalyst. The content of nickel during activation in the loaded aqueous base or, if the liquid circulation stream is used for activation, in the circulation stream is preferably at most 0.1% by weight, particularly preferably at most 100 ppm by weight, in particular at most 10 ppm by weight. The determination of the nickel content can be done by elemental analysis. The same advantageous values are usually also achieved in the following process steps, such as treatment of the activated fixed bed with a washing medium, treatment of the fixed bed with a dopant and use in a hydrogenation reaction. The inventive method allows a homogeneous distribution of the catalytically active Raney metal on the moldings used and a total of the resulting activated fixed bed. No or only a slight gradient with respect to the distribution of the catalytically active Raney metal in the flow direction of the activation medium through the fixed bed is formed. In other words, the concentration of catalytically active sites upstream of the fixed bed is substantially equal to the concentration of catalytically active sites downstream of the fixed bed. This advantageous effect is achieved in particular if the aqueous base used for activation is at least partially guided in a liquid circulation stream. The inventive method also allow a homogeneous distribution of the leached second component, for. As the aluminum, on the moldings used and a total of the resulting activated fixed bed. There is no or only a slight gradient with respect to the distribution of the dissolved-out second component in the flow direction of the activation medium through the fixed bed.

Another advantage, if the aqueous base used for activation is at least partially conducted in a liquid circulation stream, is that the required amount of aqueous base can be significantly reduced. For example, a straight pass of the aqueous base (without recycling) and the subsequent removal of the laden base result in a high requirement for fresh base. By supplying suitable amounts of fresh base in the recycle stream, it is ensured that there is always sufficient base for the activation reaction. All in all, significantly lower quantities are required for this. After passing through the fixed bed, a laden aqueous base is obtained which, compared to the aqueous base, has a lower base concentration before passing through the fixed bed and which is enriched in the reaction products formed and at least partially soluble in the base. Preferably, at least part of the loaded aqueous base is discharged. Thus, even if a portion of the aqueous base is passed in a recycle stream, excessive dilution and accumulation of undesirable impurities in the aqueous base used for activation can be avoided. The amount of aqueous base freshly supplied per unit time preferably corresponds to the amount of laden aqueous base removed.

A discharge of laden aqueous base is preferably taken from the activation and subjected to a gas / liquid separation, a hydrogen-containing gas phase and a liquid phase being obtained. For gas / liquid separation, it is possible to use the customary devices known to the person skilled in the art, such as the usual separation tanks. The hydrogen-containing gas phase obtained in the phase separation can be discharged from the process and z. B. a thermal utilization can be supplied. The liquid phase obtained in the phase separation, which contains the discharged laden aqueous base, is preferably at least partially recycled as a liquid circulation stream into the activation. Preferably, part of the liquid phase obtained in the phase separation, which contains the discharged laden aqueous base, is discharged. Thus, as previously described, excessive dilution and accumulation of undesirable impurities in the aqueous base used for activation can be avoided.

To control the progress of the activation and to determine the amount of the second component dissolved out of the shaped catalyst bodies, e.g. As aluminum, the amount of hydrogen formed during the activation can be determined. In the case in which aluminum is used, in each case 3 mol of hydrogen are produced by the dissolution of 2 mol of aluminum.

The activation according to the invention preferably takes place at a temperature of at most 50 ° C., preferably at a temperature of at most 40 ° C. The activation according to the invention preferably takes place at a pressure in the range from 0.1 to 10 bar, more preferably from 0.5 to 5 bar, especially at ambient pressure.

Treatment with a Wash Medium (Step d)) In optional step d) of the process according to the invention, the loaded fixed bed obtained in step b) or the activated fixed bed obtained in step c) is subjected to a treatment with a washing medium which is selected from water, C4 alkanols and mixtures thereof. Suitable C 1 -C 4 -alkanols are methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.

Preferably, the washing medium used in step d) contains water or consists of water.

Preference is given to carrying out the treatment with the washing medium in step d) until the effluent washing medium has a conductivity at a temperature of 20 ° C. of not more than 200 mS / cm, more preferably not more than 100 mS / cm, in particular not more than 10 mS / cm, having. In step d), water is preferably used as the washing medium and the treatment with the washing medium is carried out until the effluent washing medium has a pH at 20 ° C. of not more than 9, particularly preferably not more than 8, in particular not more than 7.

The treatment with the washing medium is preferably carried out in step d) until the effluent washing medium has an aluminum content of at most 5% by weight, more preferably of at most 5000 ppm by weight, in particular of at most 500 ppm by weight.

Preferably, in step d), the treatment with the washing medium at a temperature in the range of 20 to 100 ° C, more preferably from 20 to 80 ° C, in particular from 25 to 70 ° C, performed.

Doping (step e))

A doping refers to the introduction of foreign atoms in a layer or in the base material of a catalyst. The amount introduced in this process is generally small compared to the rest of the catalyst material. The doping specifically changes the properties of the starting material

In a specific embodiment, the fixed catalyst bed after activation (ie following step c), if performed) and optionally after treatment with a wash medium (ie also subsequent to step d), if performed) with a Dopant in contact, which has at least one element which is different from the first metal and the second component of the catalyst molding used in step a). Such elements are referred to hereinafter as "promoter elements". Preferably, contacting with the dopant occurs during and / or after treatment of the activated fixed catalyst bed with a wash medium (i.e., during and / or after step d)).

The dopant used according to the invention preferably contains at least one promoter element which is selected from Ti, Ta, Zr, V, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Ce and Bi.

It is possible that the dopant contains at least one promoter element which simultaneously fulfills the definition of a first metal in the sense of the invention. such Promoter elements are selected from Ni, Fe, Co, Cu, Cr, Pt, Ag, Au, Pd, Mn, Re, Ru, Rh and Ir. In this case, the monolithic molded article contains, based on the reduced metallic form, a major amount (ie, more than 50% by weight) of the first metal and a minor amount (ie, less than 50% by weight) of a different metal as a dopant , When specifying the total amount of the first metal containing the monolithic catalyst form body, however, all metals that meet the definition of a first metal according to the invention are calculated with their full weight fraction (regardless of whether they act as hydrogenation-active component or as a promoter).

In a specific embodiment, the dopant does not contain a promoter element which fulfills the definition of a first metal in the sense of the invention. The dopant then preferably contains exclusively a promoter element or more than one promoter element which is selected from among Ti, Ta, Zr, V, Mo, W, Bi and Ce.

Preferably, the dopant contains Mo as a promoter element. In a specific embodiment, the dopant contains Mo as the sole promoter element.

The promoter elements are particularly preferably used for doping in the form of their salts. Suitable salts are, for example, the nitrates, sulfates, acetates, formates, fluorides, chlorides, bromides, iodides, oxides or carbonates. The promoter elements either separate by themselves in their metallic form due to their nobler character compared to Ni or can be brought into contact with a reducing agent such as e.g. As hydrogen, hydrazine, hydroxylamine, etc., are reduced in their metallic form. If the promoter elements are added during the activation process, then they can also be in their metallic form. In this case, it may be useful for the formation of metal-metal compounds to subject the fixed catalyst bed after the storage of the promoter metals first an oxidative treatment and then a reducing treatment.

In a specific embodiment, the fixed catalyst bed is contacted during and / or after treatment with a wash medium in step c) with a dopant containing Mo as a promoter element. More specifically, the dopant contains Mo as the sole promoter element. Suitable molybdenum compounds are selected from molybdenum trioxide, the nitrates, sulfates, carbonates, chlorides, iodides and bromides of molybdenum and the molybdates. Preference is given to the use of ammonium molybdate. In a preferred embodiment, a molybdenum compound is used which has good water solubility. A good solubility in water means a solubility of at least 20 g / l at 20 ° C. the. When using molybdenum compounds, which have a lower water solubility, it may be useful before they are used as a dopant to filter the solution. Suitable solvents for doping are water, polar solvents which are different from water and solvents which are inert to the catalyst under the doping conditions, and mixtures thereof. Preferably, the solvent used for doping is selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and mixtures thereof.

The temperature during the doping is preferably in a range from 10 to 100 ° C., more preferably from 20 to 60 ° C., in particular from 20 to 40 ° C.

The concentration of the promoter element in the dopant is preferably in a range of about 20 g / L to the maximum soluble amount of the dopant under the doping conditions. As a rule, one will assume a maximum of one solution saturated at ambient temperature.

The duration of the doping is preferably 0.5 to 24 hours.

It may be advantageous for the doping to take place in the presence of an inert gas. Suitable inert gases are z. As nitrogen or argon.

In a specific embodiment for doping foam-shaped shaped catalyst bodies, a molybdenum source is dissolved in water and this solution is passed through the previously activated foam. When using hydrates of ammonium molybdate, such as. B. (ΝΗ4) 6Μθ7θ24 x 4 H2O, this is dissolved in water and this solution used. The usable amount depends strongly on the solubility of the ammonium molybdate and is in principle not critical. Conveniently, less than 430 grams of ammonium molybdate are dissolved per liter of water at room temperature (20 ° C). If the doping is carried out at a higher temperature than room temperature, then larger amounts can be used. The ammonium molybdate solution is then passed over the activated and washed foam at a temperature of 20 to 100 ° C, preferably at a temperature of 20 to 40 ° C. The treatment time is preferably 0.5 to 24 hours, more preferably 1 to 5 hours. In a specific embodiment, the contacting takes place in the presence of an inert gas, such as nitrogen. The pressure is preferably in a range of 1 to 50 bar, especially at about 1 bar absolute. Thereafter, the doped Raney nickel foam can be used either without further workup or after repeated washing for the hydrogenation. The doped catalyst bodies preferably contain 0.01 to 10 wt .-%, particularly preferably 0.1 to 5 wt .-%, promoter elements based on the reduced metallic form of the promoter elements and the total weight of the shaped catalyst bodies.

The fixed catalyst bed may contain the promoter elements substantially homogeneously or heterogeneously distributed in their concentration. In a specific embodiment, the fixed catalyst bed has a gradient in the flow direction with respect to the concentration of the promoter elements. In particular, the fixed catalyst bed contains or consists of Ni / Al catalyst moldings which are activated by the process according to the invention and / or which are doped with Mo and has a gradient with respect to the Mo concentration in the flow direction.

It is possible to obtain a fixed bed catalyst which is fixedly installed in a reactor and which contains at least one promoter element which substantially homogeneously distributes its concentration, i. H. not in the form of a gradient. To provide such a fixed bed catalyst, it is possible not to dope the catalyst in built-in form in the fixed bed reactor itself, possibly with circulation, whereby a concentration gradient can arise. Preferably, the doping is then carried out in an external container without circulation, which is infinitely back-mixed, such. B. a batch reactor without continuous feed and drain. After doping and, if appropriate, washing, such catalysts can be incorporated in a fixed bed reactor with or without a circulation and are therefore without gradients.

To provide a fixed catalyst bed having a gradient in the flow direction with respect to the concentration of promoter elements, one can proceed by passing a liquid stream of the dopant through the fixed catalyst bed. If the reactor has a circulation stream, it is alternatively or additionally possible to feed the dopant in liquid form into the circulation stream. In such an approach, a concentration gradient of the promoter elements is formed over the entire length of the fixed catalyst bed in the flow direction. If it is desired that the concentration of the promoter element in the flow direction of the reaction medium of the reaction to be catalyzed decreases, the liquid flow of the dopant is conducted in the same direction as the reaction medium of the reaction to be catalyzed by the fixed catalyst bed. If it is desired for the concentration of the promoter element in the direction of flow of the reaction medium of the reaction to be catalyzed to increase, the liquid flow of the dopant will be increased in the opposite direction as the reaction medium of the reaction to be catalyzed passed through the fixed catalyst bed.

In a first preferred embodiment, the activated catalyst fixed bed obtained by the process according to the invention or a reactor containing such an activated fixed catalyst bed for the hydrogenation of 1, 4-butynediol to give 1, 4-butanediol. It has now surprisingly been found that a particularly high selectivity is achieved in the hydrogenation, if one uses a fixed catalyst bed containing Ni / Al catalyst, which are activated by the novel process and / or which are doped with Mo and wherein the concentration of molybdenum increases in the flow direction of the reaction medium of the hydrogenation reaction. Preferably, the molybdenum content of the shaped catalyst bodies at the entry of the reaction medium in the fixed catalyst bed 0 to 3 wt .-%, particularly preferably 0 to 2.5 wt .-%, in particular 0.01 to 2 wt .-%, based on metallic molybdenum and the Total weight of the shaped catalyst bodies. The molybdenum content of the shaped catalyst bodies at the outlet of the reaction medium from the fixed catalyst bed is preferably from 0.1 to 10% by weight, more preferably from 0.1 to 7% by weight, in particular from 0.2 to 6% by weight, based on metallic molybdenum and the total weight of the shaped catalyst bodies.

In a second preferred embodiment, the activated catalyst fixed bed obtained by the process of the present invention or a reactor containing such an activated fixed catalyst bed is used for the hydrogenation of butyraldehyde to give n-butanol. It has now surprisingly been found that a particularly high selectivity is achieved in the hydrogenation, if one uses a fixed catalyst bed containing Ni / Al catalyst, which are activated by the novel process and / or which are doped with Mo and wherein the concentration of molybdenum decreases in the direction of flow of the reaction medium of the hydrogenation reaction. Preferably, the molybdenum content of the catalyst molding is at the entry of the reaction medium in the fixed catalyst bed 0.5 to 10 wt .-%, particularly preferably 1 to 9 wt .-%, in particular 1 to 7 wt .-%, based on metallic molybdenum and the total weight of catalyst bodies. Preferably, the molybdenum content of the catalyst molding is at the outlet of the reaction medium from the fixed catalyst bed 0 to 7 wt .-%, particularly preferably 0 to 5 wt .-%, in particular 0.01 to 4.5 wt .-%, based on metallic molybdenum and the Total weight of the shaped catalyst bodies.

It has been found that it is important for the efficiency of the doping of Raney metal catalysts and especially Raney nickel catalysts with a promoter element, especially Mo, is advantageous if, after activation and before doping, the activated fixed catalyst bed is subjected to a treatment with a washing medium. This is especially true when foam-like Raney nickel catalysts are used for the doping. It has been found, in particular, that the adsorption of molybdenum on the shaped catalyst bodies is incomplete if, after activation, the content of washable aluminum is still too high. Preferably, therefore, the treatment with a washing medium in step d) is carried out before the doping in step e) until the effluent washing medium at a temperature of 20 ° C has a conductivity of at most 200 mS / cm. The treatment with the washing medium is preferably carried out in step d) until the effluent washing medium has an aluminum content of at most 500 ppm by weight.

The activated catalyst fixed beds obtained by the process according to the invention, which contain doped shaped catalyst bodies, are generally distinguished by high mechanical stability and long service lives. Nevertheless, the fixed bed catalyst is mechanically stressed when it is flowed through in the liquid phase with the components to be hydrogenated. In the long term, wear or removal of the outer layers of the active catalyst species may occur. If the Raney nickel foam catalyst was prepared by leaching and doping, then the subsequently doped metal element is preferably on the outer active catalyst layers, which can also be removed by mechanical liquid or gas loading. If the promoter element is removed, this can result in a reduced activity and selectivity of the catalyst. Surprisingly, it has now been found that the original activity can be restored by the doping process is carried out again. Alternatively, the dopant can also be added to the hydrogenation, which is then post-doped in situ (Method 4).

Hydrogenation (step f))

In the context of the invention, hydrogenation is understood in general to mean the reaction of an organic compound with H 2 addition to this compound. Preferably, functional groups are hydrogenated to the correspondingly hydrogenated groups. These include, for example, the hydrogenation of nitro groups, nitroso groups, nitrile groups or imine groups to amine groups. This includes, for example, the hydrogenation of aromatics to saturated cyclic compounds. This also includes, for example, the hydrogenation of carbon-carbon triple bonds to double bonds and / or single bonds. This includes, for example, the hydrogenation of carbon-carbon double bonds to single bonds. Also includes finally, for example, the hydrogenation of ketones, aldehydes, esters, acids or anhydrides to alcohols.

The hydrogenation of carbon-carbon triple bonds, carbon-carbon double bonds, aromatic compounds, carbonyl-containing compounds, nitriles and nitro compounds is preferred. Carbonyl-containing compounds suitable for hydrogenation are ketones, aldehydes, acids, esters and anhydrides. Particularly preferred is the hydrogenation of carbon-carbon triple bonds, carbon-carbon double bonds, nitriles, ketones and aldehydes.

The hydrogenatable organic compound is particularly preferably selected from 1,4-butynediol, 1,4-butenediol, 4-hydroxybutyraldehyde, hydroxypivalic acid, hydroxypivaldehyde, n- and isobutyraldehyde, n- and isovaleraldehyde, 2-ethylhex-2 -enal,

2-ethylhexanal, the isomeric nonanals, 1, 5,9-cyclododecatriene, benzene, furan, furatural, phthalic acid esters, acetophenone and alkyl-substituted acetophenones. Very particular preference is given to the hydrogenatable organic compound selected from 1,4-butynediol, 1,4-butenediol, n- and isobutyraldehyde, hydroxypivalaldehyde,

2-ethylhex-2-enal, the isomeric nonanals and 4-isobutylacetophenone.

The hydrogenation according to the invention leads to hydrogenated compounds which accordingly no longer contain the group to be hydrogenated. Contains a compound at least 2 different hydrogenatable groups, it may be desirable to hydrogenate only one of the unsaturated groups, for. For example, when a compound has an aromatic ring and additionally a keto group or an aldehyde group. This includes z. B. the hydrogenation of 4-isobutylacetophenone to 1- (4'-isobutylphenyl) ethanol or the hydrogenation of a C-C unsaturated ester to the corresponding saturated ester. In principle, at the same time or instead of a hydrogenation in the context of the invention, an undesired hydrogenation of other hydrogenatable groups can be carried out, for. As of carbon-carbon single bonds or C-OH bonds to water and hydrocarbons. This includes z. B. the hydrogenolysis of

1, 4-butanediol to propanol or butanol. These latter hydrogenations usually lead to undesirable by-products and are therefore not desirable. Preferably, the hydrogenation according to the invention in the presence of a suitably activated catalyst is characterized by a high selectivity with respect to the desired hydrogenation reactions. These include in particular the hydrogenation of 1, 4-butynediol or 1, 4-butenediol to 1, 4-butanediol. In particular, this includes the hydrogenation of n- and iso-butyraldehyde to n- and iso-butanol. This includes further in particular the hydrogenation of hydroxypivalaldehyde or hydroxypivalic acid to neopentyl glycol. In particular, this includes the hydrogenation of 2-ethylhex-2-enal to 2-ethylhexanol. In particular, this includes the hydrogenation of nonanals to nonanols. In particular, this includes the hydrogenation of 4-isobutylacetophenone to give 1- (4'-isobutylphenyl) ethanol.

The hydrogenation is preferably carried out continuously.

In the simplest case, the hydrogenation takes place in a single hydrogenation reactor. In a specific embodiment of the process according to the invention, the hydrogenation is carried out in n hydrogenation reactors connected in series (in series), n being an integer of at least 2. Suitable values for n are 2, 3, 4, 5, 6, 7, 8, 9 and 10. Preferably, n is 2 to 6 and in particular 2 or 3. In this embodiment, the hydrogenation is preferably carried out continuously.

The reactors used for the hydrogenation may have a fixed catalyst bed, which is formed from the same or different shaped catalyst bodies. The fixed catalyst bed may have one or more reaction zones. Various reaction zones may have shaped catalyst bodies of different chemical composition of the catalytically active species. Different reaction zones may also have catalyst moldings of the same chemical composition of the catalytically active species but in different concentrations. If at least two reactors are used for the hydrogenation, the reactors may be the same or different reactors. These can be z. B. each have the same or different mixing characteristics and / or be subdivided by internals one or more times.

Suitable pressure-resistant reactors for the hydrogenation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. B. tube reactors, tube bundle reactors and gas circulation reactors. A special embodiment of the tube reactors are shaft reactors.

The process according to the invention will be carried out in a fixed bed procedure. The fixed bed mode can be z. B. in sump or in trickle run.

The reactors used for the hydrogenation contain a catalyst fixed bed activated by the method according to the invention, through which the reaction medium flows. The fixed catalyst bed can be made of a single type of catalyst form or be formed from various shaped catalyst bodies. The fixed catalyst bed may have one or more zones, wherein at least one of the zones contains a material active as a hydrogenation catalyst. Each zone can have one or more different catalytically active materials and / or one or more different inert materials. Different zones may each have the same or different compositions. It is also possible to provide a plurality of catalytically active zones, which are separated from each other, for example, by inert beds or spacers. The individual zones may also have different catalytic activity. For this purpose, various catalytically active materials can be used and / or at least one of the zones an inert material can be added. The reaction medium flowing through the fixed catalyst bed contains at least one liquid phase. The reaction medium may also contain a gaseous phase in addition. During the hydrogenation, the CO content in the gas phase within the reactor is preferably in a range from 0.1 to 10,000 ppm by volume, more preferably in a range from 0.15 to 5000 ppm by volume, in particular in a range from 0, 2 to 1000 ppm by volume. The total CO content within the reactor is composed of CO in the gas and liquid phases, which are in equilibrium with each other. Conveniently, the CO content is determined in the gas phase and the values given here refer to the gas phase.

In this case, a concentration profile over the reactor is advantageous, wherein the concentration of CO in the flow direction of the reaction medium of the hydrogenation along the reactor should increase.

It has now surprisingly been found that a particularly high selectivity is achieved in the hydrogenation, when the concentration of CO in the flow direction of the reaction medium of the hydrogenation reaction increases. The CO content at the outlet of the reaction medium from the fixed catalyst bed is preferably at least 5 mol% higher, more preferably at least 25 mol% higher, in particular at least 75 mol% higher, than the CO content when the reaction medium enters the fixed catalyst bed. To generate a CO gradient in the flow direction of the reaction medium through the fixed catalyst bed, for example, CO can be fed into the fixed catalyst bed at one or more points.

The content of CO is determined, for example, by gas chromatography via removal of individual samples or preferably by online measurement. When samples are taken, it is particularly advantageous in front of the reactor, both gas and Remove fluid and relax it so that a balance between gas and liquid has formed; the CO content is then determined in the gas phase.

The online measurement can be done directly in the reactor, z. B. before the reaction medium enters the fixed catalyst bed and after the exit of the reaction medium from the fixed catalyst bed.

The CO content may, for. B. be adjusted by the addition of CO to the hydrogen used for the hydrogenation. Of course, CO can also be fed separately from the hydrogen in the reactor. If the hydrogenation reaction mixture is at least partly conducted in a liquid circulation stream, CO can also be fed into this circulation stream. CO can also be formed from components contained in the hydrogenation reaction mixture, e.g. B. as educts to be hydrogenated or as incurred in the hydrogenation intermediate or by-products. So can CO z. B. be formed by decarbonylation present in the reaction mixture of the hydrogenation formic acid, formates or formaldehyde. Similarly, CO can also be formed by decarbonylation of aldehydes other than formaldehyde or by dehydrogenation of primary alcohols to aldehydes and subsequent decarbonylation. These undesirable side reactions include, for. As C-C or C-X cleavages, such as the formation of propanol or butanol formation of 1, 4-butanediol. It was further found that the conversion in the hydrogenation can only be insufficient if the CO content in the gas phase within the reactor is too high, d. H. specifically above 10,000 ppm by volume. The conversion in the hydrogenation is preferably at least 90 mol%, particularly preferably at least 95 mol%, in particular at least 99 mol%, especially at least 99.5 mol%, based on the total molar amount of hydrogenatable compounds in the starting material used for the hydrogenation , The conversion refers to the amount of target compound obtained, regardless of how many molar equivalents of hydrogen have taken up the starting compound to reach the target compound. When a starting compound used in the hydrogenation contains a plurality of hydrogenatable groups or contains a hydrogenatable group which can take up several equivalents of hydrogen (eg an alkyne group), the desired target compound can be both the product of a partial hydrogenation (eg alkyne to alkene) or a complete hydrogenation (eg, alkyne to alkane).

It is important for the success of the hydrogenation according to the invention that the reaction mixture of the hydrogenation (ie gas and liquid stream) predominantly by the structured catalyst flows through and does not flow past him, as is the case for example with ordinary, packed fixed-bed catalysts.

Preferably, more than 90% of the material stream (i.e., the sum of gas and liquid streams) should flow through the fixed catalyst bed, preferably over 95%, more preferably> 99%.

The fixed catalyst beds used according to the invention preferably have free surface at any section in the normal plane to the flow direction (ie, horizontal) through the fixed catalyst bed, based on the total area of the section, preferably at most 5%, particularly preferably at most 1%, in particular at most 0.1% free area, which is not part of the catalyst bodies. The area of the pores and channels which open at the surface of the shaped catalyst body is not calculated to this free area. The indication of the free area refers exclusively to sections through the fixed catalyst bed in the region of the shaped catalyst bodies and not any internals, such as power distributors.

If the catalyst fixed beds used in accordance with the invention comprise shaped catalyst bodies which have pores and / or channels, then at least 90% of the pores and channels, more preferably at least 98% of the pores and channels, have an area at any section in the normal plane to the flow direction through the fixed catalyst bed of not more than 3 mm ² .

If the catalyst fixed beds used in accordance with the invention comprise shaped catalyst bodies which have pores and / or channels, then at least 90% of the pores and channels, more preferably at least 98% of the pores and channels, have an area at any section in the normal plane to the flow direction through the fixed catalyst bed of at most 1 mm ² . If the catalyst fixed beds used in accordance with the invention comprise shaped catalyst bodies which have pores and / or channels, then at least 90% of the pores and channels, more preferably at least 98% of the pores and channels, have an area at any section in the normal plane to the flow direction through the fixed catalyst bed of at most 0.7 mm ² .

In the case of the fixed catalyst beds according to the invention, at least 95% of the reactor cross-section, more preferably at least 98% of the reactor cross-section, is preferably at least 90% in the direction of flow through the fixed catalyst bed. in particular at least 99% of the reactor cross-section filled with shaped catalyst bodies.

In order for good mass transfer to take place in the structured catalysts, the rate at which the reaction mixture flows through the fixed catalyst bed should not be too low. The flow rate of the liquid reaction mixture through the reactor containing the fixed catalyst bed is preferably at least 30 m / h, preferably at least 50 m / h, in particular at least 80 m / h. The flow rate of the liquid reaction mixture through the reactor containing the catalyst fixed bed is preferably at most 1000 m / h, particularly preferably at most 500 m / h, in particular at most 400 m / h.

The flow direction of the reaction mixture is, in principle in an upright reactor, not of critical importance. The hydrogenation can thus be carried out in bottoms or Rieselfahrweise. The upflow mode, wherein the reaction mixture to be hydrogenated is fed to the marsh side of the fixed catalyst bed and is discharged at the top end after passing through the fixed catalyst bed, may be advantageous. This is especially true when the gas velocity should be low (eg <50 m / h). These flow rates are generally achieved by recycling a portion of the liquid stream leaving the reactor, with the recycle stream combining with the reactant stream either before the reactor or in the reactor. The educt stream can also be supplied distributed over the length and / or width of the reactor. In a preferred embodiment, the hydrogenation reaction mixture is at least partially conducted in a liquid recycle stream.

The ratio of reaction mixture conducted in the circulation stream to freshly fed educt stream is preferably in a range from 1: 1 to 1000: 1, preferably from 2: 1 to 500: 1, in particular from 5: 1 to 200: 1.

A discharge is preferably taken from the reactor and subjected to a gas / liquid separation, a hydrogen-containing gas phase and a product-containing liquid phase being obtained. For gas / liquid separation, it is possible to use the devices customary for this purpose and known to the person skilled in the art, such as the usual separating containers (separators). The temperature in the gas / liquid separation is preferably equal to or lower than the temperature in the reactor. The pressure in the gas / liquid separation is preferably equal to or less than the pressure in the reactor. The gas / liquid separation preferably takes place essentially at the same pressure as in the reactor. This is particularly the case when the liquid phase and optionally the gas phase are conducted in a circulation stream. The pressure difference between the reactor and gas / liquid separation is preferably at most 10 bar, in particular at most 5 bar. It is also possible to design the gas / liquid separation in two stages. The absolute pressure in the second gas / liquid separation is then preferably in a range of 0.1 to 2 bar.

The product-containing liquid phase obtained in the gas / liquid separation is generally at least partially discharged. From this discharge, the product of the hydrogenation can be isolated, if appropriate after a further work-up. In a preferred embodiment, the product-containing liquid phase is at least partially recycled as a liquid circulation stream in the hydrogenation.

The hydrogen-containing gas phase obtained in the phase separation can be at least partially discharged as exhaust gas. Furthermore, the hydrogen-containing gas phase obtained in the phase separation can be at least partially attributed to the hydrogenation. The amount of hydrogen discharged via the gas phase is preferably 0 to 500 mol% of the amount of hydrogen which is consumed in molar amounts of hydrogen in the hydrogenation. For example, with a consumption of one mol of hydrogen, 5 mol of hydrogen can be discharged as exhaust gas. Particularly preferably, the amount of hydrogen discharged via the gas phase is at most 100 mol%, in particular at most 50 mol%, of the amount of hydrogen which is consumed by molar amount of hydrogen in the hydrogenation. By means of this discharge stream can control the CO content in the gas phase in the reactor. In a specific embodiment, the hydrogen-containing gas phase obtained in the phase separation is not recycled. However, if it should be desired, this is preferably up to 1000% of the amount based on the amount of gas required chemically for the reaction, more preferably up to 200%. The gas loading, expressed by the gas empty tube velocity at the reactor outlet, is generally at most 200 m / h, preferably at most 100 m / h, particularly preferably at most 70 m / h, in particular at most 50 m / h. The gas loading consists essentially of hydrogen, preferably at least 60% by volume. The gas velocity at the reactor inlet is extremely variable, since hydrogen can also be added to intermediate feeds. If all the hydrogen is added at the reactor inlet, the gas velocity is generally higher than at the reactor outlet. The absolute pressure in the hydrogenation is preferably in a range from 1 to 330 bar, particularly preferably in a range from 5 to 100 bar, in particular in a range from 10 to 60 bar. The temperature in the hydrogenation is preferably in a range of 40 to 300 ° C, particularly preferably from 70 to 220 ° C, in particular from 80 to 200 ° C.

In a specific embodiment, the fixed catalyst bed has a temperature gradient during the hydrogenation. Preferably, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed is maintained at a maximum of 50 K. Preferably, the temperature difference between the coldest point of the fixed catalyst bed and the warmest point of the fixed catalyst bed is maintained in a range of 0.5 to 40K, preferably in a range of 1 to 30K.

The process according to the invention offers a technically easily implementable possibility of discharging any spent catalyst without having to open the reactor. After switching off the feeds and any purging to remove residual product from the reactor, the circulation stream is turned off and rinsed with a suitable flushing medium, the reactor in the reverse flow direction of the reaction to be catalyzed, wherein the spent as catalyst is flushed out of the packing. Thus, for example, in the case of a reaction in the upflow mode, the rinsing takes place in trickle mode. This can be z. B. with water or other suitable solvents such as alcohols, esters, ketones, hydrocarbons or mixtures thereof. Thus, it is advantageous to rinse the reactor with the rinsing liquid and to bring out the flushed catalyst from the reactor into a suitable collecting vessel. This can be done at elevated temperatures, but preferably below 50 ° C. The amount of rinsing liquid depends on the nature of the packing and the catalyst, generally based on the reactor volume, the 5- to 500-fold rinse volumes are used. In this way can easily remove over 90% of the catalyst, which can then be replaced by fresh again.

The following examples serve to illustrate the invention without limiting it in any way.

EXAMPLES

Example 1 Hydrogenation of 4-isobutylacetophenone to give 1- (4'-isobutylphenyl) -ethanol A wire cloth in a linen weave of an aluminum-containing ferritic chromium steel alloyed with yttrium and hafnium with the material No. 1 .4767 with a mesh width of 0.18 mm and a wire diameter of 0.1 12 mm was partially corrugated by means of a gear wheel. This corrugated fabric was folded with a smooth fabric strip and wound up. This gave a monolithic shaped body which was fixed by spot welding. The diameter of the winding was 2.5 cm, the length 20 cm. The monolith thus obtained was fitted into the apparatus used for the hydrogenations, described below, so that edge-side passage of the reaction mixture between fixed catalyst bed and reactor inner wall was practically impossible.

The hydrogenation apparatus consisted of a storage vessel, a feed pump, a compressed gas supply, a jacketed tubular reactor which was heated in the outer jacket with oil, a gas-liquid separator and a circulation pump. In the separator, the reactor discharge into reactor exhaust gas and liquid discharge was separated, the gas via a pressure-holding valve and the liquid discharged in a controlled manner (that is, depending on the liquid level in the separator). The gas and Eduktzulaufstelle was between circulation pump and reactor inlet. The system was filled with water until a circulating flow (liquid circulation) was possible in the apparatus (about 20 liters / h, sumping method). Subsequently, about 5 g of molybdenum-doped Raney nickel (BK1 1 1 W, Evonik) slurried in 100 ml of water introduced into the separator and pumped. After 3 h, sampling indicated that there was no Raney nickel in the recycle stream. Subsequently, about 3 standard liters / h of hydrogen were further added under a circulation flow of 20 liters / h, the system brought to 40 bar pressure and heated to 60 ° C. A sample of the reactor effluent again indicated that no Raney nickel was being discharged. Subsequently, a feed of 4-isobutylacetophenone of 20 g / h was set. The amount of exhaust gas was about 0.4 standard liters / h. After an operating time of 48 hours, an analysis of the discharge gave a conversion of 99.2% of 4-isobutylacetophenone with a selectivity of greater than 99.6%. As a minor component, 4-isobutylethylbenzene was obtained. The hydrogenation was run for 10 days without any adverse effect on catalyst activity and selectivity. No Raney nickel was found in the recycle stream during the entire operating time.

Example 2: Hydrogenation of 4-isobutylacetophenone to give 1- (4'-isobutylphenyl) ethanol

Analogously to Example 1, 5 g of a pulverized Cu catalyst (X 540 T, BASF Corporation, Florham Park, NJ 07932, USA) were used instead of a Mo doped Raney nickel. Siebfraktion between 10 and 50 μηη, activated with H at 180 ° C in water) slurried. As in Example 1 was hydrogenated, but at 120 ° C. The conversion was 99.5% after 48 h, with a selectivity of 99.7%. As in Example 1, no catalyst was found in the recycle stream during the entire hydrogenation time. After 10 days of operation, the hydrogenation was turned off, the system cooled and relaxed. Thereafter, about 10 liters of water were flushed over the top of the reactor and collected at the bottom of the reactor. In the rinse water found about 95% of the catalyst again. With this method, deactivated catalyst can be easily removed and then introduce fresh catalyst into the reactor.

Example: 3 hydrogenation of 1,4-butynediol

From a commercially available nickel foam with a pore size of 580 μηη, a thickness of 1, 7 mm, a porosity of 90%, a geometric surface of 6.9 m ² / L and a surface density of 1 150 g / cm ² were Slices with one

Cut diameter of 2.5 cm by means of a water jet cutter and 1 18 of which are built into a reactor as defined in Example 1 stacked at a height of about 20 cm. Care was taken that edge-side passage of the reaction mixture between the catalyst fixed bed and the reactor inner wall was practically impossible and no gaps between the panes occurred. As in Example 1, after filling the reactor system with water, about 15 g of molybdenum doped Raney nickel were slurried into the reactor. Subsequently, the reactor was brought to 50 bar by means of hydrogen and heated to 145 ° C and then fed 15 Normliter hydrogen / h. After 30 minutes with a circulatory flow of 20 kg / h, no Raney nickel was found in the recycle stream. Then 45 g / h of an aqueous 1, 4-butynediol starting material was metered into the hydrogenation, which was prepared according to Example 1 of EP 2121549 A1. The feed had a pH of 7.5 and in addition to 1, 4-butynediol and water contained about 1 wt .-% propynol, 1, 2 wt .-% formaldehyde and a number of other by-products with proportions of significantly less 1% by weight. After 48 h reaction time, the discharge had no

Raney nickel, the conversion was complete and consisted by GC analysis (surface anhydrous) from about 94% 1, 4-butanediol, 0.15% 2-methylbutanediol, 2.2% propanol, 1, 9% butanol, 1, 5% methanol and other components, but no more than 500 ppm in volume. The CO content at the reactor inlet was 2 ppm, at the discharge at 25 ppm.

Example 4: Hydrogenation of n-butyraldehyde Analogously to Example 3 was hydrogenated at 40 bar and 130 ° C n-butyraldehyde to n-butanol. At a feed rate of 50 g / h and a hydrogen flow of 20 standard liters / h, no catalyst was found in the discharge after 48 hours. The following products were found (GC area%): 99.6% n-butanol, 0.05% butyl acetate, 0.01% dibutyl ether, 0.05% isobutanol and 0.07% ethylhexanediol. The CO content before entering the reactor was 0.5 ppm and after leaving the reactor it was 10 ppm.

Example 5 Hydrogenation of 4-hydroxypivalaldehyde Analogously to Example 3, 4-hydroxypivalaldehyde (HPA) was hydrogenated to neopentyl glycol (NPG). In the feed were (wt .-%) about 10% HPA, about 25% water, 61% NPG, and together about 3.5% of the following components: iso-butyraldehyde, formaldehyde, trimethylamine and its formate, hydroxypivalic -NPG esters as well as other, quantitatively insignificant components. The pH was 8. The hydrogenation was carried out at 135 ° C, a reactant feed of 150 g / h and a supplied amount of hydrogen of about 5 standard liters / h. After 48 h, no catalyst was found in the effluent and the HPA conversion was 96%. According to GC analysis, virtually all sales to NPG took place. The CO content before entering the reactor was 0.2 ppm and after leaving the reactor it was 15 ppm

Claims

claims

1 . A method of providing a catalytically active packed bed containing monolithic shaped bodies as a catalyst support or consisting of monolithic shaped bodies loaded with a catalyst containing at least one metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag , Au, Pd, Mn, Re, Ru, Rh and Ir, in which one introduces into a reactor a fixed bed containing monolithic moldings or consists of monolithic moldings, the fixed bed with a suspension of the at least one catalyst or the precursor thereof in one liquid medium is brought into contact and the suspension of the at least one catalyst or the precursor thereof is at least partially conducted in a liquid circulation stream, wherein the catalyst or the precursor contains at least one metal which is selected from Ni, Fe, Co, Cu, Cr , Pt, Ag, Au, Pd, Mn, Re, Ru, Rh, and Ir, yielding a fixed bed loaded with the catalyst or precursor d, if appropriate, subjecting the loaded fixed bed obtained in step b) to activation, optionally subjecting the loaded fixed bed obtained in step b) or the activated fixed bed obtained in step c) to a treatment with a washing medium selected from water, C 1 -C 4 Alkanols and mixtures thereof, optionally contacting the fixed bed obtained after activation in step c) or after the treatment in step d) with a dopant having at least one element other than the metal used to load the fixed bed.

The method of claim 1, wherein the monolithic shaped bodies, based on the entire shaped body, a smallest dimension in a direction of at least 0.3 cm, preferably at least 1 cm, more preferably at least 2 cm, in particular at least 3 cm, especially at least 5 cm, exhibit.

A process according to any one of the preceding claims, wherein in step b) at least 90% by weight of the at least one catalyst or precursor thereof, based on the total weight of the catalyst or precursor thereof, has a particle size in the range 0.1 to 200 μηη, preferably in the range of 1 to 100 μηη, in particular in the range of 5 to 50 μηη having.

4. The method according to any one of the preceding claims, wherein the bulk density of the catalyst used in step b) or the precursor thereof at least 0.8 g / mL, preferably at least 1 g / mL, in particular at least 1, 5 g / mL ,

5. The method according to any one of the preceding claims, wherein the monolithic moldings are in the form of a foam.

6. The method according to any one of claims 1 to 5, wherein in step b) brings the fixed bed with an active catalyst in contact and wherein the active catalyst is selected from catalysts which are subjected to the activation of a treatment with a reducing gas, preferably hydrogen were and Raney metal catalysts.

7. The method according to any one of claims 1 to 5, wherein in step b) brings the fixed bed with a catalyst precursor in contact containing at least one metal in oxidic form and the obtained in step b) loaded fixed bed in step c) for activating a Treatment with a reducing gas, preferably hydrogen.

8. The method according to any one of claims 1 to 5, wherein in step b) brings the fixed bed with an alloy containing at least one first metal selected from Ni, Fe, Co, Cu, Cr, Pt, Ag , Au and Pd, and containing at least one second component selected from Al, Zn and Si, and subjecting the loaded fixed bed obtained in step b) in step c) to activation with an aqueous base.

9. The method according to any one of the preceding claims, wherein the fixed bed at any section in the normal plane to the flow direction through the fixed bed, based on the total area of the section, at most 5%, preferably at most 1%, in particular at most 0.1% free area, which is not part of the moldings.

10. The method according to any one of the preceding claims, wherein the fixed bed contains moldings having pores and / or channels and wherein at any cut in the normal plane to the flow direction through the fixed bed at least 90% of the pores and channels, more preferably at least 98% of the Po - ren and channels, have an area of at most 3 mm ² .

Method according to one of the preceding claims, wherein the catalytically active fixed bed after step b) or after step c) or after step d) or after step e) in a further step f) is reacted with a hydrogenatable organic compound and hydrogen in at least one reactor and during step f) the CO content in the gas phase within the reactor is in a range of 0.1 to 10,000 ppm by volume.

A process as claimed in claim 11, wherein the hydrogenatable organic compounds in step f) are selected from 1,4-butynediol, 1,4-butenediol, 4-hydroxybutyraldehyde, hydroxypivalic acid, hydroxypivalaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, iso-valeraldehyde, 2-ethylhex-2-enal, 2-ethylhexanal, the isomeric nonanals, 1, 5,9-cyclododecatriene, benzene, furan, furfural, phthalic esters, acetophenone and alkyl substituted acetophenones.

Method according to one of claims 1 1 or 12, wherein the reactor in the flow direction of the reaction medium through the catalytically active fixed bed has a gradient with respect to the CO concentration. 14. The method according to any one of claims 1 1 to 13, wherein the catalytically active

Fixed bed during step f) has a temperature gradient.