WO2015018793A1 - Catalyseur contenant de l'iridium et procédé pour une réaction de guerbet en phase gazeuse - Google Patents

Catalyseur contenant de l'iridium et procédé pour une réaction de guerbet en phase gazeuse Download PDF

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Publication number
WO2015018793A1
WO2015018793A1 PCT/EP2014/066727 EP2014066727W WO2015018793A1 WO 2015018793 A1 WO2015018793 A1 WO 2015018793A1 EP 2014066727 W EP2014066727 W EP 2014066727W WO 2015018793 A1 WO2015018793 A1 WO 2015018793A1
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Prior art keywords
catalyst
range
weight
condensation
alcohols
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PCT/EP2014/066727
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German (de)
English (en)
Inventor
Andreas Kuschel
Stephan Schunk
Andreas Lanver
Stephan Deuerlein
Gauthier Luc Maurice AVERLANT
Michal Ludwik LEJKOWSKI
Verena MORMUL
Guido WASSERSCHAFF
Regine Helga BEBENSEE
Andreas Strasser
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Basf Se
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Priority to EP14749771.3A priority Critical patent/EP3030346A1/fr
Publication of WO2015018793A1 publication Critical patent/WO2015018793A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

Definitions

  • the invention relates to a process for the condensation of alcohols having one to five carbon atoms.
  • ethanol is used as starting material.
  • the process of this invention is for the synthesis of branched and unbranched alcohols having from three to ten carbon atoms, preferably the process is used to synthesize butanol (i.e., a C4 alcohol).
  • the inventive method is characterized in that it is environmentally friendly and energy-saving.
  • the technical requirements associated with carrying out the method according to the invention are lower than is the case for carrying out corresponding methods from the prior art.
  • this method is also suitable for decentralized plant operation. Decentralized plant operation is of particular interest when only relatively small quantities of products are required for local markets.
  • the invention has a high economic potential for all countries looking for alternatives to petroleum-based fuels. Even today, the addition of ethanol has a high economic importance in the production of gasoline fuels, but there is also the fear that this leads to increased wear on parts of the engine or the lines.
  • butanol is also suitable as an additive to diesel fuels, which is not the case with ethanol.
  • gas phase Guerbet reaction described here could extend the potential uses of ethanol (converted to butanol) as a fuel and thus further contribute to the success of the biorefinery idea.
  • the reaction mechanism underlying the Guerbet reaction is shown in Scheme 1. According to this mechanism, the reaction is a combination of the following three reactions: 1. Formation of aldehyde from starting alcohol by dehydration of the alcohol, 2. Aldol reaction (aldol condensation) of aldehyde to, -unsaturated aldehyde, 3. Hydrogenation of the, -unsaturated aldehyde to the product alcohol.
  • Scheme 1 :
  • the dimerization of low molecular weight alcohols is the subject of numerous publications, which is certainly due to the great economic importance of the products.
  • the following is a brief overview of the state of the art in the field of dimerization reactions of alcohol molecules.
  • the implementation of the method is to differentiate between the gas phase process and the liquid phase process, in the discussion given here first the state of the art for gas phase process and then the state of the art for liquid phase process is reproduced.
  • catalysts based on hydrotalcite-containing carrier oxides or hydrotalcite-containing precursors and their use in catalytic processes for the dimerization of alcohols has been the subject of several publications that have appeared in recent years. The following section gives a brief description of these publications. For example, C. Carlini et al. on the implementation of Guerbet condensation using bifunctional catalysts based on magnesium and aluminum-containing mixed oxides (see C. Carlini et al., Journal of Molecular Catalysis A: Chemical 232 (2005) 13-20). As active metals, the catalysts may comprise the elements Pd, Rh, Ni and Cu. Furthermore, it is shown that the magnesium- and aluminum-containing
  • the catalysts may comprise the metals from the group Pd, Ag, Mn, Fe, Cu, Sm, Yb as active metals.
  • Du Pont de Nemours discloses a process for the catalytic conversion of ethanol in the presence of hydrogen.
  • the inventors are R. Ozer, K. Kourtakis and E. Grayson, and the PCT application has 28.01 .2009 as filing date.
  • the process is based on catalysts which have thermally decomposed hydrotalcite, the catalyst synthesis being characterized in that it is carried out in the presence of EDTA (ethylenediaminetetraacetic acid) as a complexing agent.
  • EDTA ethylenediaminetetraacetic acid
  • the preparation of catalysts with cobalt as the active metal is disclosed.
  • the catalyst may comprise active metals from a large group of divalent and trivalent noble metals which may be present as a mixture or individually on the carrier oxide.
  • the Exxon Research and Engineering Company discloses a catalyst for the synthesis of isobutanol.
  • the catalyst contains precious metal on a support and the support comprises a first phase of crystallites of a mixed oxide containing zirconium, manganese, zinc and a second phase of zirconium doped hetaryolite particles containing manganese and zinc.
  • the carrier may also have a third phase of manganese, zinc and zirconium.
  • Characteristic of the catalyst is that the crystals of the first phase range in size from 40 ⁇ to 100 ⁇ , the crystallites of the second phase range in size from 200 ⁇ to greater than 2000 ⁇ , and the crystallites of the third phase are one size ranging from 1000 ⁇ to greater than 4000 ⁇ .
  • An object of the invention is to provide an improved process for the condensation of alcohols in the gas phase.
  • the process should also be able to be used in particular for the production of butanol from ethanol.
  • the method should also be suitable for the preparation of branched and unbranched C3 to C10 alcohols.
  • a suitable catalyst for the process according to the invention should be provided. I. Catalyst according to the invention
  • a catalyst for the condensation of alcohols could be found, the thermally partially or completely decomposed Carrier material in contact with iridium and / or ruthenium as promoter, this catalyst being characterized in that:
  • the partially or completely decomposed carrier material comprises hydrotalcite-like compounds, preferably hydrotalcite, and / or precursor material of hydrotalcite-like compounds, preferably hydrotalcite precursor material, as starting material,
  • the average particle size of the promoter particles ⁇ 100 nm, preferably ⁇
  • the thermally decomposed carrier material has an Mg / Al ratio in the range from 90/10 to 40/60, preferably from 90/10 to 70/30, wherein the ratio is based on the weight of the respective oxides.
  • the catalyst according to the invention comprises the promoter element Ir.
  • the promoter particles preferably iridium-containing, are embedded in the matrix of the thermally partially or completely decomposed carrier material and are highly dispersed, which has a beneficial effect on the properties of the material and thus constitutes an essential aspect of the invention.
  • the catalysts according to the invention have a high sintering resistance during the performance of the process according to the invention, which shows to the effect that the promoter particles hardly show any sintering effects after several process cycles on the basis of TEM investigations.
  • the indication in relation to the particle size is to be understood such that at least 90% of the catalyst particles are within the claimed target range, preferably even 95% of the catalyst particles.
  • the percentage refers to the number of promoter particles.
  • the particle size distribution of the promoter particles is in a narrow range, which can be seen from the TEM images.
  • a particularly suitable catalyst could be found, which has completely exceptional performance characteristics with respect to the inventive method. The catalysts and processes known from the prior art are thus superior to the catalyst according to the invention.
  • the content of iridium-containing and / or ruthenium-containing promoter is very low and still very good performance in relation to the inventive method for the condensation of alcohols with the catalyst according to the invention can be achieved.
  • the catalyst according to the invention may have at least one further promoter element.
  • the further promoter elements comprise elements from the group Pt, Rh, Ru, Pd, Co, Ni, Pd, Cu, Ag and / or Au, wherein it is preferred that the content of further promoter elements or on further promoter element in the range of 0.01 - 4 wt .-%, preferably 0.02 - 3 wt .-% is.
  • the further promoter element, or the other promoter elements can lead to higher costs, since it is usually the elements of the group of noble metals in the promoter elements. It should be taken into account that a regeneration of the catalyst according to the invention is possible after carrying out the catalytic process.
  • a regeneration of the catalyst according to the invention is possible after carrying out the catalytic process.
  • the catalyst according to the invention can thus be carried out a catalytic process for the condensation of alcohols, in which the catalyst is subjected to at least one or more times a regeneration process. Following regeneration, the catalyst has nearly the same performance characteristics as a catalyst that has not yet been used (i.e., a so-called fresh catalyst).
  • the advantageous properties with regard to the regenerability of the catalyst are also indications which indicate a good long-term stability of the catalyst.
  • the catalyst according to the invention is also characterized in particular by low contents of alkali components.
  • the catalyst preferably has a content of alkali components of ⁇ 1% by weight and preferably ⁇ 0.5% by weight.
  • the content of alkali components in the catalyst is essentially influenced by the production process of the catalyst according to the invention. Yet another performance increase of the catalyst in connection with the method according to the invention could thus be achieved.
  • a sodium-free or alkali-free precipitating agent is used to prepare the catalyst. If a sodium-containing or alkali-containing precipitating agent is used to precipitate the hydrotalcite precursor material, the result is a precipitation product which contains a certain amount of alkali components, which is extremely undesirable in the context of the present invention.
  • the preparation of the catalyst based on a sodium-containing or alkali-containing precipitating agent should not be completely ruled out if the precipitated product is subjected to a thorough washing and it is possible to substantially reduce the alkali component from the precipitated product.
  • the catalyst has a certain minimum content of chloride, since this has an advantageous effect on the performance characteristics of the catalyst when carrying out condensation reactions.
  • divalent metals for example, metals from the group of Mg, Zn, Cu, Ni, Co, Mn, Ca and / or Fe and as trivalent metals, for example, metals from the group AI, Fe, Co, Mn, La, Ce and / or Cr be used.
  • the hydrotalcite-like compound is hydrotalcite.
  • the hydrotalcites used for the process according to the invention comprise magnesium as bivalent metal and aluminum as trivalent metal.
  • the metals of the hydrotalcites used consist predominantly of magnesium and aluminum.
  • hydrotalcite-like compounds and the oxidic aggregate have a very intimate mixing.
  • Such mixing can be carried out, for example, by physical mixing of hydrotalcite-like and aluminum hydroxide-containing powders.
  • suitable technical equipment such as mixers.
  • Such mixing methods are known to the person skilled in the art.
  • Another possibility is to mix the hydrotalcite-like and the aluminum hydroxide-containing powders in suitable dispersing agents.
  • suitable dispersing agents for example, water, alcohols, such as methanol, ethanol, propanol, butanol, ethylene glycol and / or butanediol, and ketones, such as acetone or methyl ethyl ketone, can be used as the dispersing agent.
  • dispersants are present as mixtures and contain surface-active agents such as surfactants.
  • surfactants include polyethylene glycols, mersolates, carboxylates, long chain ammonium compounds such as CTAB.
  • Hydrotalcites or hydrotalcite-like compounds of particular purity are preferably used for the process according to the invention. The process for the preparation of these hydrotalcite-like compounds which are used with particular preference in the process according to the invention is described by JP van Berge et al. disclosed in DE 195 03 522 A1.
  • the hydrotalcites or hydrotalcite-like compounds are formed by the hydrolysis of metal alcoholates with water and subsequent drying of the precipitated hydrolysis products.
  • the metal alkoxides are formed by reacting mono-, di- and / or trivalent alcohols with one or more divalent metals and / or one or more trivalent metals.
  • the water used for the hydrolysis preferably contains water-soluble anions selected from the group consisting of hydroxide anions, organic anions, in particular alcoholates, alkyl ether sulfates, aryl ether sulfates and / or glycol ether sulfates and / or inorganic anions, in particular carbonate, bicarbonate, chloride, nitrate, sulfate and / or polyoxometalanions.
  • the counterion used is preferably ammonium.
  • Suitable starting materials are commercially available hydrotalcites, which are obtainable, for example, under the name Pural MG from Sasol.
  • the hydrotalcites or the hydrotalcite precursor materials can also be prepared by themselves - for example via the precipitation products of metal salts which are precipitated in the appropriate stoichiometric proportions and converted by heat treatment into the desired structures / desired structure.
  • the starting materials are a mixture of magnesium and aluminum, present either as an oxide mixture or as a mixture of oxides and elemental metals.
  • hydrotalcite and / or hydrotalcite precursor material as a starting material (the so-called carrier precursor) of a finely dispersed aluminum oxide and aluminum hydroxide mixture, such as the commercially available material disperal (Sasol), and to synthesize from a suitable magnesium source.
  • the magnesium source for example, any water-soluble salt may be used, with magnesium nitrates being particularly suitable.
  • the magnesium cations or atoms can be partially replaced by other cations or atoms, while preserving the catalytic properties of the material.
  • the calcium and aluminum oxides should be present in a ratio of 90/10 to 40/60, preferably from 90/10 to 70/30.
  • any water-soluble salt can be used as the magnesium-containing compound, with magnesium nitrates being particularly suitable.
  • the present specification refers to the weight ratio of the oxides.
  • the appropriate starting material ie carrier precursor
  • an aqueous solution of the mixture of magnesium and aluminum-containing salts is prepared so that magnesium and aluminum cations are present in the ratio described below. All water-soluble salts are suitable for the preparation of the salt mixture, and the nitrates have proven to be particularly suitable.
  • the starting material or the carrier precursor
  • a finely dispersed aluminum oxide and aluminum hydroxide mixture for example the commercially available material Disperal (Sasol)
  • a suitable magnesium source for example, any water-soluble salt may be used, with magnesium nitrates being particularly suitable.
  • suitable starting materials for the deposition or the preservation of the noble metal-containing promoters from the group Pt, Rh, Ru, Pd, Co, Ni, Pd, Cu, Ag, Au and Ir can be used for the synthesis of the following compounds: halides or other inorganic salts such as sulfates and nitrates, as well as acetates, acetylacetonates and oxalates, but also olefin complexes, complexes with pyridine or other amine ligands, carbonyl complexes and finally also complexes with phosphanes, phosphides and phosphates.
  • Ru-containing compounds Ru (NO) (NO 3 ) 3 , Ru (NO 3 ) 3 , RuCl 3 , RuCl 3 -xH 2 O,
  • Ru 3 (CO) i2 Ru (OAc) 3 , Ru (acac) 3 , Ru (CO) 2 (OAc) 2 , RuCl 2 (cod), [RuCl 2 (C 6 H 6 )] 2, Ru (Cp) CI (PPh 3 ) 2 , [Cp * RuCl] 4 , RuHCl (PPh 3 ) 3 , RuH 2 (CO) (PPh 3 ) 3 , RuCl 2 (PPh 3 ) 3 and RuH 2 (PPh 3 ) 4 .
  • Examples of iridium-containing compounds IrCl 3 , IrCl 3 -xH 2 O, IrCl 4 -xH 2 O, IrO 2 , Ir (OAc) 3 , Ir (acac) 3 , Ir (cod) (acac), Ir (CO ) (PPh 3 ) 3 , [Cp * IrCl 2 ] 2 , [IrcI (cod)] 2, and Ir 4 (CO) i 2 .
  • RhCl 3 Rh (OAc) 3 , [Rh (OAc) 2 ] 2 , Rh (acac) (CO) 2 , [Rh (OAc) (cod)] 2 , [RhCl (cod)] 2 , RhCl (PPh 3 ) 3 , [Cp * RhCl 2 ] 2 , RhH (CO) (PPh 3 ) 3, and Rh 4 (CO) i 2 .
  • nickel-containing compounds NiCl 2 , NiBr 2 , Ni (NO 3 ) 2 , NiSO 4 , Ni (cod) 2 , Ni (acac) 2 , Ni (OAc) 2 -4H 2 O, NiCl 2 (Ph 2 PCH 2 CH 2 PPh 2 ) and NiCl 2 (PPh 3 ) 3 .
  • Examples of palladium-containing compounds Pd (0), PdCl 2, PdBr 2, PdCl 2 (cod), PdCl 2 (PPh 3) 2, Pd (PPh 3) 4, Pd 2 (dba) 3, K 2 PdCl 4, PdCl 2 (CH 3 CN) 2 , Pd (dba) 2 , Pd (NO 3 ) 2 , Pd (OAc) 2 , PdSO 4 and Pd (acac) 2 .
  • Examples of platinum-containing compounds PtBr 2 , PtCl 4 , Pt (acac) 2 ,
  • PtH (OH) 6 PtHfCle, PtCl 2 (PPh 3 ) 2 , PtCl 2 (cod), PtCl 2 (CH 3 CN) 2 , PtCl 2 (PhCN) 2 , Pt (PPh 3 ) 4 , K 2 PtCl 4 , Na 2 PtCl 6 and HPtCl 6.
  • the invention also relates to a catalyst for the condensation of alcohols, the thermally partially or completely decomposed carrier material in contact with iridium and / or ruthenium comprises as promoter, wherein the catalyst according to the invention can be produced by subsequent steps by
  • hydrotalcite-like compound-containing carrier material preferably hydrotalcite-containing carrier material, and / or precursor material of a hydrotalcite-like compound, preferably hydrotalcite precursor material
  • promoter source b) an intimate mixture of hydrotalcite-like compound-containing carrier material, preferably hydrotalcite-containing carrier material, and / or precursor material of a hydrotalcite-like compound, preferably hydrotalcite precursor material, and the promoter source is prepared
  • the intimate mixture of hydrotalcite-containing compound-containing carrier material, preferably hydrotalcite-containing carrier material, and / or precursor material of a hydrotalcite-like compound, preferably hydrotalcite precursor material, and the promoter source is thermally treated, wherein the thermal treatment a calcination process at a temperature in the range of 200 - 1000 ° C. , preferably 200-900 ° C and especially preferably 200-850 ° C.
  • the catalyst according to the invention is based on a thermally partially or completely decomposed carrier material, wherein the thermal decomposition according to step c) of the preparation is based on a calcining treatment.
  • the thermal decomposition according to step c) of the preparation is based on a calcining treatment.
  • the thermal decomposition according to step c) of the preparation is based on a calcining treatment.
  • the manufacturing process may comprise a multi-stage calcination process with a treatment at a first temperature level and a treatment at a second temperature level.
  • the catalyst preparation process may also include a molding step.
  • the shaping process of the catalyst is adapted in each case to the intended use of the catalyst and may deviate from the procedure described here.
  • the shape of the catalyst generally depends on the apparatus or on the system in which the catalyst is used in the catalytic process. In connection with the catalyst according to the invention, it is not necessary to apply this to a shaped body or to deposit it on a shaped body.
  • One aspect of the catalyst according to the invention is also that it can be processed into the desired shaped body.
  • the shaping step is, for example, tableting, extrusion, spray-drying, granulation or similar processes known to those skilled in the art.
  • an extrusion or tabletting process is used to prepare the catalyst.
  • the molded articles obtained in this way can be obtained in different sizes and shapes.
  • tablets have dimensions of 3 mm in length and 6 mm in diameter, 5 mm in length and 5 mm in diameter or 5 mm in length and 8 mm in diameter. In this case, it is important that the tablet size is adapted to the specific dimensions of the reactor used in the process.
  • the shaping must always be carried out before the calcination step or the high-temperature calcination step, in the case of multi-stage calcination.
  • the shaping step may be carried out prior to impregnation of the starting material with the promoter.
  • the catalyst can be prepared in the form of granules.
  • the Kompaktiansstress was partly carried out several times in succession to increase the efficiency. Studies were carried out in which the starting materials were compacted one to ten times. Preferably, methods in which the compacting is repeated three to five times. These compaction operations were carried out with a roller compactor on powdery starting materials. Here, the starting materials and small amounts of water can be supplied to convert the powder into a kneadable paste.
  • the material was exposed to a contact pressure in a range from 150 to 250 bar, preferably from 200 to 250 bar, particularly preferably from 225 to 250 bar.
  • the mass to be compacted was then further processed, with the roll revolution number ranging from 1 to 10, preferably from 3 to 10, and more preferably from 5 to 10.
  • the catalyst particles may have a size in the range of 0.4 to 5 mm, and preferably in the range of 0.5 to 1.5 mm.
  • Prior to calcination such granules may be characterized in that the loss on ignition of the materials in the range 35- 50 wt .-% is preferably 40- 48 wt .-%.
  • the water absorption of the granules before calcining is in the range of 0.25-0.55 ml / g, preferably 0.3.5-0.47 ml / g.
  • the calcining process takes place in such a way that it comprises a multi-stage temperature control of the catalyst at at least two different temperature stages. It is advantageous to use preferred heating rates when heating the samples in order to avoid local exothermic burn-off processes and associated sintering processes within the catalyst. In addition, it may be preferable to subject the samples to predrying. to start the calcination process with samples whose water content is not higher than 50% by weight.
  • the sample soaked in promoter species is calcined in a two-step process, wherein the thermal treatment of the sample in the first calcining step ranges from 200 ° C to 300 ° C, preferably from 250 ° C to 300 ° C , and the thermal treatment of the sample in the second calcining step is in a range of 350 ° C to 1000 ° C, preferably 400 ° C to 900 ° C, and more preferably 400 ° C to 850 ° C.
  • the impregnated sample at a controlled heating rate to the target temperatures, with a preferred heating rate providing a temperature increase of 0.5-3.0 K / min, preferably 0.5-1.5 K / min .
  • the calcination is carried out under air atmosphere, wherein the air is further preferably passed through the sample at a flow rate of 3-10 L / min, more preferably from 5 to 8 l / min. The amount of air directed through the oven depends on the respective furnace volume.
  • permanent gases such Methane, propane and carbon monoxide
  • the catalyst according to the invention has a high specific surface which can be determined by means of nitrogen sorption.
  • a high specific surface which can be determined by means of nitrogen sorption.
  • particular preference is given to those catalysts whose BET surface area is greater than 60 m 2 / g, preferably greater than 70 m 2 / g, particularly preferably greater than 80 m 2 / g.
  • the data relating to the BET surface areas refer to the catalysts in the fresh state, ie before use in the process according to the invention.
  • the invention also relates to a process for the condensation of alcohols by contacting an alcohol-containing educt gas stream, alcohol selected from the group C1 to C5 alcohol, with a catalyst in one of the embodiments shown here.
  • the process temperature is carried out in the range from 200 to 450 ° C, preferably from 250 ° C to 400 ° C,
  • the process pressure is in the range from 0.05 to 60 bar, more preferably 0.1 to 40 bar, especially preferably 0.5 to 10 bar, even more preferably in the range from 1 to 5 bar,
  • the alcohol content of the educt gas stream in the range from 0.1 to 90% by volume, preferably in the range from 0.5 to 70% by volume and more preferably from 0.5 to 50% by volume lies,
  • the educt gas stream has a GHSV in the range from 500 to 5000 hr.sup.- 1 , preferably in the range from 1000 to 4000 hr.sup.- 1 , in particular preferably in the range from 1000 to 2500 hr.sup.- 1 .
  • the alcohol in the educt stream is ethanol, which is converted to butanol.
  • the alcohol preferably ethanol
  • the alcohol is fed to the catalyst in a carrier fluid stream, the process being conducted in a continuous process.
  • the educt stream consists of alcohol and carrier fluid stream.
  • the carrier fluid stream comprises inert gas and preferably inert gas together with reactive gas, wherein the reactive gas is preferably hydrogen.
  • the inert gas is preferably nitrogen, which undergoes no reaction itself under the process conditions of the process according to the invention. Suitable inert gases are all gases which do not undergo any reaction under the process conditions themselves, with the costs of the inert gases playing a role in the industrial sector, which probably makes the use of argon rather uneconomical.
  • the process is characterized in that a preferred ratio of alcohol to reactive gas is used, since in this way conversions, yields and selectivities can be further improved.
  • a ratio of alcohol to reactive gas in the range from 40: 2.5 to 20: 10, preferably from 20: 2.5 to 20: 20.
  • the ratio of alcohol to Reactive gas is in a range of 100: 1 to 1:10.
  • a particularly preferred method according to the present invention is given when the process is carried out with ethanol as the alcohol and hydrogen as the reactive gas.
  • the catalyst according to the invention and the process according to the invention have the advantage that they are suitable for decentralized use in smaller plants, since the process parameters with regard to pressure and temperature are within a range which does not impose such high technical requirements in the form of small-scale industrial plants put the operator, as is the case with high-pressure processes in large-scale plants.
  • particularly preferred low-pressure conditions ie particularly preferably 0.5-10 bar and very particularly preferably 1-5 bar
  • the method according to the invention are of great importance, since in this operating parameter space essential fields of application can be developed in which such a process Procedure could not be used yet.
  • the high efficiency of the process according to the invention in relation to the high conversion, the good yields and selectivities with respect to the target compound, preferably butanol, contribute in particular to the fact that an economical process could be developed that was still in the state of the art in this efficiency was not known.
  • Products desired in the reaction of ethanol are those products which can be readily converted to 1 -BuOH, such as e.g. B. 1-butanal and crotonaldehyde.
  • those products that can be converted by post-treatment into value products such as acetaldehyde.
  • unwanted products are gases such as CO, propane and methane, which can not be further converted under the present reaction conditions.
  • high-boiling compounds without functional groups are undesirable, which can be formed by the uncontrolled further reaction of Dimermaschines interleviations.
  • the inventive method for the condensation of alcohols is characterized in that the method according to the invention is preceded by a step in which the catalyst for pretreatment and / or conditioning is thermally pretreated in a gas stream.
  • the promoter elements can be converted to metallic species in the presence of a reductive atmosphere.
  • the catalyst is treated by a regeneration process which contributes to the catalyst being able to recover at least a large proportion of its original activity.
  • the process is characterized in that the reactant fluid stream used for carrying out the process has a high alcohol content.
  • the alcohol content of the educt fluid stream is> 10% by volume, preferably> 15% by volume, more preferably> 20% by volume.
  • This embodiment is also a special aspect of the present invention. In the case of alcohol mixtures (for example of branched and unbranched alcohols), this information refers to the sum of all present in the reactant stream alcohols. A derar The current technical embodiment offers a great advantage in terms of energy efficiency and the associated economic efficiency.
  • the alcohol content in the educt fluid stream is in the range from 10 to 90% by volume, preferably from 15 to 70% by volume, in particular preferably in the range from 20 to 65% by volume.
  • the process according to the invention preferably relates to the conversion of gaseous reactant streams, which in the context of the present disclosure are also referred to as reactant stream or educt gas stream. It is known to the person skilled in the art that film formation can take place on the catalyst and therefore also partially liquid phases in the process according to the invention can be of importance. Therefore, the term educt fluid stream can also be used.
  • a further preferred embodiment of the process according to the invention relates to the condensation of n-butanol, the process for preparing 2-ethylhexanol (2-EH) being used.
  • the educt gas stream preferably also comprises a reactive gas in addition to butanol, the ratio of butanol to reactive gas being in the range from 40: 2.5 to 20:10, preferably from 20: 2.5 to 20:20.
  • the ratio of alcohol to reactive gas be in the range of 100: 1 to 1:10.
  • Hydrogen is used as the preferred reactive gas.
  • the process relates to the condensation of different alcoholic components.
  • the process for the condensation of alcohols in connection with the catalyst according to the invention is characterized in that
  • the process temperature is carried out in the range from 200 to 450 ° C, preferably from 250 to 400 ° C,
  • the process pressure is in the range of 0.05-60 bar, more preferably 0.1-40 bar, especially preferably 0.5-10 bar, even more preferably in the range of 1-5 bar,
  • the alcohol content the educt (gas) stream in the range of 0.1 to 90 vol .-%, preferably in the range of 0.5 to 70 vol .-% and more preferably from 0.5 to 65 vol .-% and at least two or comprises several alcohols from the group of C1 to C5 alcohols,
  • the educt gas stream has a GHSV in the range from 500 to 5000 hr.sup.- 1 , preferably in the range from 1000 to 4000 hr.sup.- 1 , in particular preferably in the range from 1000 to 2500 hr.sup.- 1 .
  • the alcohol-containing educt gas stream comprises at least two different alcoholic components from the group of the C 1 to C 5 alcohols.
  • the first of the at least two components is methanol (ie component 1)
  • the second of the at least two components (ie component 2) is a component from the group C2 to C5 alcohols.
  • the second of the at least two components is a component from the group C2 to C4 alcohols.
  • the second of the at least two components is a C2 or a C3 alcohol.
  • the molar proportion of methanol is higher than the molar proportion of the at least second component from the group of C2 to C5 alcohols.
  • the molar ratio of methanol to component 2 is in the range of 1: 1 to 50: 1, more preferably in the range of 2: 1 to 40: 1, and most preferably in the range of 2.5: 1 to 20: 1.
  • the educt gas stream comprises a carrier gas.
  • the carrier gas is an inert gas (for example nitrogen) or a reactive gas (for example hydrogen).
  • the reactant gas comprises reactive gas, wherein the reactive gas may be present in the presence of inert gas.
  • the process according to the invention relates to the condensation of methanol and n-propanol to produce isobutanol.
  • the proportion of methanol five to ten times higher than the proportion of n-propanol.
  • the process of the invention relates to the condensation of methanol and ethanol to produce isobutanol.
  • the embodiment relates to a method in which each one ethanol molecule are reacted with two methanol molecules each.
  • the proportion of methanol is five to ten times higher than the proportion of ethanol.
  • the process according to the invention relates to the condensation of methanol and ethanol, which are reacted in a ratio of one methanol molecule each with one ethanol molecule.
  • the process is used to produce propanol.
  • the reactant gas stream is contacted under the reaction conditions specified in the disclosure with the catalyst according to the invention, which is disclosed in more detail in the present specification and claims, and the alcoholic components are reacted ,
  • the ratio of alcohol-containing components to reactive gas it is preferable that it is in the range of 40: 2.5 to 20:10, preferably 20: 2.5 to 20:20.
  • hydrogen is used as the reactive gas.
  • the ratio of alcohol to reactive gas be in the range of 100: 1 to 1:10. It is known to the person skilled in the art that the amount of reactive gas used also depends on the respective process parameters and the information given here should not be limiting. In particular, an optimization of the process parameters can also lead to the fact that the preferred amount of reactive gas used depends on the particular alcohol components and the reaction conditions.
  • the catalyst precursor material is free from ethylenediaminetetraacetic acid or anions of ethylenediaminetetraacetic acid.
  • the intimate mixture of hydrotalcite-containing compound-containing support material, preferably hydrotalcite-containing support material, and / or precursor material of a hydrotalcite-like compound, preferably hydrotalcite precursor material, and the promoter source is prepared, the mixture preferably having no ethylenediaminetetraacetic acid or anions of ethylenediaminetetraacetic acid ,
  • the catalyst samples B1 to B4 are samples prepared from iridium chloride.
  • the catalyst samples B5 and B6 are samples prepared from iridium chloride and platinum nitrate.
  • Sample BR7 was prepared from ruthenium nitrate for the promoter element.
  • Table 1 a summarized overview of the sample samples used for the catalytic test studies and their chemical composition with respect to the promoter elements and the starting materials used for the synthesis or the base of the carrier oxide.
  • the abbreviation PMG 70 means that for the synthesis of the catalyst Pural MG70 from Sasol was used. These are hydrotalc cit.
  • the samples were all calcined at 400 ° C. In principle, the samples at 400 ° C kal
  • Table 1.b summary overview of the sample samples with 1, 0 wt .-% iridium and production based on Pural MG70. Sample samples had been calcined at different temperatures.
  • Table 1.c shows a summary of the sample samples containing 1.0% by weight of iridium and preparation based on Pural MG70, samples Nos. 30-44 during the preparation of a first mechanical treatment and sample No. 52 of a subjected to a second mechanical treatment - and with 1, 3 wt .-% also had a slightly higher iridium content than the untreated samples.
  • Example Sample B14 was prepared to demonstrate the reproducibility of Sample Sample B1 in a second synthetic approach.
  • Table 1 d summary of thirteen sample samples prepared as comparative examples.
  • the base of the carrier oxide was changed in some comparative examples.
  • Comparative Examples VB17 to VB20 the incorporation of the iridium-containing promoter component had only been carried out after the calcination.
  • Comparative Example VB8 had a cobalt content of 2.8% by weight.
  • sample samples prepared on commercially available hydrotalcite were prepared by a procedure in which the steps Compaction and impregnation were combined.
  • the production process is exemplified here for the production of example sample B1, the sample samples B2, B3, B5, B6, BR7, B8, VB1 -VB4, B9, B10, BR1-BR4, B12, B13, B15-B18, B21 and BR8 were prepared by the same method, which differs only in terms of the amounts and type of doping elements.
  • a commercially available finely divided hydrotalcite powder with a granulator in the present case a roller compactor
  • the coarse-grained granules were rubbed through a sieve with a mesh size of 1 mm and sieved finely divided material (500 ⁇ mesh size), after which a compacted hydrotalcite powder having a particle size in the range of 0.5 - 1 mm was obtained.
  • hydrotalcite As commercially available hydrotalcite became Pural MG 70
  • the granulator used was a roller compactor from Powtec (type RC 100x30). During compaction, 250 g of finely divided powder were treated in several passes with a contact pressure of 250 bar each with a corrugated roll mill. The rollers had a rotation speed of 5 rpm. The granulator was equipped with a sieve insert with a mesh size of 1, 6 mm.
  • the compacted hydrotalcite powder had a water holding capacity (or liquid holding capacity) of 0.46 ml / g, and the loss on ignition of the dense hydrotalcite powder determined at 600 ° C. was 44.7% by weight. From one approach to the next approach, the water uptake capacity and the loss on ignition of the sample produced in each case could be subject to small deviations, which was then taken into account in the addition of impregnating impregnation solution in a corresponding manner.
  • the application of the promoter elements was carried out on the compacted hydrotalcite powder by impregnation impregnation.
  • 12 g of the compacted Hydrotalcitpulvers were presented in individual porcelain dishes with 8 cm diameter.
  • the respective porcelain dishes were then dosed with the metal salt solutions in the previously determined concentrations and liquid quantities in order to apply the desired target amount of metal species while not exceeding the liquid absorption capacity of the powder.
  • This dry powder impregnation impregnation process is an Incipient Wettness process with full pore filling.
  • the porcelain dishes filled with powder samples were moved or rotated during and after the addition of the impregnating solution by means of a laboratory shaker, at a speed of 1000 rpm.
  • the porcelain dish filled with the sample was first stored for 12 hours at 80 ° C. in a circulating air drying cabinet. Subsequently, the sample was calcined in a calcination furnace (Model LH 120/12 from Nabertherm). For calcination, the sample was first heated in the oven to 250 ° C and 4 hours at 250 ° C annealed. Subsequently, the sample was heated to 400 ° C, 4 hours at 400 ° C annealed and cooled to room temperature within 8 hours. Throughout the calcination phase and the cooling phase, an air flow of 6 L / min was fed to the furnace. In the heating phases, a heating rate of 1 K / min was used.
  • part of the sample samples were calcined at higher or lower temperatures, as shown in Tables 1.b and 1.d.
  • the calcined sample material was screened to obtain the sample with a particle size of 0.5-1 mm. For this, sieves with a mesh size of 1 mm and 0.5 mm were used and the powder samples were first spread over the screen surface of the coarse sieve with the edge of a spatula, and then the fines were removed via the fine sieve. ii. precipitation method
  • Example Sample B4 (in Table 1 .a), 127.82 g of powdered Mg (NO 3 ) 2 -6H 2 O (99.99% purity) and 55.81 g of powdered Al (NO 3 ) 3 were prepared -9H 2 0 (with purity of 99.2 wt .-%) filled in a four-necked flask with 2 L capacity and mixed to dissolve with 250 mL H 2 0. The solution was mixed with a stirrer. The stirrer was connected via a stirring shaft to a drive motor, which was arranged above the glass bulb.
  • (NH 4) 2 C03 solution added by means of a dropping funnel. During the addition of the (NH 4 ) 2 C03 solution, a milky suspension formed. After the addition of the (NH 4 ) 2 C03 solution, the pH is adjusted to 9.5 by means of the NH 4 OH solution. For controlled aging of the suspension, this was heated to 60 ° C and held for one hour at 60 ° C with simultaneous mixing by means of the stirrer. During the aging process, the pH was controlled and controlled in each case by the addition of further NH 4 OH solution that this was 9.5. The precipitated solid was filtered off using a filter chute with a paper filter (black belt). The filter cake was washed at room temperature with 5 L of distilled water.
  • the nitrate content in the washing water was checked to check the effectiveness of the washing process.
  • the aim was to obtain a largely nitrate-free wash water. This goal was achieved when there was a nitrate content of less than 100 ppm.
  • the solid was placed in a porcelain dish and stored for drying at 80 ° C for 12 hours in a convection oven. For comminution, the dried powder was forced through a sieve (mesh size 1 mm) with a spatula.
  • the sample was calcined using a calcining program, annealed at 250 ° C for 4 hours and tempered at 400 ° C.
  • the furnace was heated to the target temperature at a rate of 1 K / min.
  • the furnace was cooled to room temperature over a period of 8 hours (i.e., at a cooling rate of about 0.8 K / min).
  • the calcination was carried out in a chamber furnace type LH 120/12 from Nabertherm. During calcination and during the cooling process, air was passed through the furnace at a flow rate of 6 L / min.
  • Example B4 After calcining, the sample material was pushed through the mesh of a 1 mm mesh sieve using a spatula to obtain a target fraction having particles in the range 0.5-1.0 mm.
  • sample samples B19 and B20 were also prepared. Similar procedure was also used in the synthesis of the comparative example samples listed in Table 1.d. However, in the synthesis of Comparative Examples VB1 1 to VB14, VB15 and VB16, it should be noted that the zirconia was supplied in the form of the oxide. Comparative Examples VB8 and VB9 were made according to the description disclosed in patent application WO 2009/097310 (by DuPont).
  • Comparative Example C 10 In the preparation of Comparative Example C 10, a part of the sample VB9 was subjected to a washing process after precipitation and aging, based on the disclosure of WO 2009/097310.
  • Table 1.d these comparative examples are characterized by the term EDTA synthesis, since EDTA was added to the synthesis system.
  • WO 2009/097310 although in the description also the iridium is disclosed as a promoter element, but is not mentioned as an example.
  • a sodium-containing precipitant is preferably used.
  • Comparative Examples VB17 -VB20 in Table 1 .d refer to a mixed oxide carrier oxide of magnesium and aluminum oxide in which disperal was used as alumina source and magnesium nitrate as source of magnesium oxide for the preparation of the hydrotalcite-containing material.
  • the loading of the carrier oxide with the promoter carried out component after the calcination of the carrier oxide, which did not lead to the catalysts of the invention.
  • Comparative Example VB10 was subjected to a washing process, large part iridium particles were identified by TEM examination. The particle size of these large-scale iridium-containing particles is in the range of 50 to 500 nm.
  • the starting amounts of magnesium and aluminum nitrate were chosen to produce a hydrotalcite having the empirical formula (Mg6Al2 (OH) i6C03-4H20) and then to obtain this with an iridium loading of 1% by weight.
  • the catalyst samples were characterized by TEM (Transmission Electron Microscopy) studies.
  • the TEM instrument used was a 200kV Tecnai G20 from FEI equipped with FEG-TEM, HAADF-STEM, EDXS and SAD analytical methods.
  • FEG-TEM mean that it was a Field Emission Gun (TEM) TEM, HAADF-STEM that could be made in High Angle Annular Dark Field (Scanning Transmission Electron Microscopy)
  • EDXS that the device was equipped with an energy-dispersive detector (Energy Dispersive X-Ray Spectroscopy (Z> 8)) and the TEMS in selected areas and Diffraktorgramme could be recorded (SAD equipment for Selected Area Diffraction).
  • image areas in the range of 1: 20,000 to 1: 1 .000,000 were analyzed, the magnification range being 1:
  • Example sample B1 had an iridium content of 1.0% by weight.
  • the TEM studies carried out on sample samples of the invention after the catalytic test showed that the size of the iridium particles increased somewhat. It is also noteworthy that in the example samples loaded with higher iridium content, ie 1, 1 and 2.2% by weight, only very small iridium particles in the range from 0.5 to 2 nm were recognizable.
  • the size of the iridium particles in the sample samples according to the invention after the catalytic test was in the range from 0.5 to 6 nm.
  • the TEM images of Example B2 In Fig. 2, the TEM image is taken from the fresh catalyst sample B2, and in Fig. 3, the TEM image from the aged catalyst sample B2, that is, after the performance of the catalytic test assay, is shown. At the highest magnification, all sample samples according to the invention had a porous or sponge-like surface structure. The bright or white ones Points are assigned to the finely divided iridium particles.
  • the TEM images of Sample Example B3 showed the same nature.
  • the TEM images on the inventive sample samples after the catalytic test showed that the iridium particles had an extremely homogeneous distribution. Iridium particles smaller than 0.2 nm could no longer be detected in the TEM images because of the resolution limit.
  • the size of the irdidium particles could, within certain limits, also be controlled by the calcination temperature, with those samples calcined at 800 ° C having slightly larger iridium particles than the samples calcined at lower temperatures.
  • sample sample VB10 in FIG.
  • This is the iridium-containing sample prepared by EDTA.
  • the slightly larger agglomerates have an increased iridium content and are accompanied by magnesium oxide-containing material.
  • the analyzes also showed that this is a phase mixture or the purity was not as high as in the case of the catalysts of the invention.
  • agglomerates were detected, which had a high iridium content.
  • Such agglomerates sometimes had a particle size in the range of 50-600 nm, whereby the components of these particles could be attributed to the iridium with high probability due to the contrast of the TEM images. (EDXS were measured on these particles which showed a high Ir content.)
  • Example VB8 A slightly different sample structure compared to the iridium-containing samples could be seen in the cobalt-containing catalyst sample (see the example of Example VB8 shown in FIG. 4).
  • the cobalt-containing sample sample VB8 showed an aggregation of small platelets, but not the spongy or porous expression of the catalyst samples according to the invention. There were no small cobalt particles.
  • the surface of the sample samples was further characterized by nitrogen adsorption measurements. For this a Tristar measuring device of the company Micromeritics was used. It was found that the example samples of the invention, which had been examined before the catalytic test, had BET surface areas of more than 150 m 2 / g. In addition, even after carrying out the catalytic tests, high BET surface areas were still detected on the sample samples, which were in the range of more than 100 m 2 / g. It is worth noting that the Sample samples described here showed high catalytic performance even after the catalytic test studies. Due to the stress during the catalytic test studies, a decrease in the BET surface was observed, but this was of a magnitude that could prove the high stability of the sample samples.
  • the retention of BET surface area (ie, the BET surface area) associated with the method of the invention is greater than 45%, preferably greater than 50%, and most preferably greater than 55%.
  • Table 1 shows the BET surface areas which were determined in a characterization of selected example samples before and after the conduct of the catalytic test investigations.
  • the fresh sample samples were labeled with an a and the aged sample samples with an a.
  • Comparative Examples VB18, VB19 and VB20 are the catalyst samples that were impregnated with iridium solution only after calcination. (The n.a. means here that the value was not analyzed.)
  • the chemical analyzes were each performed on small quantities of the sieved sample batches prepared for catalytic testing. Slight deviations in the chemical composition, which were found in the chemical analysis compared to the calculated composition - possibly in connection with abrasion and / or variation in the water content of the starting material - were not completely excluded.
  • the chemical components of the samples - such as Ir and Ru - were quantified by elemental analysis using an ICP-OES (device type: Vista Pro) from VARIAN.
  • the chloride content was determined after combustion with tin capsules by titration with aqueous AgNO 3 solution using a standard titration unit (eg from Metrohm). IV.3 Catalytic Investigations
  • the results of the catalytic tests for the condensation of ethanol are shown in Tables 2 to 7.
  • the catalytic test investigations were - with a few exceptions - carried out in each case on 1 ml_ of powdered sample samples, for which purpose a split fraction was used with a particle size in the range of 0.5 to 1 mm. Exceptions are the sample samples B10 / 35 - B10 / 38, in which the GHSV of 2000 r 1 and 5000 h -1 was used. The increase in GHSV was achieved in these cases through the use of smaller amounts of sample (ie, 0.2 ml_ sample at the GHSV 5000 h -1 and 0.5 ml_ sample at the GHSV 2000 r 1 ).
  • the samples were positioned in tubular reactors on a catalyst chair or on an inert particle bed, the loaded reactors were installed in the catalytic apparatus and the samples contained therein were subjected to the test protocols.
  • the test protocols usually provided that the samples were subjected to activation prior to the catalytic experiments.
  • some of the samples were also subjected to a conditioning treatment which was varied over the course of the treatment. All catalytic experiments were performed at temperatures within the range of 250 to 325 ° C.
  • a mass spectrometer-coupled gas chromatograph (a so-called Agilent GC-MS) equipped with FID and TCD was used.
  • Example B1_S1 Apart from that, investigations in an ethanol content of 1% by volume were also carried out in Example B1_S1.
  • the nitrogen content varied in the range from 75 to 94% by volume, the amount of nitrogen mainly depending on whether and in what amount hydrogen was also added to the reactant stream.
  • Table 3 shows the results of the catalytic tests on different catalyst samples in which the educt gas stream was in each case charged with 1% by volume of ethanol.
  • the catalyst samples in Comparative Examples VB1, VB2 and VB3 were added with the alkali metal elements Li, K or Cs in the preparation.
  • the alkaline catalyst samples (VB1-VB3) showed significantly lower yields of butanol and lower conversions of ethanol than the catalyst samples according to the invention such as in Examples B8 and B9 to B10.
  • the influence of the iridium content in the catalyst samples on the catalytic properties can be seen.
  • the catalyst sample VB4 has a significantly higher iridium content and lower catalytic performance properties than the catalyst samples according to the invention.
  • the catalysts in Examples BR1-BR4 were prepared with Ru as the active component, with the ruthenium content in the examples being varied in the range of 0.4 to 2.0% by weight.
  • the catalysts in Examples BR1 and BR2 showed good performance characteristics, with a decrease in butanol yield as the ruthenium content in samples BR3 and BR4 increased.
  • Both the iridium-containing catalysts (ie B8, B9, B10) and the ruthenium-containing catalysts (BR1-BR4) showed higher butanol conversions than the catalysts from the comparative examples (VB1-VB4), the catalysts according to the invention performing somewhat better with iridium than the catalysts catalysts of the invention with ruthenium.
  • the temperature used in the calcination of the catalysts shows an influence on the catalytic properties in the ethanol dimerization, as shown in Table 4.
  • the catalyst sample in Example B10 / 01 had been calcined at a temperature of 250 ° C during catalyst preparation.
  • Table 6 are the results of the catalytic tests, which were achieved with several inventive and non-inventive catalyst samples with respect to the dimerization of ethanol under high ethanol load in the reactant stream.
  • High ethanol load means that the educt stream was loaded with 20% by volume of ethanol - and in some cases even 30% by volume.
  • the loading of the gas stream with such high ethanol contents places very high technical demands on the performance characteristics of the catalysts used. Since the technical requirements also depend on the pressure, it should also be emphasized that the method according to the invention can be operated above the atmospheric pressure. At the same time, however, this also provides the opportunity to identify those catalysts that provide good performance in terms of the catalytic process under practical conditions.
  • the catalyst samples shown in Examples VB8 and VB9 were prepared in the presence of EDTA as the complexing agent according to a synthetic procedure disclosed in the patent application WO 2009/097310 (by DuPont).
  • the catalytic test data in these examples showed extremely low ethanol conversions and also low butanol yields. It has been found that the catalytic properties of the catalysts prepared by the EDTA synthesis route can be improved if a washing step is added to the production process, by which the content of alkaline species is reduced.
  • the alkaline species are water-soluble and the content of alkali species can be reduced by intensive washing. In the washing step, a part of the noble metal-containing component may be removed, which is undesirable.
  • the washing step also increases the amount of process water needed for the preparation of the catalyst.
  • the composition of the carrier material has a great influence on the catalytic properties.
  • Numerous iridium-containing catalyst samples were investigated in which the iridium was not present on the support material according to the invention.
  • the comparative examples VB1 1 to VB16 be mentioned, in which the iridium particles were present on zirconia or also the comparative examples VB17 to VB20, although the magnesia oxide and alumina in the carrier had, but not in the proportions and / or the structural nature of the invention.
  • Example B1_W1 describes a reaction of B1 under an acetaldehyde-containing feed.
  • a reaction catalyzed by the B1 partially deactivated in Experiment B1_W1 is described under 1% by volume of EtOH feed.
  • R1_S1 is a reaction in which the catalyst B1 was regenerated after the reaction with acetaldehyde with hydrogen according to the regeneration process described below R1 and then in the implementation of EtOH was used.
  • B1 R1_S1 is a reaction analogous to Example B1 R1_S1, in which the catalyst B1 but was regenerated according to the regeneration method R2 described below.
  • Catalyst B1 was synthesized according to the protocol described above and tested as a catalyst in the reaction with acetaldehyde as a feed (Table 8 Experiment B1_W1) according to the protocol described in the "Catalysis Studies" section of this document
  • the regeneration process R1 (see below) is reactivated, and the catalyst obtained thereafter bears the designation B1_R1.
  • Catalyst B1 was synthesized according to the procedure described above and tested as a catalyst in the reaction with acetaldehyde as feed (Table 8 Experiment B1_W1) according to the protocol described in the "Catalysis Studies" section of this document was re-activated according to the regeneration process R2 (see below), the catalyst obtained after that being designated B1_R2.
  • the reactor was charged with 9.8 g of the sample Example B1 / 02 Catalyst 1, 7% by weight Ir (based on Pural MG70, reproduction of B1), which was stored on quartz rings 3 mm.
  • the first cold trap was cooled to 2 ° C and the second cold trap was cooled by solid dry ice which sublimated at about -78 ° C.
  • the catalyst was heated to 400 ° C. under nitrogen, and then treated with 4 L / h of hydrogen and 18 L / h of nitrogen for 8 h. Subsequently, the reactor temperature was lowered to 325 ° C and the catalyst was under a stream of 1 1, 8 vol% n-butanol in nitrogen for 6 h at a GHSV of 1020 r 1 conditioned. Then successive tests were carried out under different conditions (different total gas flow, with and without hydrogen) (see Table 8.b). The different settings were maintained for 6 h, then the condensate from the discharge vessel and cold trap was combined and analyzed by GC analysis (offline analysis, uncalibrated GC). As Edukgasstrom nitrogen was charged with butanol.
  • Tables 9-23 further investigation results are shown in relation to embodiments of the inventive method for the reaction of alcohols, in which different alcoholic components are brought to the condensation reaction.
  • the catalytic test studies were carried out with the same experimental set-up which was also used for carrying out the test studies which were shown in Tables 2 to 7.
  • Tables 2 to 7 show the results of the process according to the invention for the condensation of ethanol to produce 1-butanol.
  • Tables 9-13 show the results of tests for the conversion of 1-propanol and methanol to iso-butanol.
  • Tables 14-17 show the results of the test studies to convert ethanol and methanol to iso-butanol.
  • Tables 18-23 show the results of tests to convert ethanol and methanol to 1-propanol (or n-propanol, respectively).
  • 1-butanol is synonymous with n-butanol.
  • Comparative Example CB30 the catalytic activity of a reactor tube filled with corundum was determined.
  • the corundum sample VB30 was subjected to the same experimental conditions as the example samples listed in the respective table.
  • Table 2 shows a summary of the reaction conditions and the conversions.
  • the addition of the S to the sample number of the example refers to the respective examination stages performed on the samples considered.
  • Sample B1 was tested in six steps from S1 to S6. At stages S2 to S6, the reactor temperature was gradually increased by 10 ° C. before the test experiment was carried out.
  • Example sample B1 ' is from the same synthetic approach as sample B1, but was treated according to K2 conditioning protocol.
  • Table 3 shows the results of the catalytic tests for the reaction of ethanol at a reaction temperature of 250 ° C and a GHSV of 1000 r 1 .
  • Table 5 shows the results of the catalytic test studies on the conversion of ethanol at a reaction temperature of 300 ° C and a GHSV of 1000 hr. 1 Carrying out the catalytic test on sample B10 / 07, wherein the ethanol content in the feedstream had been changed stepwise from stage 1 to stage 5.
  • EtOH BuO BuOH GHS
  • Table 6 shows the results of the catalytic tests for the conversion of ethanol at a reaction temperature of 325 ° C and a GHSV of 1000 h-1.
  • TRAY1 B 10/23 1.3% by weight of lr; 325 20 65 10 21,48 60,60 13,02 PMG 70;
  • Table 7 shows the results of the catalytic tests for the reaction of ethanol at a reaction temperature of 325 ° C and a variation of GHSV.
  • Table 8 shows a summary of the reaction conditions and the sales of the experiments with acetaldehyde-containing feed and with the under hydrogen regenerated catalysts.
  • Table 8.b shows a summary of the test conditions and results obtained by reacting n-butanol to produce 2-ethylhexanol (2-EH). It should be noted that the analytical data are based on an off-line method. where the calculation of sales, selectivities and yields is based on the determination of the GC area, which was determined relative to the liquid products.
  • Table 9 shows the results of the catalytic test studies for the reaction of 1-PrOH at a reaction temperature of 325 ° C. and a GHSV of 1000 r 1 under feed with the 1 -PrOH and MeOH in a molar ratio of 1:10. The results shown in Table 9 had been achieved with a hydrogen-free educt gas stream.
  • Table 10 shows the results of the catalytic tests for the reaction of ethanol at a reaction temperature of 300 ° C and a GHSV of 1000 r 1 under feed with the 1 -PrOH and MeOH in a molar ratio 1:10. The results shown in Table 10 were achieved with a hydrogen-free educt gas stream.
  • Table 12 shows the results of the catalytic test studies for the reaction of 1-PrOH with three selected catalysts at a GHSV of 1000 r 1 under feed with the 1-PrOH and MeOH in the molar ratio 1:10. The results shown in Table 12 were achieved with a hydrogen-free educt gas stream.
  • Table 13 shows the results of the catalytic test studies for the reaction of 1-PrOH with three selected catalysts at a reaction temperature of 325 ° C at a GHSV of 1000 hr 1 and at a GHSV of 2000 hr 1 under feed with the 1 -PrOH and MeOH in a molar ratio of 1:10. The results shown in Table 13 were achieved with a hydrogen-free educt gas stream.
  • Table 14 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 r 1 under feed with the EtOH and MeOH in the molar ratio 1:20 in the presence of 30 vol.% H2.
  • Table 15 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 hr 1 under feed with the EtOH and MeOH in the molar ratio 1: 20. The results shown in Table 15 were with a hydrogen-free Eduktgasstrom been achieved. P-No Example EtOH MeOH EtOH / so-butanol / so-butanol
  • Table 16 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 r 1 under feed with the EtOH and MeOH in a molar ratio of 1: 20. The results shown in Table 16 had been achieved with a hydrogen-free educt gas stream.
  • Table 17 shows the results of the catalytic tests for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 1000 hr 1 under feed with the EtOH and MeOH in a molar ratio 1:10. The results shown in Table 17 were achieved with a hydrogen-free educt gas stream. P-No Example Temp. EtOH MeOH EtOH 1 - 1 - [° C] [vol.%] [Vol%] conversion Propanol Propanol
  • Table 18 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 r 1 under feed with the EtOH and MeOH in the molar ratio 1:20 in the presence of 30 vol .-% H2.
  • Table 19 shows the results of the catalytic test studies for the reaction of EtOH at a reaction temperature of 325 ° C and a GHSV of 1500 r 1 under feed with the EtOH and MeOH in a molar ratio of 1: 20.
  • the results shown in Table 20 had been achieved with a hydrogen-free educt gas stream.
  • Table 20 shows the results of the catalytic test studies for the reaction of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 r 1 under feed with the EtOH and MeOH in a molar ratio of 1: 20.
  • Table 21 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2500 r 1 under feed with the EtOH and MeOH in the molar ratio 1:20.
  • Table 22 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 2000 r 1 under feed with the EtOH and MeOH in a molar ratio of 1:20.
  • the results shown in Table 23 had been achieved with a hydrogen-free educt gas stream.
  • Co-precipitation B15 1, 7% by weight 1 20 70.31 27.62 19.42 lr / 0.2% by weight
  • Table 23 shows the results of the catalytic test studies for the conversion of EtOH at a reaction temperature of 325 ° C and a GHSV of 1500 r 1 under feed with the EtOH and MeOH in a molar ratio of 1:20.
  • the test results shown in Table 24 had been achieved with a hydrogen-free educt gas stream.
  • Figure 1 shows the TEM uptake of catalyst sample B1 of the present invention containing 1.0% by weight of irididium from the fresh catalyst (i.e., prior to conducting the catalytic test assay).
  • FIG. 2 shows the TEM image of the catalyst sample B2 according to the invention before the catalytic test investigation.
  • Figure 3 shows the TEM uptake of catalyst sample B2 of the present invention with 1.1% by weight iridium from the aged catalyst (i.e., after conducting the catalytic assay.
  • Figure 4 shows the TEM image of the cobalt-containing catalyst sample VB8 prior to conducting the catalytic assay. This is a bright field recording - in contrast to the other recordings, the dark field recordings (HAADF).
  • Figure 5 shows the TEM image of the iridium-containing catalyst sample VB10 prior to conducting the catalytic assay.
  • Fig. 6 shows the TEM image of the iridium-containing catalyst sample VB10 after the sample has been subjected to a washing process.
  • the areas of the sample identified by the three arrows have an increased concentration of iridium.
  • the sample areas with the increased iridium content are slightly lighter.
  • the scaling bar in the sub-area on the right-hand side has a length of 200 nm.

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Abstract

L'invention concerne un catalyseur et un procédé de condensation d'alcools en phase gazeuse par réaction de guerbet. De préférence, le catalyseur selon l'invention est utilisé dans un procédé de production de butanol par condensation d'éthanol. Le catalyseur comporte un matériau de support en composés similaires à de l'hydrotalcite, en particulier de l'hydrotalcite, partiellement ou totalement thermiquement désintégré, en contact avec de l'iridium et/ou du ruthénium comme promoteur, la teneur en iridium et/ou en ruthénium étant de l'ordre de 0,05 - 4 % en poids, de préférence de 0,1 - 3,5 % en poids et idéalement de 0,2 - 3,0 % en poids et la taille moyenne des particules de promoteur étant < 100 nm, de préférence < 75 nm , mieux encore < 50 nm et idéalement < 20 nm. La teneur en alcali des catalyseurs est très faible, c'est-à-dire < 1 % en poids, de préférence < 0,5 % en poids. Dans un mode de réalisation préféré, le procédé est mis en œuvre à une température de l'ordre de 0 - 450 °C, une pression de l'ordre de 0,05 - 60 bar et une teneur en alcool dans le courant de substance de départ de l'ordre de 0,5 - 90 % en volume.
PCT/EP2014/066727 2013-08-07 2014-08-04 Catalyseur contenant de l'iridium et procédé pour une réaction de guerbet en phase gazeuse WO2015018793A1 (fr)

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US9725393B2 (en) 2014-10-08 2017-08-08 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US9765001B2 (en) 2014-01-17 2017-09-19 Basf Se Method for producing arylpropenes
CN107469861A (zh) * 2017-08-30 2017-12-15 江南大学 一种用于双酚F合成的Ir@Cu@BINAL@HT催化剂及制备方法
US10160711B2 (en) 2015-12-15 2018-12-25 Chevron Phillips Chemical Company Lp Formation of α,β-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10308580B2 (en) 2015-07-15 2019-06-04 Basf Se Process for preparing an arylpropene
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10544080B2 (en) 2017-06-14 2020-01-28 Chevron Phillips Chemical Company Lp Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor
US10550061B2 (en) 2017-06-14 2020-02-04 Chevron Phillips Chemical Company Lp Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide
CN111468185A (zh) * 2020-04-16 2020-07-31 江苏星诺新材料科技有限公司 一种负载型光催化剂及其制备方法与应用
CN113398925A (zh) * 2021-07-07 2021-09-17 南京工业大学 一种负载铱多相催化剂及其制备方法和应用
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US9765001B2 (en) 2014-01-17 2017-09-19 Basf Se Method for producing arylpropenes
US9416087B2 (en) 2014-10-08 2016-08-16 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US9725393B2 (en) 2014-10-08 2017-08-08 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US9783478B2 (en) 2014-10-08 2017-10-10 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US10584088B2 (en) 2014-10-08 2020-03-10 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US9896405B2 (en) 2014-10-08 2018-02-20 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US10155711B2 (en) 2014-10-08 2018-12-18 Chevron Phillips Chemical Company Lp Methods for the production of alpha, beta-unsaturated carboxylic acids and salts thereof
US10155712B2 (en) 2014-10-08 2018-12-18 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US10308580B2 (en) 2015-07-15 2019-06-04 Basf Se Process for preparing an arylpropene
US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10941101B2 (en) 2015-12-15 2021-03-09 Chevron Phillips Chemical Company, Lp Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes
US10160711B2 (en) 2015-12-15 2018-12-25 Chevron Phillips Chemical Company Lp Formation of α,β-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes
US11530177B2 (en) 2015-12-15 2022-12-20 Chevron Phillips Chemical Company Lp Formation of α,β-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes
US10988430B2 (en) 2017-06-14 2021-04-27 Chevron Phillips Chemical Company Lp Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor
US10926247B2 (en) 2017-06-14 2021-02-23 Chevron Phillips Chemical Company Lp Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide
US10550061B2 (en) 2017-06-14 2020-02-04 Chevron Phillips Chemical Company Lp Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide
US11491473B2 (en) 2017-06-14 2022-11-08 Chevron Phillips Chemical Company, Lp Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide
US10544080B2 (en) 2017-06-14 2020-01-28 Chevron Phillips Chemical Company Lp Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor
CN107469861A (zh) * 2017-08-30 2017-12-15 江南大学 一种用于双酚F合成的Ir@Cu@BINAL@HT催化剂及制备方法
US11174213B2 (en) 2018-10-12 2021-11-16 Chevron Phillips Chemical Company, Lp Effects of catalyst concentration and solid activator on nickel-mediated olefin/carbon dioxide coupling to acrylates
CN111468185A (zh) * 2020-04-16 2020-07-31 江苏星诺新材料科技有限公司 一种负载型光催化剂及其制备方法与应用
CN113398925A (zh) * 2021-07-07 2021-09-17 南京工业大学 一种负载铱多相催化剂及其制备方法和应用

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