FR3013609A1 - PROCESS FOR THE CONVERSION OF CARBONYLIC ORGANIC COMPOUNDS AND / OR ALCOHOLS IN THE PRESENCE OF AN ALUMINATE COPPER CATALYST - Google Patents

Abstract

The invention relates to a catalyst comprising at least one aluminate of a metal M, at least one alkali metal or alkaline earth metal, at least one hydrogenating transition metal chosen from the group consisting of nickel, palladium and platinum. copper, rhodium and ruthenium and in which at least 5% of the total weight of metal M is leachable, as well as the use of this catalyst in a process for converting organic compounds carbonyls and / or alcohols by aldolization, crotonization and hydrogenation, in a single reaction vessel, in the presence of hydrogen, operated in the vapor phase at a temperature between 150 and 400 ° C, at a pressure of between 0.1 and 2.0 MPa, with a molar ratio H2 / compounds between 0 and 5 and a PPH between 0.25 and 20 h-1.

Description

The invention relates to the production of methyl isobutyl ketone (MIBK) and di-isobutyl ketone (DIBK) from carbon monoxide and / or alcohols in the presence of a copper aluminate catalyst. TECHNICAL FIELD OF THE INVENTION from organic carbonyl compounds and / or alcohols by aldolisation, crotonisation and hydrogenation, in a single reaction chamber. PRIOR ART The scarcity of petroleum resources, as well as the global warming caused by greenhouse gas emissions, lead to the development of new processes for the sustainable production of fuels and chemicals. In this context, lignocellulosic biomass appears as an alternative resource for fuel production because it is abundant, renewable and does not compete with food resources. In fact, the hydrolysis of the cellulosic and hemicellulosic fraction of the lignocellulosic biomass leads to molecules with 5 or 6 carbon atoms which can then be converted into hydrocarbons or alcohols. When the oxygen of the biomass is removed in the form of water, the length of the carbon chain is not changed. However, the loss of oxygen leads to the formation of unsaturated products: double and triple bonds carbon-carbon or carbon-oxygen, aromatic structures. The products thus obtained are not directly incorporable to fuel (gasoline or diesel) because these molecules are too polar, too short and / or too unsaturated. The decrease in polarity or unsaturations can be ensured by a selective hydrogenation, but it is in any case necessary to increase the average molecular weight of these compounds, especially if the targeted target is kerosene or diesel. Several reactions can be envisaged to increase the length of the chain: the oligomerization of olefins obtained by dehydration of alcohol, the etherification, the esterification, the decarboxylating coupling or the aldolisation of oxygenated compounds. The essential point lies in the creation of carbon-carbon bonds.

Carbonyl compounds transformable by aldolization can be obtained from cellulose. Hydrolysis of cellulose produces glucose which after transformation gives 5-hydroxymethylfurfural (5-HMF). The acidic hydrolysis of 5-HMF makes it possible to obtain levulinic acid. More generally, it is possible to obtain carbonyl compounds from sugars (such as for example glucose or sorbitol) by reaction on a Pt-Re / Carbon catalyst at 225 ° C. The mixture of products obtained contains carbonyl compounds but also alcohols, acids and cyclic molecules. For example, MIBK and DIBK are prepared by condensation of acetone in the liquid phase, generally with a higher yield of MIBK than DIBK. DIBK is generally obtained as a by-product during the manufacture of MIBK, but with low selectivity. The transformation of the acetone molecule into MIBK is described for example in Martinez-Ortiz et al. The "one-pot" synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone over PdCu catalysts prepared from layered double hydroxides, Journal of Molecular Catalysis A: Chemical, 2003, 201, pp.199-210. A one-step gas phase process using a bifunctional catalyst capable of performing both aldolization, dehydration and hydrogenation would reduce the costs of the conventional liquid phase process. These costs are mainly due to the separation and neutralization steps, the corrosion problems induced by liquid acidic and basic catalysts and the large quantities of waste generated by the liquid phase processes. The interest of a one-step process for the aldolization of acetone is even greater than the product formed during this reaction is highly recoverable. Indeed the MIBK (160000 tons / year) is used as a solvent in many applications such as the production of paints, varnishes, resins. It is also a solvent for cellulose, which explains why its transformation is widely studied in the literature. However, the transformation of oxygenated compounds to longer carbon chain molecules such as DIBK is poorly studied. Many processes for the conversion of carbonyl compounds using multifunctional catalysts have been described in the literature.

EP 0 888 185 discloses a process for producing a catalyst comprising a copper oxide on alumina support and free of chromium. The catalyst may also contain a crystalline structure of copper aluminate (spinel) type. The absence of spinel phase results in a larger amount of leachable ions than a calcined catalyst having a spinel phase. This document recommends, for the reactions studied, less than 5% leachable copper ions. The presence of sodium has negative effects on the performance of the hydrogenation catalysts. This document teaches that an ideal catalyst should have a low percentage of leachable cations. This catalyst is only applied to hydrogenolysis or hydrogenation reactions, in particular hydrogenation of aldehydes. FR 2 968 002 describes a process for producing DIBK from dehydration and the hydrogenation of triacetone dialcohol (TDA) in the presence of a bifunctional catalyst which may comprise an alumina and copper. The reaction is carried out in the liquid phase.

The disadvantage of the liquid phase process is the multiplication of the reaction stages, thus the use of several catalysts which increases the production costs. This also causes catalyst stability problems including sintering of the metal phases but also the leaching of the catalyst in the acidic liquids, as mentioned in the text EP 0 888 185. On the other hand, the leaching of the catalyst in the products of the reaction entails additional costs of treatment of the effluents of the process. Finally, the TDA must be obtained in an additional step during which 3 molecules of acetone are condensed. FR 2 969 148 describes a process for producing DIBK from acetone and MIBK and using a multifunctional catalyst capable of carrying out an addition reaction of aldol, a dehydration and a hydrogenation at a temperature between 100 and 140 ° C. The reaction is carried out in the liquid phase and at high pressure. It is therefore necessary to have previously synthesized the MIBK in a previous step.

The patent application WO2007 / 038440 proposes a process for producing MIBK and DIBK from acetone and / or isopropyl alcohol (IPA) in the presence of any type of catalyst that can be used for the production reactions of MIBK and DIBK. in the gas phase, the use of a pressure greater than 207 kPa making it possible to improve the degree of conversion to MIBK and DIBK and increasing the MIBK / DIBK ratio. In the examples of catalysts using copper, copper is always associated with chromium. The disadvantage of chromium, also emphasized by the document EP 0 888 185 is its toxicity. US 6,916,457 discloses a chromium-free copper-aluminum catalyst containing less than 60% by weight of an oxide of spinel structure, and wherein less than 10% of the copper is leachable. The activity of the catalyst is optimal for Na 2 O sodium oxide contents of less than 0.5%. This catalyst is used in particular to catalyze the hydrogenolysis reaction. This text highlights the necessary presence of copper oxide, a content of 40 to 80% copper oxide to achieve performance equivalent to Cu / Cr catalysts. US Pat. No. 6,977,314 teaches a process for the aldolisation / dehydration / hydrogenation of ketones in the presence of hydrogen and a polysulfonated ion exchange resin containing 0.1 to 2% of metal (Pd, Pt, Ir , Rh, Ru, Os, Cu, Ni, Zr), said process being operated in the liquid phase, at high pressure. This process promotes the production of dimer (MIBK) with a conversion of the order of 40%, and a selectivity of the order of 98%. This text therefore does not use a catalyst based on a metal aluminate. None of these documents teaches a catalyst capable of converting organic carbonyl compounds and / or alcohols into a single reaction chamber having improved stability and significant conversion to MIBK and DIBK. OBJECT AND INTEREST OF THE INVENTION An object of the invention is a catalyst comprising: at least one aluminate of a metal M belonging to columns 9, 12 of the periodic table of elements whose molar ratio M / Al is included between 0.2 and 0.8; at least one alkali metal or alkaline earth metal, the content of which represents from 0.05 to 4% of the total weight of said catalyst; at least one hydrogenating transition metal selected from the group consisting of nickel, palladium, platinum, copper, rhodium and ruthenium, alone or as a mixture; wherein at least 5% of the total weight of metal M is leachable, as determined by the reaction of 100 ml of 10% acetic acid with 10 g of powder catalyst for 1 hour with continuous stirring.

Another subject of the invention is a process for converting organic carbonyl compounds and / or alcohols by aldolization, crotonization and hydrogenation, in a single reaction chamber, in the presence of hydrogen and a catalyst according to the invention, such as said process is carried out in the vapor phase at a temperature of between 150 and 400 ° C., at a pressure of between 0.1 and 2.0 MPa and with a molar ratio of H 2 / organic compounds of between 0 and 5 and with a PPH included between 0.25 and 20 h -1, the PPH ("Weight per Weight per Hour" or "Weight Hourly Space Velocity" in English) being equal to the mass flow rate of reactor inlet charge (kg / h) divided by the mass of catalyst in the reactor in kg.

An advantage of the invention is to carry out the transformation of organic compounds of carbonyl type and / or alcohols in a single step using a single multifunctional catalyst.

Another advantage is to produce a catalyst with improved stability which is more active in charge conversion and more selective for the formation of long-chain carbon molecules. A further advantage of the invention is to obtain MIBK and DIBK with a very low hydrogenation of the carbonyl function, even when multiple aldolization reactions are chained. DETAILED DESCRIPTION OF THE INVENTION The invention relates to a catalyst comprising: at least one aluminate of a metal M belonging to columns 9, 12 of the periodic table of elements whose molar ratio M / Al is between 0.2 and 0.8; at least one alkali metal or alkaline earth metal, the content of which represents from 0.05 to 4% of the total weight of said catalyst; at least one hydrogenating transition metal selected from the group consisting of nickel, palladium, platinum, copper, rhodium and ruthenium, alone or as a mixture; wherein at least 5% of the total weight of metal M is leachable, as determined by the reaction of 100 ml of 10% acetic acid with 10 g of powder catalyst for 1 hour with continuous stirring.

Said metal M is preferably chosen, alone or as a mixture, from the group consisting of cobalt, copper, zinc and nickel, preferably from the group consisting of cobalt, copper and zinc, very preferably among the group consisting of cobalt and copper. Said metal M is advantageously copper.

Said molar ratio M / Al is preferably between 0.3 and 0.7, preferably between 0.3 and 0.6 and very preferably between 0.4 and 0.6. Preferably, at least 60% of the total weight of said catalyst is in the form of metal aluminate M, that is to say in spinel MAI204 form, very preferably at least 65% by weight, even more preferably at least 70% by weight, and advantageously at least 78% by weight. The presence of this spinel phase makes it possible to improve the hydrothermal resistance of the catalyst. Said metal A is preferably an alkali metal, preferably sodium, lithium or potassium, very preferably sodium or potassium, and advantageously sodium. The content of said metal A preferably represents from 0.08 to 4% of the total weight of said catalyst, and preferably from 0.08 to 2% of the total weight of said catalyst. The presence of at least one alkali metal or alkaline earth metal selected from Ni, Na, K, Rb, Cs, Be, Mg, Ca and Sr, preferably from K and Na, and preferably Na, allows on the one hand to improve the stability of said catalyst and, on the other hand, by adjusting the content of said metal A, to control the selectivity to MIBK or DIBK. Said catalyst is advantageously free of chromium. The catalyst which is the subject of the invention makes it possible to carry out the aldol condensation, the crotonization and the hydrogenation in the gas phase of acetone and / or isopropyl alcohol to give mainly MIBK and DIBK. To carry out the aldolization and dehydration reactions, the catalyst must have an acid-base phase. The dehydrogenation and hydrogenation reactions are mainly provided by a metal phase.

The catalyst according to the invention is therefore a bifunctional catalyst having both condensation sites, associated with metal sites such as transition metals. According to the invention, said catalyst comprises at least one hydrogenating transition metal selected from the group consisting of nickel, palladium, platinum, copper, rhodium and ruthenium alone or as a mixture. Said hydrogenating transition metal advantageously represents from 0.01 to 10% of the total weight of said catalyst, preferably between 0.05 and 10% by weight, very preferably between 0.1 and 5% by weight, and advantageously between 0.1 and 2%. weight. According to a preferred embodiment, when said metal M is copper, said catalyst comprises at least one hydrogenating transition metal selected from the group consisting of nickel, palladium, platinum, copper, rhodium and ruthenium alone or in mixture.

According to another preferred embodiment, when said metal M is copper, said hydrogenating transition metal is copper. The catalyst according to the invention is prepared either by co-kneading or co-precipitation but preferably by co-precipitation to homogenize the catalyst composition. The alkali metal or alkaline earth metal A present in the catalyst according to the invention may be introduced during the co-precipitation or be impregnated to a higher content after drying of the precipitate or after calcination. This solid can then advantageously undergo an impregnation of a hydrogenating metal to introduce hydrogenation sites, typically transition metals chosen from Ni, Pd, Pt, Cu, Rh, and Ru, in particular when said metal M n ' is not copper. The hydrogenating metal may be introduced either by excess impregnation or incipient wetness impregnation, or by any other technique known to those skilled in the art.

The catalyst is activated by in situ reduction between 200 ° C. and 300 ° C. under hydrogen flow prior to its use for the aldolization, crotonization and hydrogenation reaction. The catalyst according to the invention thus comprises, prior to its activation, a reducible phase under the activation conditions (200-300 ° C. under a stream of hydrogen). The invention also relates to a process for converting organic carbonyl compounds and / or alcohols by aldolization, crotonization and hydrogenation, in a single reaction chamber, in the presence of hydrogen and a catalyst according to the invention, operated in the vapor phase at a temperature of between 150 and 400 ° C, advantageously between 200 and 300 ° C, and preferably between 190 and 250 ° C, at a pressure of between 0.1 and 2.0 MPa, advantageously between 0.1 and 1 MPa, and preferably between 0.1 and 0.3 MPa, with a molar ratio H 2 / organic compounds of between 0 and 5 and with a PPH of between 0.25 and 20 h -1, and advantageously between 0 , 25 and 1 h-1.

When said organic compounds are carbonyl compounds, said molar ratio H2 / organic compounds is between 0.25 and 5. When said organic compounds are alcohols, said molar ratio H2 / organic compounds is between 0 and 5, preferably between 0 and 5. , 01 and 5, and preferably between 0.1 and 5.

The process for converting organic carbonyl molecules and / or alcohols into long carbon chain molecules according to the invention is a process carried out in a single reaction chamber using as catalyst the only catalyst according to the invention. In this reaction chamber occur the reactions of aldol condensation, crotonization and hydrogenation. The conversion process according to the invention is carried out in the gaseous phase so as to avoid the problems of solubilization of the catalyst in the reaction medium which may result in degradation of the quality of the final product. The gaseous phase makes it possible to avoid the solubility problems of hydrogen in the liquid phase but also to improve the stability of the catalyst. Operating temperature below 150 ° C runs the risk of condensation of the heavy molecules formed during the reaction, while temperatures above 300 ° C are to be avoided so as to minimize catalyst deactivation and increase hydrogenation reactions at the expense of aldolization reactions. A low PPH makes it possible to favor the aldolization reactions.

EXAMPLES Description of the Catalytic Test Unit: The reactor used in the following examples consists of a stainless steel tube 24 cm long and 16.1 mm in diameter. The reactor is first loaded with the catalyst diluted in carborundum, then quartz wool to delimit the catalytic bed and finally carborundum supplementing the remaining empty volume. The temperature of the reactor is controlled with a tubular furnace with three heating zones. The liquid charge of acetone or isopropanol is injected via a pump. The liquid and gaseous streams are vaporized in the heated lines by a tracer before entering the reactor. The products formed in the vapor phase are analyzed by gas chromatography installed in line (HP 5890) and equipped with a capillary column CP-WAX-52 CB of dimension 10 m × 0.1 mm × 0.1. The catalyst is activated in situ. under pure H2 at 300 ° C. The operating conditions are as follows: T = 200 ° C., P = 0.2 MPa, H 2 / organic compound molar ratio = 3, PPH = 111-1 (hourly mass flow rate in g / h per g of catalyst).

Example 1 according to the invention: Catalyst A (Cu / Al = 0.37) The material is prepared by coprecipitation at a constant pH: 97.4 g of copper nitrate and 417.4 g of aluminum nitrate are dissolved in 900 ml of deionized water. The solution containing the precursors of copper and aluminum is added at a constant rate (30 ml / min) using a peristaltic pump in a reactor containing a foot of water of 600 ml at 50 ° C. and whose pH was previously adjusted to 8 using a 30% solution of sodium hydroxide. The reaction medium is stirred mechanically (600 rpm), and the coprecipitation pH is continuously maintained around 8 (+/- 0.5) by addition of a 30% sodium hydroxide solution. The suspension obtained is filtered to obtain a cake, which is washed with 3 I of deionized water. The cake is then dried at 120 ° C. for 24 hours.

The CuAI powder is calcined in a muffle furnace with a stage of 2 hours at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. Despite the Cu / Al ratio <0.5 (measured by ICP), the X-ray diffractogram of the calcined material at 800 ° C indicates the presence of CuA1204 spinel and CuO (-1% weight), with no trace of alumina.

The residual Na content measured by ICP is 7744 μg / g, ie 0.7% by weight of the catalyst. Example 2 Non-Conforming to the Invention: Catalyst B (Cu / Al = 0.46) The material is prepared by coprecipitation at a constant pH: 276.3 g of a solution of copper nitrate at 13.7% by weight Cu 492.1 g of aluminum nitrate dissolved in 2 l of deionized water are added. The solution containing the precursors of copper and aluminum is added at a constant rate (70 ml / min) using a peristaltic pump in a reactor containing a foot of water of 700 ml at 50 ° C. and whose pH was previously adjusted to 8 with a 30% solution of sodium hydroxide. The reaction medium is stirred mechanically (600 rpm), and the coprecipitation pH is continuously maintained around 8 (+/- 0.5) by addition of a 30% sodium hydroxide solution. The suspension obtained is filtered to obtain a cake, which is washed with 6 1 of deionized water. The cake is then dried at 120 ° C. for 24 hours. The CuAI powder is calcined in a muffle furnace with a stage of 2 hours at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. Despite the ratio Cu / Al <0.5, the X-ray diffractogram of the calcined material at 800 ° C indicates the presence of CuA1204 spinel and CuO. The residual Na content measured by ICP is 88 μg / g, ie 0.01% by weight of the catalyst.

Example 3 in Accordance with the Invention: Catalyst C (Cu / Al = 0.51) The material is prepared by coprecipitation at a constant pH: 305.7 g of a solution of copper nitrate at 13.7% by weight Cu are added to 492.1 g of dissolved aluminum nitrate and 492.1 g of aluminum nitrate dissolved in 2 l of deionized water. The solution containing the precursors of copper and aluminum is added at a constant rate (70 ml / min) using a peristaltic pump in a reactor containing a foot of water of 700 ml at 50 ° C. and whose pH was previously adjusted to 8 with a 30% solution of sodium hydroxide. The reaction medium is stirred mechanically (600 rpm), and the coprecipitation pH is continuously maintained around 8 (+/- 0.5) by addition of a 30% sodium hydroxide solution. The suspension obtained is filtered to obtain a cake, which is washed with 3 I of deionized water. The cake is then dried at 120 ° C. for 24 hours. The CuAI powder is calcined in a muffle furnace with a stage of 2 hours at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. The X-ray diffractogram of the material calcined at 800 ° C. indicates the presence of CuA1204 spinel and CuO (-6% by weight).

The residual Na content measured by ICP is 1644 μg / g, ie 0.16% by weight of the catalyst. Example 4 not in accordance with the invention: Catalyst D (Cu / Al = 0.54) The material is prepared by coprecipitation at constant pH: 122.5 g of copper nitrate and 350.1 g of aluminum nitrate are dissolved in 900 ml of deionized water. The solution containing the precursors of copper and aluminum is added at a constant rate (30 ml / min) using a peristaltic pump in a reactor containing a foot of water of 600 ml at 50 ° C. and whose pH was previously adjusted to 8 using a 30% solution of sodium hydroxide. The reaction medium is stirred mechanically (600 rpm), and the coprecipitation pH is continuously maintained around 8 (+/- 0.5) by addition of a 30% sodium hydroxide solution. The suspension obtained is filtered to obtain a cake, which is washed with 6 I of deionized water. The cake is then dried at 120 ° C. for 24 hours. The CuAI powder is calcined in a muffle furnace with a stage of 2 hours at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. The X-ray diffractogram of the material calcined at 800 ° C. indicates the presence of CuA1204 spinel and CuO (-6% by weight). The residual Na content measured by ICP is 175 μg / g, ie 0.02% by weight of the catalyst. Example 5 Non-Conforming to the Invention Catalyst E (Zn / Al = 0.5) Zinc aluminate is prepared by a synthesis method known as coprecipitation at a constant pH. 450 ml of 0.6 mol / l zinc nitrate solution is diluted in 1 l of deionized water. Similarly, 900 ml of 0.6 mol / l aluminum nitrate solution is diluted in 1.3 l of deionized water. In a reactor of several liters of capacity, 700 ml of deionized water at pH 6.5 are prepared. Solutions of zinc nitrate and aluminum nitrate are added at the same time into the reactor. A 25% ammonium hydroxide solution is also added to the reactor to maintain the pH of the solution at around 6.5. The precipitation is carried out at room temperature. The suspension obtained is filtered and the cake obtained is washed with 3.2 l of deionized water. The cake is then dried at 120 ° C. for 24 hours. The ZnAl powder is calcined in a muffle furnace with a stage of 2 h at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. The X-ray diffractogram of the material calcined at 800 ° C indicates the presence of spinel ZnA1204 and does not show the presence of ZnO. There is no residual Na.

Example 6 Non-Conforming to the Invention: Catalyst F (Co / Al = 0.5) The material is prepared by coprecipitation at a constant pH: 82.2 g of cobalt nitrate and 210.4 g of aluminum nitrate are dissolved in 500 ml of deionized water, the solution containing the precursors of copper and aluminum is added at a constant flow rate (17 ml / min) using a peristaltic pump in a reactor containing a foot of water of 550 ml at 50 ° C and whose pH was previously adjusted to 8 with a 30% solution of sodium hydroxide. The reaction medium is stirred mechanically (600 rpm), and the coprecipitation pH is continuously maintained around 8 (+/- 0.5) by addition of a 30% sodium hydroxide solution. The suspension obtained is filtered to obtain a cake, which is washed with 3 I of deionized water. The cake is then dried at 120 ° C. for 24 hours. The CuAI powder is calcined in a muffle furnace with a stage of 2 hours at 150 ° C. and then for 5 hours at a temperature of between 600 ° C. and 850 ° C., preferably at 800 ° C., with a temperature ramp of 10 ° C. C per minute. The X-ray diffractogram of the calcined material at 800 ° C indicates the presence of CoAl2O4 spinel.

The residual Na content measured by ICP is 1015 μg / g, ie 0.10% by weight of the catalyst. Catalyst G is obtained from non-conforming catalyst E by dry impregnation with a solution of sodium nitrate Na (NO 3). The catalyst G obtained is doped with 1% Na. Example 8 Catalysts H (Conforming) and I (Non-Conforming) Catalyst D was doped with two sodium contents, the doping being carried out by dry impregnation of a 0.1M sodium hydroxide solution. The catalyst H compliant is obtained after doping at a low sodium content (about 0.4% by weight). The non-compliant catalyst I is obtained after doping with a high sodium content (approximately 5% by weight). Catalyst D Catalyst H Catalyst I Content (leg) in sodium 175 4112 47900 (ie 0.02% by weight) (ie 0.41% by weight) (ie 4.79% by weight) Example 9 non-compliant: Catalyst J Catalyst C is treated in an acidic medium. An acid treatment has the effect of leaching the copper present in the catalyst. The impact of copper leaching was evaluated on catalyst C with a molar ratio Cu / Al equal to 0.52. The catalyst is brought into contact with a solution of acetic acid (10% by weight) for 1 hour at room temperature and the solid is then washed with distilled water and dried. The Cu / Al ratio then increases from 0.52 to 0.48, thus approaching catalyst B. With the washing, the sodium level has also decreased. Catalyst C thus has a leachable copper amount of 7.7% by weight of the total copper.

The resulting catalyst is catalyst J. This catalyst, obtained after leaching of the catalyst C, practically no longer comprises leachable copper (content less than 1%). Catalyst Na (μg / g) Ratio Cu / Al (mol) Catalyst C 1644 0'52 (0.16% wt) Catalyst J 0 0.48 (0.01 The following is a summary table of all the mixed oxides Catalyst Composition M, Al Ratio M / AI content of Na (μg / g) Na (% wt) A Cu, Al 0.37 7784 0.78 B Cu, Al 0.46 88 0 , 01 C Cu, Al 0.52 1644 0.16 D Cu, Al 0.54 175 0.02 E Zn, Al 0.50 0 0.00 F Co, Al 0.50 1362 0.14 G Zn, Al 0.50 9695 0.97 H Cu, Al 0.54 4112 0.41 I Cu, Al 0.54 47900 4.79 J Cu, Al 0.48 50 0.01 Example 10: Catalysts K, L, M and N Catalysts K, L , M and N are obtained respectively by impregnation of palladium on the catalysts A, G, F and E.

A palladium hydrogenating phase was added by dry impregnation of an aqueous solution of PdNO 3 at 0.792% by weight of Pd on solids A, G, F and E. The solution is added dropwise to the solid to be impregnated. The solid resulting from the impregnation is then dried overnight in an oven at 110 ° C and calcined under 2L / h / g of air at 450 ° C for 2 hours. The references of the solids resulting from the impregnation are given in the table below. Catalyst after Catalyst before Amount of impregnated impregnated impregnation impregnation (%) KA 0.2 LG 0.2 MF 0.2 NE 0.2 When the catalyst according to the invention comprises a copper aluminate, it is not necessary to add another hydrogenating metal. In order to compare the reductibility of the various Cu / Al, Zn / Al and Co / Al mixed oxides, TPR (thermal reduction reduction) measurements under 5% H2 in helium with ramp of 5 ° C / min were carried out. The monitoring of the water signal produced during the reduction by TCD analyzer as a function of the temperature makes it possible in particular to quantify the reduction of the catalysts. The temperature at which the reduction peaks appear is an indication of the reducibility of the solids. The table below shows the reduction temperature of the 1st and 2nd peak for catalysts having no added palladium (A, G and F) and for catalysts containing 0.2% by weight of Pd (K, L and M). . Impregnated Pd Catalyst Temperature Temperature (%) 1st peak reduction in TPR (° C) 2nd peak reduction in TPR A no 200 400 G no F no 850 K yes 180 360 L yes 180 M yes 180 800 Note that the Catalyst A containing no Pd has a low temperature reduction peak, which corresponds to the formation of metallic Cu. This phenomenon is not observed for the other catalysts Zn and Co (respectively G and F) which are not reduced under the activation conditions of the catalytic test.

EXAMPLE 11 Catalytic Test Results, Effect of Addition of a Hydrogenating Metal by Dry Impregnation Catalysts A, G, F (without palladium) and K, L and M (0.2% of palladium) were tested in the acetol aldolization reaction after activation in situ under pure H2 at 300 ° C. The results are described in terms of aldol formation. As a reminder, the formation of aldol only requires the presence of acid-base functions. In the absence of reducible metal function under the process conditions, the formation of DIBK and MIBK does not take place. Catalyst A Catalyst G Catalyst F Catalyst K Catalyst L Catalyst M Aldol products Yes Yes Yes Yes Yes Yes MIBK, DIBK Yes No No Yes Yes Yes These results highlight the properties of Catalyst A, which has a hydrogenating activity after H2 activation. without the addition of Pd, unlike catalysts G and F. Thus, Cu / Al catalysts can be used without impregnation of Pd. EXAMPLE 12 Catalytic Test Results, Na Effect and Cu / Al Ratio Catalysts A, B, C, D, H, I and J were tested in the aldolisation reaction of acetone without addition of Pd in the conditions described above. The results are presented below in terms of conversion, selectivity to dimer and non-hydrogenated trimers of acetone (MIBK and DIBK), dimer and trimer hydrogenated acetone (MIBA and DIBA), selectivity to tetramers + unknown and of selectivity to light products (C1-C4) products of cracking side reactions. The rate of deactivation was also measured, it is described by the size: "Relative loss of yield of aldolization products after 24h" in the table below. Catalyst ABCDHIJ (comparative) (comparative) (comparative) (comparative) t = 0.5h conversion 57.7 77.0 70.0 74.5 60.0 53.0 62.0 acetone selectivity 33.4 26.0 25.0 24.7 30.6 38.3 27.8 MIBK selectivity 37.0 36.9 47.0 44.7 37.3 29.0 19.5 DIBK Catalyst ABCDHIJ (comparative) (comparative) (comparative) (comparative) selectivity 6.1 10.2 7.4 3.9 4.2 2.2 3.2 tetramers + unknown selectivity 3.0 2.7 2.5 2.3 3.2 4.1 2.9 alcohol MIBA selectivity 0 0 0 0 1.6 1.3 0 alcohol DIBA selectivity 16.0 11.0 9.0 7.6 15.4 20.1 17.3 IPA selectivity 6.6 10.8 6.7 13.5 6.6 3.3 26.3 C1-C4 efficiency 45.9 58.4 57.3 56.3 46.1 39.7 33.1 in aldol products t = 24h conversion 55.0 34.1 64.3 31.4 53.3 37.6 31.9 acetone selectivity 33.1 22.8 28.8 24.3 37.6 38.0 19.9 MIBK selectivity 36.2 3.2 42.1 3.0 32.7 14.2 1.9 DIBK selectivity 5.8 2.5 6.3 0.4 3.0 0.8 0.6 tetramers selectivity 1.3 2.6 2.8 2.8 3.8 4.1 2.2 alcohol MIBA selectivity 0 0.16 1.8 0 1.5 0.7 0 alcohol DIBA selectivity 18.0 46.5 11.1 52.9 19.2 39.2 50.5 IPA selectivity 6.1 22.8 6.2 16.0 5.2 2.2 24.4 C1-C4 efficiency 42.0 10.7 52.1 9.5 41.9 21.7 7.8 in aldol products Relative loss of 8.5% 81.7% 9.1% 83.1% 9.1% 45.3% 76.4% efficiency in aldolization products after 24h It is noted that the relative loss in yield of aldolization products after 24 hours on the catalysts A, C, H is very low, the conversion of acetone remains very stable after 24 hours of testing for these solids . On the other hand, for all the solids containing a too low content of Na, the deactivation is much more marked (solid B, D, I and J). For a close Cu / Al ratio (0.48 for the catalyst treated with the acid J and 0.52 for the catalyst C), but with a different Na content (501..tg / g for the leached catalyst J and 16444 / g for catalyst C), the relative loss of yields of aldol products is very different. The same observation is made for solids D, H and I with a Cu / Al molar ratio of 0.54 but of variable Na content (175, 4112 and 479004 / g respectively). The solids most loaded with Na also have a better selectivity for the desired products DIBK, MIBK and tetramers, the selectivity of Cl-C4 (light products) is more, higher on the solids with a low Na content. This can probably be explained by a neutralization of the acidic sites responsible for the cracking reactions responsible for the formation of C1-C4 products by Na. EXAMPLE 13 Catalytic Test Results, Effect of Na on L, M and N Catalysts L, M, N catalysts are respectively Zn, Co and Zn catalysts on which 0.2% Pd has been impregnated. The difference between L and N is in the sodium content, since N does not have one, unlike L (and M). They were tested under the same conditions as those of Example 12. MNL Catalyst (Comparative) t = 0.5h conversion 47.7 38.8 39.1 acetone selectivity MIBK 41.6 42.3 43.3 selectivity DIBK 16 , 1 11.9 12.7 selectivity 14.0 2.9 3.2 tetramers + unknown selectivity alcohol 3.6 4.6 3.5 MIBA selectivity alcohol 0 0 0 DIBA selectivity IPA 18.6 36.8 36.2 selectivity C1-C4 6.1 1.4 1.1 yield 35.9 23.9 24.5 aldolization products t = 24h conversion 45.4 30.1 38.2 acetone selectivity MIBK 43.3 33.3 42, 0 selectivity DIBK 15.7 4.6 11.2 selectivity 12.6 0.8 2.9 tetramers + unknown selectivity alcohol 3,4 3,6 4,5 MIBA selectivity alcohol 0 0,2 0 DIBA selectivity IPA 18, 9 55; 1 37.9 selectivity C1-C4 6.1 2; 1 1.5 yield 34.1 12.8 23.1 aldolization products 5% relative loss 46.4% 5.7% yield of aldol products after 24 h It is noted that sodium has the same effect on zinc aluminate or cobalt. Its presence greatly limits the loss of yield and the aging of the catalyst, which makes it possible to maintain a high yield of aldolisation products. As for Example 12 and by comparison between L and N, it is possible to deduce that the presence of sodium can make it possible to increase the yield of aldolization products, in particular by reducing the Cl -C 4 products (olefins and paraffins having between 1 and 4 carbon atoms). EXAMPLE 14 Comparison IPA Charge or Acetone The same catalytic test conditions as for Examples 12 and 13 were applied, the acetone charge was simply replaced by isopropanol. catalyst CC load acetone isopropanol t = 0.5h conversion charge 70.0 91.7 selectivity MIBK 25.0 18.8 selectivity DIBK 47.0 23.8 selectivity 7.4 4.2 tetramers + unknown selectivity MIBA 2.5 1, 9 selectivity DIBA 0 0 selectivity IPA 9.0 selectivity acetone --- 46.8 selectivity C1-C4 6.7 8.2 yield in products 57.3 44.7 aldolization t = 24h conversion acetone 64.3 89, 9 selectivity MIBK 28.8 18.0 selectivity DIBK 42.1 21.7 selectivity 6.3 3.6 tetramers + unknown selectivity alcohol 2,8 1,8 MIBA selectivity alcohol 1,8 0,4 DIBA selectivity IPA 11,1 selectivity acetone --- 50.6 selectivity C1-C4 6.2 3.9 yield of products 52.6 40.9 of aldolization Relative yield loss in 8% 9% aldolization products after 24h The behavior of the catalyst the isopropanol charge is the same as that of acetone in terms of product distribution and catalyst stability. It can therefore work indifferently with an alcoholic or carbonyl charge or a mixture of both.

Claims (2)

REVENDICATIONS1. Catalyst comprising: at least one aluminate of a metal M belonging to the columns 9 to 12 of the periodic table of elements whose molar ratio M / Al is between 0.2 and 0.8; at least one alkali metal or alkaline earth metal, the content of which represents from 0.05 to 4% of the total weight of said catalyst; at least one hydrogenating transition metal selected from the group consisting of nickel, palladium, platinum, copper, rhodium and ruthenium, alone or as a mixture; wherein at least 5% of the total weight of metal M is leachable, as determined by the reaction of 100 ml of 10% acetic acid with 10 g of powder catalyst for 1 hour with continuous stirring. Catalyst according to Claim 1, characterized in that the said metal M is chosen from the group consisting of cobalt, copper, nickel and zinc. Catalyst according to claim 1 characterized in that said metal M is copper. Catalyst according to claim 3 characterized in that said hydrogenating transition metal is copper. Catalyst according to one of Claims 1 to 4, characterized in that the said molar ratio M / Al is between 0.3 and 0.7. Catalyst according to one of Claims 1 to 4, characterized in that the said molar ratio M / Al is between 0.3 and 0.6. Catalyst according to one of claims 1 to 6 characterized in that said metal A is sodium, lithium or potassium. 10 15 2. 203. 4. 25 5. 6. 30 7.8. Catalyst according to one of claims 1 to 7 characterized in that said metal A represents from 0.08 to 4% of the total weight of said catalyst. 9. Catalyst according to one of claims 1 to 7 characterized in that said metal A represents from 0.08 to 2% of the total weight of said catalyst. 10. Catalyst according to one of claims 1 to 9 characterized in that it is free of chromium. 11. Catalyst according to one of claims 1 to 10 characterized in that at least 60% of the total weight of said catalyst is in the form of metal aluminate M. 12. Process for converting organic compounds carbonyls and / or alcohols aldolisation, crotonisation and hydrogenation, in a single reaction chamber, in the presence of hydrogen and of a catalyst according to one of claims 1 to 11, such that said process is carried out in the vapor phase at a temperature between 150 and 400 ° C, at a pressure between 0.1 and 2.0 MPa and with a molar ratio H2 / organic compounds of between 0 and 5 and with a PPH between 0.25 and 20 h-1.