EP3322532A1

EP3322532A1 - Ta-nb catalyst for the production of 1,3-butadiene

Info

Publication number: EP3322532A1
Application number: EP16736077.5A
Authority: EP
Inventors: Nicolas Cadran; Alexandra Chaumonnot
Original assignee: Michelin Recherche et Technique SA Switzerland; Compagnie Generale des Etablissements Michelin SCA; IFP Energies Nouvelles IFPEN; Michelin Recherche et Technique SA France
Current assignee: Compagnie Generale des Etablissements Michelin SCA; IFP Energies Nouvelles IFPEN; Michelin Recherche et Technique SA France
Priority date: 2015-07-13
Filing date: 2016-07-05
Publication date: 2018-05-23
Also published as: US10792644B2; FR3038850B1; US20180200696A1; WO2017009108A1; FR3038850A1

Abstract

The invention relates to a catalyst including a mesoporous oxide matrix, said matrix including at least one oxide of an element X selected from among silicon and titanium, taken alone or in a mixture, said catalyst including at least the element tantalum and the element niobium, the mass of tantalum making up from 0.1 to 30% of the mass of the mesoporous oxide matrix, the mass of niobium making up from 0.02 to 6% of the mass of the mesoporous oxide matrix, the mass content of the element tantalum being no lower than the mass content of the element niobium. The invention also relates to the use of said catalyst in a method for producing 1,3-butadiene from a feedstock including at least ethanol.

Description

CATALYST Ta-Nb FOR THE PRODUCTION OF 1,3-BUTADIENE

State of the art

Butadiene is widely used in the chemical industry especially as a reagent for the production of polymers. Currently, butadiene is almost entirely produced from steam cracking units of which it is a valuable by-product. The fluctuation in the price of oil and the ever greater demand for this chemical intermediary have made its price very volatile, which encourages a diversification of the means of supply. It is well known to those skilled in the art that 1,3-butadiene can be produced from ethanol. Two processes have been industrialized on a large scale: the "S. K. Process" and the "Carbide Process". In the "SK Process", 1,3-butadiene is produced from ethanol in one step, whereas in the "Carbide Process", 1,3-butadiene is produced in two steps: ethanol is first converted to acetaldehyde, then an ethanol-acetaldehyde mixture is converted to 1,3-butadiene. The main distinction between the catalysts involved in these processes is that one (SK Process) is capable of dehydrogenating ethanol to acetaldehyde while producing butadiene from the mixture so formed while the other is hence the need for a first dehydrogenation step on a specific catalyst. The most effective catalyst components for this butadiene production method are magnesium, tantalum, zirconium, hafnium, with butadiene selectivities of 50 to 69%, with niobium (or columbium) considered an unattractive element with selectivities of less than 40% (BB Corson, HE Jones, CE Welling, JA Hinckley, EE Stahly, Ind. Eng Chem, 1950, 42 (2), p 359-373).

Whatever the process (one or two steps), the overall assessment of the main reaction is as follows:

2 CH ₃ CH ₂ OH - CH ₂ CHCHCH ₂ + H ₂ + 2H ₂ 0 Behind this global balance is hidden many chemical reactions including a dehydrogenation reaction to generate acetaldehyde (I), an aldolization / crotonization reaction from acetaldehyde to crotonaldehyde (II), a Merwein-Pondorff-Verley (MPV) reaction between ethanol and crotonaldehyde (III) and finally a dehydration step of crotyl alcohol to butadiene (IV). I: CH ₃ CH ₂ OH ≠ CH ₃ CHO + H ₂

II: 2 CH ₃ CHO ≠ CH ₃ CHCH-CHO + H ₂ 0

III: CH ₃ CHCH-CHO + CH ₃ CH ₂ OH CH ₃ CHCH-CH ₂ OH + CH ₃ CHO

This multiplicity of chemical reactions is at the origin of many by-products if the sequence of steps is not carried out in the order specified below. IV: CH ₃ CHCH-CH ₂ OH - CH ₂ CHCHCH ₂ + H ₂ 0 above, with in particular the presence of secondary dehydration and condensation reactions. In addition, other reactions may occur (such as isomerization, cyclization, Diels reaction and Assist, etc.) further increasing the number of by-products. At this point, note that, following the nature of the catalyst used for the conversion of ethanol (or ethanol-acetaldehyde mixture) to 1,3-butadiene, the distribution of said by-products can change significantly. Thus, the addition of an acidic element will increase the production of dehydration products (eg ethylene or diethyl ether) while the addition of a basic element will promote the formation of multiple condensation products (eg hexenes or hexadienes).

Consequently, irrespective of the process (one or two steps), the selectivity of the conversion of ethanol (or ethanol-acetaldehyde mixture) to 1,3-butadiene is moderate. However, because of the relatively high price of the raw material, the economic study of the process shows that the efficiency of the transformation of the load constitutes an important lever to ensure its viability. Many efforts have been made to maximize this selectivity.

In particular, during the development of the butadiene production process from an ethanol acetaldehyde mixture (two-step process), the best catalyst found was a tantalum oxide deposited on an amorphous silica (Ind. Eng. Chem., 1949, 41, pp. 1012-1017). The butadiene selectivity was 69% for an initial conversion of the feed of 34%. It has also been shown that the use of this same catalyst in a "Carbide" industrial unit led to the formation of the following impurities (by-products): diethyl ether (23% weight of impurities), ethylene (11% by weight) impurities), hexenes, hexadienes (11% weight of impurities), etc. (W. J. Toussaint, J. T. Dunn, D.R. Jackson, Industrial and Engineering Chemistry, 1947, 39 (2), 120-125). Despite the presence of by-products, their formation is limited by the relatively low acidicity properties of the tantalum element. The latter also makes it possible to catalyze reactions II, III and IV very effectively. One of its only drawbacks lies in its price.

In fact, according to a report written in 2012 by Jonathan Burla, Ross Fehnel, Philip Louie and Peter Terpeluk of the University of Pennsylvania titled "TWO-STEP PRODUCTION OF 1,3-BUTADIENE FROM ETHANOL", the price of silica is around $ 0.96 / lb and that of tantalum around $ 162 / lb. As an indication, the current prices of niobium and zirconium are around $ 20 / lb and $ l / lb, which is about an order of magnitude price ratio between niobium and tantalum and two orders of magnitude. of magnitude between zirconium and tantalum.

Various studies were then carried out to optimize the effectiveness of tantalum and / or to substitute this element. For example, the application WO 2014/061917 seeks to improve the tantalum-based catalyst via the use of a silicic carrier characterized by mesopores of uniform size and morphology and periodically distributed within the material (so-called mesostructured silica ). US Pat. No. 2,421,661 (WJ Toussaint, JT Dunn, Carbide and Carbon Chemical Corporation, 1947) describes, for its part, a process for the preparation of butadiene which comprises the conversion of an acyclic mono-olefinic aldehyde (crotonaldehyde or acetaldehyde) and of a monohydroxy alcohol (ethanol) on a zirconium oxide group catalyst, tantalum oxide, niobium oxide and one of the combinations of these oxides with silica. However, according to the examples provided, the tantalum oxide used alone remains the best catalyst for converting the ethanol / acetaldehyde specific mixture. According to Ind. Eng. Chem., 1950, 42 (2), p 359-373, the best combinations for the transformation of the ethanol / acetaldehyde mixture are: Ta-Cu, Ta-Zr, Zr-Nb, Zr-Ti and Zr-Th deposited on a silicic carrier (US 2374433, US2436125, US2438464, US2357855, US2447181). More recently, most studies have sought to completely eliminate tantalum from the catalytic formulation, especially through the use of the element zirconium or magnesium:

the application WO 2014/199349 (BASF) uses a combination Zr, Zn, Cu,

the application WO 2014/180778 (Synthos) claims an association Zr, Zn, La,

the application WO 2014/049158 (Lanxess) uses a mixed oxide Mg-Si doped with elements such as Ti, V, Mo, Mn, Cu, Ni, Zn or Cr,

WO 2013/125389 (Daicel) claims the use of a metal-doped Mg-Si mixed oxide belonging to columns 4 to 13,

WO 2012/015340 (Unisit) uses the combination of an element in the metallic state of column 11 and a metal oxide selected from magnesium, titanium, zirconium, tantalum and niobium.

Summary of the invention

The invention relates to a catalyst comprising a mesoporous oxide matrix, said matrix comprising at least one oxide of an element X selected from silicon and titanium, taken alone or as a mixture, said catalyst comprising tantalum and niobium, the mass of tantalum representing from 0.1 to 30% of the mass of the mesoporous oxide matrix, the niobium mass representing from 0.02 to 6% of the mass of the mesoporous oxide matrix, the mass content of tantalum element in said catalyst being greater than or equal to the mass content of niobium element in said catalyst. Interest of the invention

One aspect of the invention is to enhance the use of niobium as a cocatalyst of tantalum in the ethanol-acetaldehyde conversion reaction to 1,3-butadiene to maximize selectivity. and the productivity of 1,3-butadiene via a synergistic process involving these two elements. The Applicant has discovered that a subtle combination of these two elements makes it possible to accelerate the formation of butadiene, by taking advantage of the affinity of tantalum for reactions II and III and that of niobium for reactions III and IV. Surprisingly, this results in a synergistic effect which can be observed by the increase in productivity compared to the weighted average of the productivities induced by the elements Ta and Nb taken separately and by the improvement of the selectivity of the reaction with respect to the weighted average of selectivities induced by elements Ta and Nb tested separately. The present invention allows an improvement of the selectivity and / or the productivity at iso-conversion of the load.

In addition, the niobium element proves to be a particularly interesting candidate for partially substituting tantalum and thus reduce the production costs of the catalyst. So for a production of butadiene given, the amount of tantalum used is reduced. The invention therefore makes it possible to improve the costs with a catalyst having at least the same performance under operating conditions but with a lower content of tantalum than a catalyst based on tantalum alone. Presentation of the invention

The present invention relates to the synergistic combination of tantalum and niobium elements on the same catalyst in a process for the production of butadiene from ethanol, which process can be carried out in several reaction steps (one step or two steps). This synergy results in both a rise in productivity and an increase in selectivity compared to the performance of tantalum catalysts (excluding niobium) and niobium catalysts (tantalum excluded) in the form of extrudates tested separately. or by mechanical mixing.

This invention therefore makes it possible to significantly improve the butadiene production process by limiting the losses of raw materials in the form of unwanted by-products and by limiting the impact of the cost of the catalyst on the latter.

The invention thus relates to a catalyst, and its use for the production of 1,3-butadiene from a filler comprising at least ethanol, comprising at least the tantalum and niobium elements and at least one mesoporous oxide matrix.

The catalyst according to the invention comprises tantalum, the tantalum mass representing between 0.1 and 30%, preferably between 0.3 and 10%, preferably between 0.5 and 5% and very preferably between 0 and 1%. , 5 and 2% of the mass of the mesoporous oxide matrix. By catalyst comprising an element A, the mass of the element A being comprised, or representing between, x and y% of the mass of the mesoporous oxide matrix, is understood to mean that said catalyst comprises between x and y parts by weight of said element A per 100 parts by weight of said mesoporous oxide matrix.

The catalyst according to the invention also comprises niobium, the mass of niobium representing between 0.02 and 6%, preferably between 0.02 and 2%, preferably between 0.05 and 1% and very preferably between 0.05 and 0.5% of the mass of the mesoporous oxide matrix.

In addition, the tantalum and niobium elements are introduced into the catalyst according to the invention so that the mass content of tantalum element expressed in% weight of metal relative to the mass of the mesoporous oxide matrix is greater than or equal to the mass content. in niobium element expressed in% weight of metal relative to the mass of the mesoporous oxide matrix, the weight% of metal being calculated as the ratio of the mass of metal to the mass of the mesoporous oxide matrix. The catalyst according to the invention advantageously also comprises at least one element selected from the group consisting of the elements of groups 1, 2, 3 and 4 of the periodic table and their mixtures, preferably of at least one element selected from the group consisting of by the elements of groups 1 and 2 of the periodic table and their mixtures and, even more preferably, of at least one element selected from the group consisting of the Cs element of group 1 and the elements Ca and Ba of group 2 of periodic table and mixtures thereof, the mass of said element representing between 0.01 and 5%, preferably between 0.01 and 1%, preferably between 0.01 and 0.5% of the mass of the mesoporous oxide matrix.

The addition of at least one element selected from the group consisting of the elements of groups 1, 2, 3 and 4 of the periodic table and their mixtures, preferably at least one element selected from the group consisting of the elements of groups 1 and 2 of the periodic table and their mixtures and, even more preferably, at least one element selected from the group consisting of the Cs element of group 1 and the elements Ca and Ba of group 2 of the periodic table and their mixtures makes it possible to improve the selectivity of the catalyst according to the invention at the cost of a loss of productivity.

In a particular arrangement, the catalyst according to the invention advantageously also comprises at least one element selected from the group consisting of the elements of groups 11 and 12 of the periodic table and their mixtures, that is to say from the periodic table of elements, more preferably at least one element selected from the elements of the group 12 of the periodic table and their mixtures and even more preferably the element Zn, the mass of said element representing between 0.5 and 10%, and preferably between 1 and 5% of the mass of said mesoporous oxide matrix based on silica. This arrangement is particularly advantageous in the case where the catalyst according to the invention is used in a one-step process, that is to say in a process treating a feed mainly comprising ethanol. By mainly ethanol, it is meant that the mass ratio of ethanol to acetaldehyde in said feedstock, when said feedstock comprises acetaldehyde, is at least greater than 1, preferably at least greater than 5, said feed also possibly not comprising of acetaldehyde.

The catalyst matrix according to the invention is mesoporous and comprises at least one oxide of an element X chosen from silicon, titanium and their mixtures. Preferably, the element X is silicon. Said oxide matrix is mesoporous, that is to say that it is characterized by the presence of pores whose size varies between 2 and 50 nm according to the IUPAC classification (KSW Sing, Everett DH, RA Haul, L Moscow, J. Pierotti, J. Rouquerol, T. Siemieniewska, Pure Appl. Chem., 1985, 57, 603). In addition to being mesoporous, said matrix may be mesostructured (that is to say have mesopores of uniform size and periodically distributed in said matrix) or hierarchically porous (presence of micropores and / or macropores additional to mesopores). Very preferably, the mesoporous oxide matrix constituting the catalyst according to the invention is a mesoporous amorphous silica with unorganized porosity without micropores. More particularly, use will be made of silicon oxides (silicas) having a specific surface area of 100 to 1200 m ² / g, and preferably of at least 400 m ² / g, a mesoporous volume of between 0.2 and 1.8. ml / g and preferably at least 0.6 ml / g and a mesopore diameter of between 4 and 50 nm and preferably at least 6 nm. For example, a Davisil Grade 636 commercial silica (SBET ~ 500 m ² / g, Vp ~ 0.9 ml / g and φ ~ 7 nm) can be used. Advantageously, the catalyst matrix according to the invention does not undergo acid washing.

More particularly, use will be made of silicon oxides (silicas) containing an alkali metal content expressed in% by weight of metal relative to the mass of the mesoporous matrix of less than 1% by weight, preferably less than 0.5% by weight, and of very preferred way less than 0, 1% weight.

The catalyst according to the invention can be prepared according to the methods known to those skilled in the art. The tantalum and niobium elements, as well as the optional additional element constituting the catalyst according to the invention can therefore be introduced by any method known to those skilled in the art and at any stage of the preparation of the catalyst according to the invention.

The catalyst according to the invention is prepared by consecutive introduction of the niobium element and then of the tantalum element. The applicant has indeed observed that, surprisingly, the catalyst according to the invention prepared by first introducing the niobium element and then the tantalum element had superior performance to the catalysts prepared by introducing first, or simultaneously, the tantalum element and then the niobium element, in particular in the uses according to the invention.

Thus, the tantalum and niobium elements, as well as the optional additional element constituting the catalyst according to the invention can be introduced by depositing precursors associated with the surface of a preformed mesoporous oxide matrix. The latter can be commercial or well synthesized according to the methods known to those skilled in the art, in particular by using so-called "sol-gel" synthesis methods (see the definition below). For example and in a non-exhaustive manner, so-called methods of dry impregnation, excess impregnation, CVD (Chemical Vapor Deposition or Chemical Vapor Deposition), CLD (Chemical Liquid Deposition or chemical deposition in liquid phase), etc. . can be used.

Another option is to use as a method for preparing the catalyst according to the invention any synthesis method known to those skilled in the art for introducing the precursors associated with tantalum and niobium elements, as well as those associated with the additional element optionally, directly during the synthesis of the chosen preformed mesoporous oxide matrix. For example and in a non-exhaustive way, the synthesis methodologies used may be inorganic "traditional" synthesis methods (precipitation / gelling from salts under mild conditions of temperature and pressure) or "modern" metallo-organic (precipitation / gelling from alkoxides under mild conditions of temperature and pressure), the latter being able to be referred to simply as "sol-gel" methods. he It is also possible to use "sol-gel" methods combined with the use of specific synthetic methods such as spray-drying (also called atomization), dip-coating, or other.

According to a preferred embodiment of the present invention, the methods making it possible to ensure the best dispersion of the tantalum and niobium elements, as well as any additional element, are chosen in order to maximize the productivity and the selectivity of the catalyst according to the invention. 'invention.

For a deposit of the precursors of these elements on the surface of the preformed mesoporous oxide matrix, the so-called dry impregnation method is preferred. No particular limitation exists as to the number of times that said dry impregnation step is repeated. The various steps can be carried out using one or more solvents or solvent mixture in which the precursors of the tantalum and niobium elements, as well as the optional additional element, are soluble. These solvents may be polar / protic such as water, methanol or ethanol, polar / aprotic such as toluene or xylene or apolar / aprotic such as hexane. The acidity of the solutions can also be adapted (addition of acid) to improve the solubility of the species. Similarly, each of the elements tantalum, niobium and any additional element, may be impregnated alone or co-impregnated with at least one of the other elements, the only limitation being the joint presence of elements tantalum and niobium at the end of the process for preparing the catalyst according to the invention. A preferred embodiment consists in producing a first dry impregnation of the niobium element and then, consecutively, a second dry impregnation of the tantalum element. A typical dry impregnation step comprises, for example, the following operations:

(a) dissolving at least one precursor of the tantalum, niobium elements and any additional element in a volume of solution corresponding to the pore volume of the chosen preformed mesoporous oxide matrix,

(b) impregnating the solution obtained during the operation (a) on the surface of the chosen preformed mesoporous oxide matrix,

(c) optionally maturing the solid thus obtained in a controlled atmosphere and temperature so as to favor the dispersion of at least said precursor used according to the invention over the entire surface of the preformed mesoporous oxide matrix chosen,

(d) post-treatment (s) (hydro) thermal (s) possible solid obtained during operation (c) (drying and / or calcination, and / or steaming, etc.) so as to obtain an intermediate solid or, in fine, the catalyst according to the invention.

For an introduction of the precursors associated with the tantalum and niobium elements, as well as those associated with the optional additional element, directly during the synthesis of the mesoporous oxide matrix, the "sol-gel" synthesis methods by precipitation and atomization are preferred. . Even more preferably, the "sol-gel" synthesis method by precipitation is favored. In the particular case of a sol-gel precipitation synthesis leading to the production of a catalyst characterized by an unorganized porosity-based mesoporous oxide matrix, the process for preparing said catalyst according to the invention comprises, for example, example, the following operations:

(a) dissolving at least one precursor of at least the constituent X element of the mesoporous oxide matrix chosen in an aqueous, organic or aquo-organic medium, optionally in the presence of an acid or a base, so to form a solution, possibly colloidal,

(b) adding to the solution obtained during the operation (a) of at least one precursor of the elements tantalum, niobium and the optional additional element, in the pure state or dissolved in a suitable medium compatible with said solution solution of the operation (a). Operation (b) can be repeated as many times as necessary, in particular during the non-joint addition of the various elements tantalum, niobium and any additional element,

(c) precipitation of the chosen mesoporous oxide matrix containing tantalum, niobium and any additional element by addition of an acid, a base or by application of a specific reaction temperature,

(d) filtration followed by possible washes or evaporation of the suspension obtained during the operation (c),

(θ) post-treatment (s) (hydro) thermal (s) of the solid obtained in step (d) (drying and calcination, or steaming, etc.) so as to obtain the catalyst used according to the invention.

The precursor (s) of at least one of said X element chosen from silicon, titanium and their mixtures and constituting the mesoporous oxide matrix, used during the operation (a) little (ven) t be any compound comprising the element X and able to release this element in solution in reactive form. Thus, the precursor (s) of at least one of said element X is (are) advantageously an inorganic salt of said element X of formula XZ _n , (n = 3 or 4), Z being a halogen, group NO ₃ or perchlorate. The precursor (s) of at least one of said X element (s) may also be a precursor (s) alkoxide (s) of formula X (OR) _n where R = ethyl, isopropyl, n-butyl, s-butyl, t-butyl, etc. or a chelated precursor such as X (C5¾02) _n, with n = 3 or 4. The (s) precursor (s) of at least said element X considered (s) bit (s) may even be a (the) oxide (s) or a hydroxide (s) of said element X. In the preferred case where X is silicon, the silicic precursor is obtained from any source of silica and advantageously a sodium silicate precursor of formula Na ₂ Si0 ₃ , a chlorinated precursor of formula SiCl ₄ , an alkoxide precursor of formula Si (OR) ₄ where R = H, methyl, ethyl or a chloroalkoxide precursor of formula Si (OR) ₄ . _a _Cl where R = H, methyl, ethyl, a is between 0 and 4. The silicic precursor can also advantageously be an alkoxide precursor having the formula Si (OR) 4_ _has R _'where R = H, methyl, ethyl and R 'is an alkyl chain or a functionalized alkyl chain, for example with a thiol, amino, β-diketone or sulfonic acid group, a being between 0 and 4. A preferred silicic precursor is tetraethylorthosilicate (TEOS).

Whatever the method of incorporation of the tantalum and niobium elements and the optional additional element, the precursors of these elements are any compound comprising at least the tantalum or niobium element or the optional additional element and which can release this element by solution in reactive form. Thus, precursors of at least the tantalum or niobium element or the optional additional element are advantageously inorganic salts and alkoxide precursors. The inorganic salts are selected from the group consisting of halides, nitrates, sulfates, phosphates, hydroxides, carbonates, carboxylates, alcoholates, and combinations of two or more thereof, more preferably selected from the group consisting of chlorides, nitrates, carboxylates, alcoholates, and combinations of two or more thereof. The alkoxide precursors have as an example for formula M (OR) _n where M = Nb, Ta, etc. and R = ethyl, isopropyl, n-butyl, sec-butyl, t-butyl, etc. or a chelated precursor such as X (C5¾O2) _n , with n = 3 or 4.

For example, the preferred precursors of tantalum are tantalum pentachloride and tantalum pentaethanoate which can be used with most organic solvents. The preferred precursors of niobium are ammonium and niobium oxalate or niobium pentaethoxide.

The catalyst according to the invention may be shaped in the form of beads, pellets, granules, or extrudates (hollow or non-hollow cylinders, multilobed rolls with 2, 3, 4 or 5 lobes, for example, twisted rolls), or rings, etc., these shaping operations being performed by conventional techniques known to those skilled in the art. Preferably, said catalyst used according to the invention is obtained in the form of extrudates with a size of between 1 and 10 mm. However, it is not excluded that said materials obtained are then, for example introduced into equipment for rounding their surface, such as a bezel or other equipment allowing their spheronization. During the shaping operation, the catalyst according to the invention may optionally be mixed with at least one porous oxide material having the role of binder so as to generate the physical properties of the catalyst which are suitable for the process (mechanical strength, resistance to attrition, etc.).

Said porous oxide material is preferably a porous oxide material chosen from the group formed by silica, magnesia, clays, titanium oxide, lanthanum oxide, cerium oxide, boron phosphates and a mixture at least two of the oxides mentioned above. It is also possible to use titanates, for example titanates of zinc, nickel or cobalt. It is still possible to use simple, synthetic or natural clays of 2: 1 dioctahedral phyllosilicate or 3: 1 trioctahedral phyllosilicate such as kaolinite, antigorite, chrysotile, montmorillonnite, beidellite, vermiculite, talc. , hectorite, saponite, laponite. These clays can be optionally delaminated. The various mixtures using at least two of the compounds mentioned above are also suitable for acting as binder.

Very preferably, the binder used is silicic in nature. For example and non-exhaustively, said silicic binder may be in the form of powders or colloidal solutions.

Preferably, said catalyst comprises and is preferably composed of 5 to 60% by weight, and preferably between 10 and 30% by weight of silicic binder, the weight percentages being expressed relative to the total mass of said catalyst. Optionally, at least one organic adjuvant is also mixed during said shaping step. The presence of said organic adjuvant facilitates extrusion shaping. Said organic adjuvant may advantageously be chosen from methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose and polyvinyl alcohol. The proportion of said organic adjuvant is advantageously between 0 and 20% by weight, preferably between 0 and 10% by weight and preferably between 0 and 7% by weight, relative to the total weight of said shaped material.

Depending on the method of preparation of the catalyst according to the invention chosen, it is also possible to carry out said shaping step directly on the mesoporous oxide matrix constitutive of the catalyst according to the invention. In this case, the introduction of the elements tantalum, niobium and any additional element is carried out as described above by depositing the precursors of these elements on the surface of the mesoporous oxide matrix preformed and shaped. Whatever the method of incorporation of the tantalum and niobium elements and the optional additional element constituting the catalyst according to the invention and whatever the shaping steps chosen, a post-treatment step (s) ( hydro) thermal (s) (drying and / or calcination, and / or steaming, etc.) is applied to obtain the catalyst according to the invention. Preferably, the post-treatment applied is a calcination under air in an oven in a temperature range of 300 to 800 ° C, preferably from T = 450 ° C to T = 700 ° C and even more preferably from T = 540 ° C to T = 700 ° C for a period of less than 24 hours and preferably less than 12 hours.

The nitrogen volumetry corresponding to the physical adsorption of nitrogen molecules in the porosity of the catalyst according to the invention via a progressive increase of the pressure at constant temperature provides information on the textural characteristics (pore diameter, pore volume, surface specific) of the material used according to the invention. In particular, it provides access to the specific surface and the mesoporous distribution of the catalyst. Specific surface area is understood to mean the BET specific surface area (SBET in m ² / g) determined by nitrogen adsorption according to the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the "The Journal of American Society, 1938, 60, 309. The representative porous distribution of a mesopore population centered in a range of 2 to 50 nm (IUPAC classification) is determined by the Barrett-Joyner-Halenda model (BJH). The nitrogen adsorption-desorption isotherm according to the BJH model thus obtained is described in the periodical "The Journal of the American Society", 1951, 73, 373, written by EP Barrett, LG Joyner and PP Halenda. In the following description, the diameter of the mesopores f of the oxide-based matrix (s) corresponds to the value of the maximum diameter read on the pore size distribution curve obtained from the adsorption branch of the the nitrogen isotherm. In addition, the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity and the presence of the possible microporosity of the catalyst according to the invention. The quantitative analysis of the microporosity of the inorganic material obtained according to the invention is carried out using the "t" methods (method de Lippens-De Boer, 1965) or "oc _s " (method proposed by Sing) which correspond to transformations of the starting adsorption isotherm as described in the book "Adsorption by powders and porous solids." Principles, methodology and applications "written by F. Rouquerol, J. Rouquerol and K. Sing, Academy Press, 1999. These methods provide access in particular to the value of the microporous volume characteristic of the microporosity of the catalyst according to the invention.

In the following description of the invention, the porous distribution measured by mercury porosimetry is determined by mercury porosimeter intrusion according to ASTM standard D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a voltage of surface of 484 dyne / cm and a contact angle of 140 °. The angle of wetting was taken equal to 140 ° following the recommendations of the book "Techniques of the engineer, treated analysis and characterization, P 1050-5, written by Jean Charpin and Bernard Rasneur".

The value at which the mercury fills all the intergranular voids is fixed at 0.2 MPa, and it is considered that, beyond this, the mercury penetrates into the pores of the solid.

In order to obtain a better accuracy, the value of the total pore volume corresponds to the value of the total pore volume measured by mercury porosimeter intrusion measured on the sample minus the value of the total pore volume measured by mercury porosimeter intrusion measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).

The macroporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm. The mesoporous volume of the catalyst is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 and 50 nm.

The use of a catalyst comprising at least the tantalum and niobium elements and at least one mesosporous oxide matrix for the conversion of ethanol or an ethanol acetaldehyde mixture to butadiene results in significant performance advantages in terms of productivity and selectivity. The representative conditions for this reaction (conditions for which better productivity and better selectivity are observed) are a temperature of between 300 and 400 ° C., preferably between 320 ° C. and 380 ° C., a pressure of between 0.15 and 0.5 MPa, preferably between 0.15 and 0.3 MPa, a space velocity between 0.5 and 5 h ^-1 , preferably between 1 and 4 h ^-1 and, in the case of the "two-step" process wherein the feedstock comprises ethanol and acetaldehyde, an ethanol / acetaldehyde mass ratio of between 1 and 30, preferably between 2 and 10. The space velocity is defined as the ratio of the mass flow rate of the feedstock to the mass. of catalyst. The invention is illustrated by means of the following examples. Examples

EXAMPLE 1 Preparation of catalyst A based on 0.5% Ta / SiO 2 ^a (0.5% by weight relative to the weight of silica) obtained by dry impregnation of the tantalum precursor associated with the surface of the silica commercial Davisil 636 (a) (comparative)

0.67 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) 5) are diluted in 96 ml of ethanol. This solution is rapidly added dropwise and mixed with 60 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ "7 nm, particle size: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst A is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 2 Preparation of catalysts B, B 'and B "based on 0.5% Nb / SiO ₂ ^a , 0.25% Nb / SiO ₂ ^a and 1% Nb / SiQ ₂ ^a (0.5% 0.25% and 1 wt% Nb relative to the mass of the silica) obtained by dry impregnation of the niobium precursor associated with the Davisil commercial silica surface 636 (a) (comparative)

1.06 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ ~ 7 nm, particle size: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst B is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Catalyst B 'is similarly prepared with a half-fold precursor content (0.53 g of niobium and pentahydrate ammonium oxalate).

Catalyst B - is similarly prepared with twice the precursor content (2.12 g of niobium and ammonium pentahydrate oxalate) Example 3: Preparation of catalyst C based on 0.5% Nb / 0.5% Ta / SiO ₂ ^a (0.5 wt% Nb and Ta relative to the mass of the silica) obtained by successive dry impregnation of the niobium and tantalum precursors associated with the Davisil 636 commercial silica surface ( a) with intermediate calcination (comparative)

1.05 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Catalyst A until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst C is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. EXAMPLE 4 Preparation of Catalyst D Based on 0.5% Nb / 0.5% Ta / SiO 2 ^a (0.5% by Weight in Nb and Ta with respect to the Weight of Silica) Obtained by Successive Dry Impregnation niobium and tantalum precursors associated with Davisil commercial silica surface 636 (a) with intermediate drying (comparative)

0.67 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 96 ml of ethanol. This solution is rapidly added dropwise and mixed with 60 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ ~ 7 nm, granulometry: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. 1.27 g of niobium oxalate and ammonium pentahydrate are diluted in 96 ml of water. This solution is rapidly added dropwise and mixed with the dried solid until a wettability of the surface of the latter is observed (dry impregnation). The latter is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst D is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

EXAMPLE 5 Preparation of Catalyst E Based on 0.5% Ta / 0.5% Nb / SiO 2 ^a (0.5% by Weight in Nb and Ta with respect to the Weight of Silica) Obtained by Successive Dry Impregnation niobium and tantalum precursors associated with the surface of Davisil commercial silica 636 (a) with intermediate calcination (according to the invention)

0.33 g of tantalum ethoxide (Ta (OCH ₂ CH ₃₎ ₅₎ are diluted in 48 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of catalyst B until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst E is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 6 Preparation of Catalyst F Based on 0.25% Nb / 0.5% Ta / SiO 9 ^a (0.25% by weight in Nb and 0.5% by weight in Ta relative to the mass of silica) obtained by dry impregnation of the niobium and tantalum precursors associated with the commercial silica surface Davisil 636 (a) (comparative)

0.53 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Catalyst A until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst F is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 7 Preparation of Catalyst F 'and F "Based on 1% Nb / 0.5% Ta / SiO 9 ^a (1% by weight in Nb and 0.5% by weight in Ta relative to the mass of the silica) obtained by dry impregnation of the niobium and tantalum precursors associated with the commercial silica surface Davisil 636 (a) (outside the invention)

2.12 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Catalyst A until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water during 3 hours, dried at 100 ° C. for 24 hours. Catalyst F 'is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

2.54 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 60 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ ~ 7 nm, granulometry: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid obtained is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours.

0.67 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 96 ml of ethanol. This solution is rapidly added dropwise and mixed with the solid obtained to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst F "is obtained by calcination of the solid dried in air at 550 ° C. for 4 hours Example 8: preparation of Catalyst G based on 1% Ta / SiO 2 ^a (1% by weight in Ta relative to the weight of the silica) obtained by dry impregnation of the tantalum precursor associated with the surface of commercial silica Davisil 636 (a) (comparative)

1.34 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) 5) are diluted in 96 ml of ethanol. This solution is rapidly added dropwise and mixed with 60 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ "7 nm, particle size: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst G is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Example 9 Preparation of the catalyst H 0.5% Ta / SiQ 2 ^{| 3} (0.5% by weight of Ta relative to the mass of the silica) obtained by dry impregnation of the tantalum precursor associated with the surface of a synthesized silica (β) according to the modern metallo-organic sol-gel pathway (comparative)

Preparation of the silica:

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. The silica powder obtained is then calcined under air at 550 ° C. for 4 hours.

Catalyst preparation:

0.11 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are dissolved in 31.7 ml of ethanol. This solution is added dropwise and mixed with 10 g of silica until a wettability of the surface of the latter (dry impregnation) is observed. The solid is then placed in an atmosphere saturated with ethanol for 3 hours, dried at 100 ° C for 24 hours. Catalyst H is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

EXAMPLE 10 Preparation of the catalyst I 0.5% Nb / SiO 9 ³ (0.5% by weight relative to the mass of the silica) obtained by dry impregnation of the precursor niobium associated with the surface of a synthesized silica (β) according to the metallo-organic modern sol-gel route (comparative)

Preparation of the silica:

Catalyst preparation:

0.17 g of niobium and ammonium oxalate are dissolved in 18 ml of water. This solution is added dropwise and mixed with 10 g of silica until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst I is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 11: Preparation of the catalyst J 05% Nb / 0.5% Ta / SiC ¹ 2 ^{| 3} (0.5% by weight in terms of Nb and 0.5% by weight relative to the weight of the silica) obtained by impregnation to dry the niobium and tantalum precursors associated with the surface of a synthesized silica (β) according to the modern metallo-organic sol-gel route (according to the invention)

Preparation of the silica:

Catalyst preparation:

0.17 g of niobium and ammonium oxalate are dissolved in 18 ml of water. This solution is added dropwise and mixed with 10 g of silica until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. 0.11 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are dissolved in 31.7 ml of ethanol. This solution is added dropwise and mixed with 10 g of the solid Nb-SiO ₂ until a wettability of the surface of the latter (dry impregnation) is observed. The solid is then placed in an atmosphere saturated with ethanol for 3 hours, dried at 100 ° C. for 24 hours. Catalyst J is obtained by calcining the dried solid under air at 550 ° C for 4 hours. preparation of the catalyst J '05% Nb / 0.5% Ta / SiO9 ^{| 3} (0.5% by weight in terms of Nb and 0.5% by weight relative to the weight of the silica) obtained by dry impregnation of the precursors niobium and tantalum associated with the surface of a synthesized silica (β) according to the modern metallo-organic sol-gel route on which 100 ppm of sodium have been deposited (according to the invention)

Preparation of the silica:

Preparation of sodium doped silica

37 mg of sodium nitrate are dissolved in 18 ml of water. This solution is added dropwise and mixed with 10 g of silica until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours and then calcined under air at 550 ° C. for 4 hours.

Catalyst preparation:

0.17 g of niobium and ammonium oxalate are dissolved in 18 ml of water. This solution is added dropwise and mixed with 10 g of silica until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. 0.11 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) 5) are dissolved in 31.7 ml of ethanol. This solution is added dropwise and mixed with 10 g of the solid Nb-SiO ₂ until a wettability of the surface of the latter (dry impregnation) is observed. The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst J is obtained by calcining the dried solid under air at 550 ° C for 4 hours. EXAMPLE 12 Preparation of catalyst K based on 2% Ta / SiO 2 ^Y (2% by weight relative to the weight of silica) obtained by dry impregnation of the tantalum precursor associated with the commercial silica surface Evonik Aerolyst 3041 (γ) (comparative)

1.35 g of tantalum ethoxide (Ta (OCH ₂ -CH ₃₎ 5) are diluted in 28 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of Evonik extrudates (SBET ~ 160 m ² / g, Vp ~ 0.9 ml / g and φ ~ 25 nm) until a wettability of the surface is observed. of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst K is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. EXAMPLE 13 Preparation of catalyst L based on 0.5% Nb / SiO 2 ^Y (0.5% by weight relative to the weight of silica) obtained by dry impregnation of the precursor niobium associated with the surface of the silica Commercial Evonik Aerolyst 3041 (γ) (comparative)

0.63 g of niobium ammonium oxalate pentahydrate is diluted in 28 ml of water. This solution is rapidly added dropwise and mixed with 30 g of Evonik extrudates (SBET ~ 160 m ² / g, Vp ~ 0.9 ml / g and φ ~ 25 nm) until a wettability of the surface is observed. of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst L is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. EXAMPLE 14 Preparation of Catalyst M Based on 0.5% Nb / 2% Ta / SiO 2 ^Y (0.5% by weight in Nb and 2% by weight relative to the mass of silica) obtained by dry impregnation niobium and tantalum precursors associated with the surface of commercial silica Evonik Aerolyst 3041 (γ) (comparative)

0.63 g of niobium ammonium oxalate pentahydrate is diluted in 28 ml of water. This solution is rapidly added dropwise and mixed with 30 g of catalyst K to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst M is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 15 Preparation of Catalysts N, N 'and N "based on 0.5% Zr / SiO ₂ ^a , 0.25% Zr / SiO ₂ ^a and 0.05% Zr / SiO 2 ^a (0.5% 0.25% and 0.05 wt% Nb relative to the mass of the silica) obtained by dry impregnation of the zirconium precursor associated with the Davisil commercial silica surface 636 (a) (comparative)

0.88 g of zirconium chloride octahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Davisil 636 silica (SBET ~ 500 m ² / g, Vp ~ 0.9 ml / g and φ ~ 7 nm, granulometry: 200-500 microns) until 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst N is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Catalyst N 'is similarly prepared with a precursor content two times lower (0.44 g of zirconium chloride octahydrate).

Catalyst N "is similarly prepared with a tenfold lower precursor content (0.04 g of zirconium chloride octahydrate).

EXAMPLE 16 Preparation of the catalyst O based on 0.5% Zr / 0.5% Ta / SiO 2 ^a (0.5% by weight in terms of Zr and Ta relative to the mass of the silica) obtained by successive dry impregnation of zirconium and tantalum precursors associated with Davisil commercial silica surface 636 (a) with intermediate calcination (comparative)

0.18 g of zirconium chloride octahydrate are diluted in 15 ml of water. This solution is rapidly added dropwise and mixed with 10 g of Catalyst A until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C for 24 hours. Catalyst O is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 17 Preparation of catalysts P and P 'based on 1% Nb / 0.5% Zr / SiO ₂ ^a and 1% Nb / 0.25% Zr / SiO ₂ ^a (0.5% or 0.25% Zr weight and 1 wt% Nb relative to the mass of the silica) obtained by successive dry impregnation of the niobium and zirconium precursors associated with the surface of Davisil commercial silica 636 (a) with intermediate calcination (comparative)

0.42 g of niobium and ammonium pentahydrate oxalate are diluted in 15 ml of water. This solution is rapidly added dropwise and mixed with 10 g of Catalyst N until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst P is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

The same operation is repeated on the catalyst N 'to obtain the catalyst P'. EXAMPLE 18 Preparation of the Catalyst R Based on 0.5% Nb / 2% Ta / SiO2 ^a (0.5% and 2% by Weight in Nb and Ta with respect to the Weight of the Silica) Obtained by Successive Dry Impregnation niobium and tantalum precursors associated with Davisil commercial silica surface 636 (a) with intermediate drying (comparative)

2.68 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) 5) are diluted in 96 ml of ethanol. This solution is rapidly added dropwise and mixed with 60 g of Davisil 636 silica (SBET "500 m ² / g, Vp" 0.9 ml / g and φ "7 nm, particle size: 200-500 microns) 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. 1.27 g of niobium oxalate and ammonium pentahydrate are diluted in 96 ml of water. This solution is rapidly added dropwise and mixed with the dried solid until a wettability of the surface of the latter is observed (dry impregnation). The latter is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst R is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

EXAMPLE 19 Preparation of the catalyst S based on 0.75% Ta / SiC ¹ ^2/3 (0.75% by weight relative to the weight of the silica) obtained by the modern metallo-organic sol-gel route ( comparative)

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. 0.25 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are then added to the taste to taste under inert conditions to the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. Catalyst S is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Example 20: Preparation of catalyst T based on 0.25% Nb / 0.5% Ta / SiO 2 (0.25% by weight in terms of Nb and 0.5% by weight relative to the weight of silica) obtained by synthesis of the Nb / SiO solid by the metallo-organic modern sol-gel route and dry impregnation of the latter by the associated tantalum precursor (according to the invention) Preparation of the Nb-SiO ₂ solid

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. 0.13 g of niobium ethoxide (Nb (OCH ₂ CH ₃ ) 5) are then added to the taste to taste in conditions inert to the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. The Nb-SiO ₂ powder obtained is then calcined in air at 550 ° C. for 4 hours.

Catalyst preparation:

0.11 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are dissolved in 31.7 ml of ethanol. This solution is added dropwise and mixed with 10 g of the solid Nb-SiO ₂ until a wettability of the surface of the latter (dry impregnation) is observed. The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst T is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

in Ta relative to the mass of the silica) obtained by the metallo-organic modern sol-gel route (comparative)

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. A solution containing 0.13 g of niobium ethoxide (Nb (OCH ₂ CH ₃ ) s), 0.25 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) s) 5 ml of ethanol and 0, 4 ml of nitric acid at 68% (volumetric) is then added to the taste to taste under inert conditions in the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. Catalyst U is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Example 22 Preparation of Catalyst V Based on 10% Ta / SiO2 ^{| 3} (10% by weight relative to the weight of silica) obtained by the modern metallo-organic sol-gel route (comparative)

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. 3.31 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are then added to the taste to taste in conditions inert to the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. Catalyst X is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Example 23 Preparation of Catalyst W Based on 7% Nb / SiO 2 (10% by weight relative to the mass of silica) obtained by the modern metallo-organic sol-gel route (comparative)

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. 3.37 g of niobium ethoxide (Nb (OCH ₂ CH ₃ ) ₅ ) are then added to the taste to taste in conditions inert to the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. Catalyst X is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

EXAMPLE 24 Preparation of Catalyst X Based on 7% Nb / 10% Ta / SiQ 9 ³ (7% by weight in Nb and 10% by weight relative to the mass of silica) obtained by the modern sol-gel route metallo-organic (except invention)

To a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH ₂ CH ₃ ) ₄ ) and 150 ml of ethanol are added 12.5 ml of 68% (volume) nitric acid solution at room temperature. The whole is left stirring for 30 min. A solution containing 3.37 g of niobium ethoxide (Nb (OCH ₂ CH ₃ ) 5), 3.31 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) s), 20 ml of ethanol and 1, 6 ml of nitric acid at 68% (volumetric) is then added to the taste to taste under inert conditions at the previous mixture. 50 ml of a solution of ammonia at 14% (volume) are then added. The system becomes cloudy and a gel is formed. 19 ml of ethanol are then added to allow additional stirring for 3 hours. The final gel is filtered, washed with ethanol and then dried at 100 ° C. for 24 hours. Catalyst X is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

EXAMPLE 25 Preparation of catalyst Y based on 5% Zn / l% Ta / SiO 2 ^a (5% by weight in Zn and 1% by weight relative to the weight of silica) obtained by successive dry impregnation of zinc precursors and tantalum associated with the Davisil commercial silica surface 636 (a) (comparative)

11.37 g of zinc nitrate hexahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Davisil 636 silica (SBET ~ 500 m ² / g, Vp ~ 0.9 ml / g and φ ~ 7 nm, granulometry: 200-500 microns) until 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. The intermediate solid is obtained by calcining the dried solid under wet (20% water) at 550 ° C for 4 hours.

0.67 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 48 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of the previously prepared solid to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst V is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. EXAMPLE 26 Preparation of catalyst Z based on 5% Zn / 0.25% Nb / SiO 2 ^a (5% by weight in Zn and 0.25% by weight relative to the weight of silica) obtained by dry impregnation successive zinc and tantalum precursors associated with the Davisil commercial silica surface 636 (a) (comparative)

0.53 g of niobium oxalate and ammonium pentahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of the previously prepared solid until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. Catalyst W is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 27: Preparation of the AA catalyst based on 10% Zn / 0.25% Nb / l% Ta / SiO 2 ^a (10% weight in Zn, 0.25% Nb and 1% weight in Ta relative to the mass of the silica) obtained by successive dry impregnation of the zinc, niobium and tantalum precursors associated with the surface of the Davisil commercial silica 636 (a) (according to the invention)

22.74 g of zinc nitrate hexahydrate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Davisil 636 silica (SBET ~ 500 m ² / g, Vp ~ 0.9 ml / g and φ ~ 7 nm, granulometry: 200-500 microns) until 'to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. The intermediate solid is obtained by calcining the dried solid under wet (20% water) at 550 ° C for 4 hours.

0.53 g of niobium oxalate and ammonium pentahydrate are diluted in 76 ml of water. This solution is rapidly added dropwise and mixed with 50 g of the previously prepared solid until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. The intermediate solid is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

0.67 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 45 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of the previously prepared solid to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst X is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. EXAMPLE 28 Preparation of the AB Catalyst Based on 10% Zn 1.7% Ta SiO 2 ^a (10% by weight in Zn and 1.7% by weight relative to the weight of the silica) obtained by successive dry impregnation of zinc and tantalum precursors associated with commercial silica surface Davisil 636 (a) (comparative)

1.14 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 48 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of the previously prepared solid to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst Y is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Example 29: Preparation of the AC catalyst based on 10% Zn / 0.5% Nb / 0.8% Ta / SiO ₂ ^a (10% by weight in Zn, 0.5% by weight in Nb and 0.8% by weight in Ta relative to the mass of the silica) obtained by successive dry impregnation of the niobium, zinc and tantalum precursors associated with the commercial silica surface Davisil 636 (a) (according to the invention)

1.06 g of niobium oxalate and ammonium pentahydrate are diluted in 76 ml of water. This solution is rapidly added dropwise and mixed with 50 g of the previously prepared solid until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. The intermediate solid is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

0.54 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 48 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of the previously prepared solid to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst Y is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Example 30: Preparation of AD catalyst 10% Zn / 0.2% Nb / l, 4% Ta / SiQ ₂ ^a (10% by weight Zn, 0.2% by weight of Nb and 4% by weight Ta relative to the mass of the silica) obtained by successive dry impregnation of the niobium, zinc and tantalum precursors associated with the commercial silica surface Davisil 636 (a) (according to the invention)

0.42 g of niobium and ammonium pentahydrate oxalate are diluted in 76 ml of water. This solution is rapidly added dropwise and mixed with 50 g of the previously prepared solid until a wettability of the surface of the latter is observed (dry impregnation). The solid is then placed in an atmosphere saturated with water for 3 hours, dried at 100 ° C. for 24 hours. The intermediate solid is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

0.95 g of tantalum ethoxide (Ta (OCH ₂ CH ₃ ) ₅ ) are diluted in 48 ml of ethanol. This solution is rapidly added dropwise and mixed with 30 g of the previously prepared solid to observe a wettability of the surface of the latter (dry impregnation). The solid is then placed in a saturated ethanol atmosphere for 3 hours, dried at 100 ° C. for 24 hours. Catalyst Y is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.

Definition of pph terms

catalyst mass (gcat)

Conversion (% wt):

, _Λ mass flow rate of ethanol at the outlet + mass flow rate of acetaldehyde at the outlet,

conversion = 100 * (1;;)

mass flow of ethanol in inputs-mass flow rate of acetaldehyde in inlet

Productivity (g _c / g _cat / h)

oc

Mass flow rate of carbon belonging to butadiene (¾-)

productivity = - - catalyst mass gcat)

Selectivity (% C)

QC

Mass flow rate of carbon belonging to butadiene (¾-)

selectivity = - -

Mass flow rate of carbon belonging to the converted load {A + B} represents the weighted activity of the catalysts A and B in the absence of any interaction between these two catalysts.

pph {A + B] = pph (A) + pph (5) productivity {A + B} = productivity (A) + productivity (B) productivity (A) * selectivity (A) + productivity (B) * selectivity (B) ) selectivity {A + B]

productivity (A) + productivity (B)

If a superior result is obtained in the combination of A and B, we can speak of synergistic interaction. If a lower result is obtained, it is an antagonistic interaction.

Description of the catalytic test unit

The reactor used in the following examples consists of a stainless steel tube 20 cm long and 10 mm in diameter. The reactor is first loaded with carborundum and then with the catalyst diluted in carborundum and finally with carborundum. Carborundum is inert to the charge and does not affect catalytic results; it makes it possible to position the catalyst in the isothermal zone of the reactor and to limit the risks of problems of transfer of heat and material. The temperature of the reactor is controlled with a tubular furnace with three heating zones. The liquid feed (mixture of ethanol and acetaldehyde in a ratio R) is injected via a double piston HPLC pump. The liquid stream is vaporized in the heated lines by a tracer before entering the reactor and is homogenized by passing through a static mixer. The products formed during the reaction are maintained in the vapor phase for online analysis by gas chromatography (PONA capillary columns and Carboxen 1010) to allow the most accurate identification of the hundreds of products formed. The catalyst is activated in situ under nitrogen at the test temperature. The specific operating conditions are described in the following examples.

Catalytic test 1: demonstration of the synergistic effect Nb / Ta - EtOH / AcH load

In this test, the Ethanol Acetaldehyde ratio is set at 2.6 (mol / mol), the temperature at 350 ° C. and the pressure at 1.5 bar. For each catalyst, the pph and thus the charge rate are adjusted to obtain a 35% charge conversion.

Carbon productivity and butadiene selectivity values are measured at this operating point. Productivity

Content Content pph Selectivity

Butadiene catalyst

in Ta in Nb (g / g _cat / h) (% C)

A 0.5 - 0.9 0.18 68

B - 0.5 0.9 0.10 61

{A + Bj 0.5 0.5 1.8 0.21 65

except

C 0.5 0.5 2.0 0.26 73

invention

except

D 0.5 0.5 1.7 0.22 73

invention

according to

E 0.5 0.5 3.0 0.39 74

the invention

except

F 0.5 0.25 1.6 0.21 74

invention

Catalyst E according to the invention has a higher selectivity and productivity than catalysts outside the invention.

The catalyst F 'with a niobium content greater than that of tantalum does not make it possible to improve the selectivity and the productivity compared with the sum of the performances of the catalysts A and B ", even by modifying the order of addition of the tantalum and niobium (F "). Catalytic test 2: demonstration of the synergistic effect Nb / Ta - EtOH / AcH load

In this test, the Ethanol Acetaldehyde ratio is set at 2.6 (mol / mol), the temperature at 350 ° C. and the pressure at 1.5 bar. For each catalyst, the pph and thus the charge rate are adjusted to obtain a 25% charge conversion.

Carbon productivity and butadiene selectivity values are measured at this operating point.

The charge rate is set to achieve a 25% load conversion.

The catalysts J and J 'according to the invention have a selectivity and a productivity greater than that of the catalysts H and I.

Catalyst X with a niobium content greater than 6% does not make it possible to improve the selectivity and the productivity compared with the sum of the performances of the catalysts V and W. Catalytic test 3: demonstration of the absence of synergy Ta / Zr- EtOH / AcH load

Unlike the tantalum / niobium combination, the association between tantalum and zirconium does not improve the selectivity of the reaction and even has an antagonistic effect on the productivity of the catalyst.

Catalyst test 4: demonstration of the absence of synergism Nb / Zr- EtOH / AcH load In this test, the ratio Ethanol / acetaldehyde is fixed at 2.6 (mol / mol), the temperature at 350 ° C. and the pressure at 1.5 bar. For each catalyst, the pph and thus the charge rate are adjusted to obtain a 35% charge conversion.

The charge rate is set to achieve 35% load conversion

Productivity

Content Content pph Selectivity

Butadiene catalyst

in Nb in Zr (g / g _cat / h) (% C)

(g / g _cat / h)

B "1 - 1.8 0.20 59

N - 0.5 2.2 0.28 64

{B "+ NJ 1 0.5 4.2 0.48 62 excluding the invention P 1 0.5 2.7 0.38 66

B "1 - 1.8 0.20 59

N '- 0.25 1.2 0.16 65

{B "+ N'J 1 0.25 3.0 0.36 62 excluding the invention P '1 0.25 1.6 0.23 66 Unlike the tantalum / niobium combination, the association between niobium and zirconium improves the selectivity of the reaction but has an antagonistic effect on the productivity of the catalyst. Catalyst test 5: demonstration of the substitution effect - EtOH / AcH load

In this test, the ratio Ethanol Acetaldehyde is set at 2.6 (mol / mol), the temperature at 350 ° C, the pph to 2.5 h ^-1 and the pressure at 1.5 bar. Carbon productivity and butadiene selectivity values are measured at this operating point.

A calibration curve of the relationship between tantalum content and butadiene productivity is achieved by varying the tantalum content between 0.25% and 5%, the catalysts being prepared following the catalyst preparation protocol A. This curve is presented in FIG. 1. The curve presented in FIG. 1 allows, according to the productivity obtained under the conditions of the test with each catalyst based on Ta and Nb, to estimate the tantalum content that would be necessary to obtain this productivity if a catalyst containing only Ta was used. The amount of tantalum saved represents the difference between this value and the actual tantalum content of the catalyst tested.

The table shows that it is possible to obtain the same performance as a tantalum catalyst with niobium and tantalum catalysts, but with lower levels of tantalum. The catalyst E prepared by consecutive introduction of the niobium element and then the tantalum element allows a much greater saving of tantalum.

Catalyst test 6: demonstration of the substitution effect - EtOH / AcH load

In this test, the Ethanol / acetaldehyde ratio is fixed at 2.6 (mol / mol), the temperature at 350 ° C, the pph at 3 h ^" and the pressure at 1.4 bar .The carbon productivity and selectivity values in butadiene are measured at this point of operation.

The table shows that it is possible to obtain the same performance as a tantalum catalyst with catalysts based on niobium and tantalum but with lower levels of tantalum, the catalyst prepared by introducing consecutively the niobium then the tantalum allowing a significant productivity gain over the catalyst U in which tantalum and niobium were added simultaneously.

Catalyst test 7: demonstration of the synergistic effect - EtOH load

In this test, the feed contains only ethanol, the temperature is set at 375 ° C and the pressure at 1.4 bar. For each catalyst, the pph and thus the charge rate are adjusted to obtain a 55% charge conversion.

The catalyst X according to the invention has a higher selectivity and productivity than the catalysts V and W.

Catalyst test 8: Demonstration of the substitution effect - EtOH load

In this test, the feed contains only ethanol, the temperature is set at 350 ° C, the pph at 3h ^_1 and the pressure at 1.4 bar. Carbon productivity and butadiene selectivity values are measured at this operating point. Content Content Productivity

Content Conversion Selectivity

Catalyst in Ta in Nb butadiene

in Zn (% wt) (C)

(% wt) (% wt) (g / gcat / h)

Y 10 1.7 ... 55 0.34 63

according to

Z 10 0.8 0.5 53 0.29 61 the invention

according to

Z '10 1.4 0.2 55 0.30 63 the invention

The table shows that it is possible in the context of a one-step butadiene production process from ethanol to obtain the same performance as a tantalum catalyst with niobium and tantalum catalysts. but with lower contents in tantalum.

Claims

Catalyst comprising a mesoporous oxide matrix, said matrix comprising at least one oxide of an element X chosen from silicon and titanium, taken alone or as a mixture, said catalyst comprising tantalum and niobium, the tantalum mass representing 0, 1 to 30% of the mass of the mesoporous oxide matrix, the mass of niobium representing from 0.02 to 6% of the mass of the mesoporous oxide matrix, the mass content of tantalum element in said catalyst being greater than or equal to the content niobium element mass in said catalyst, said catalyst being prepared by consecutive introduction of the niobium element and then the tantalum element.

The catalyst of claim 1 wherein said oxide matrix is mesostructured.

Catalyst according to one of claims 1 to 2 wherein said oxide matrix is a silicon oxide having a specific surface area of 100 to 1200 m ² / g, a mesoporous volume of between 0.2 and 1.8 ml / g and a mesopore diameter between 4 and 50 nm.

Catalyst according to claim 3 wherein said oxide matrix contains an alkali metal content expressed in% by weight of metal relative to the mass of the mesoporous matrix less than 1% by weight.

Catalyst according to one of claims 1 to 4 also comprising at least one element selected from the group consisting of the elements of groups 1, 2, 3, 4 of the periodic table and mixtures thereof, the mass of said element representing between 0.01 and 5% of the mass of said mesoporous oxide matrix.

Catalyst according to claim 5, also comprising at least one element selected from the group consisting of the elements of groups 1, 2 of the periodic table and their mixtures, the mass of said element representing between 0.01 and 5% of the mass of said oxide matrix mesoporous.

Catalyst according to claim 6 comprising at least one element selected from the group consisting of Cs, Ca, Ba and mixtures thereof, the mass of said element representing between 0.01 and 5% of the mass of said mesoporous oxide matrix.

Catalyst according to one of claims 1 to 7 also comprising at least one element selected from the group consisting of the elements of groups 11 and 12 of the periodic table and mixtures thereof, the mass of said element representing between 0.5 and 10% of the mass of said mesoporous oxide matrix.

Catalyst according to claim 8 also comprising at least the Zn element, the mass of said element representing between 0.5 and 10% of the mass of said mesoporous oxide matrix.

10. Use of the catalyst according to one of claims 1 to 9 for the production of 1,3-butadiene from a feedstock comprising at least ethanol at a temperature between 300 and 400 ° C, a pressure included between 0 15 and 0.5 MPa, a space velocity between 0.5 and 5 h ^"1. 11. Use according to claim 10 wherein the temperature is between 320 ° C and 380 ° C.

12. Use according to one of claims 10 to 11 wherein the pressure is between 0.15 and 0.3 MPa. 13. Use according to one of claims 10 to 12 wherein the space velocity is between 1 and 4 h ¹ .