• 专利附录
  • 专利说明
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    • 专利摘要:
    The invention relates to a catalyst comprising at least the tantalum element, and at least one acid-washed mesoporous oxide matrix comprising, at least before washing, 90% by weight of silica, the mass of the tantalum element representing between 0, 1 and 30% of the mass of said mesoporous oxide matrix.
    公开号:FR3038851A1
    申请号:FR1556662
    申请日:2015-07-13
    公开日:2017-01-20
    发明作者:Nicolas Cadran；Alexandra Chaumonnot
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；IFP Energies Nouvelles IFPEN；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:


    Exemple 1 - Préparation de la silice A une solution contenant 55 ml de tétraéthylorthosilicate (TEOS, Si(OCH2CH3)4) et 150 ml d’éthanol sont ajoutés 12,5 ml d’une solution d’acide nitrique à 68% (volumique) à température ambiante. L’ensemble est laissé sous agitation pendant 30 min. 50 ml d’une solution d’ammoniaque à 14% (volumique) sont alors ajoutés. Le système se trouble et un gel se forme. 19 ml d’éthanol sont alors ajoutés pour permettre une agitation supplémentaire durant 3 heures. Le gel final est filtré, lavé à l’éthanol puis séché à 100°C durant 24 heures. La poudre de silice obtenue est alors calcinée sous air à 550°C pendant 4 heures.
    Les caractéristiques des matrices oxydes mésoporeuses utilisées dans les exemples sont récapitulées ci-dessous.
    Tableau 1
    Exemple 2 - Lavage de la matrice oxyde mésoporeuse
    Les différentes matrices oxydes mésoporeuses décrites dans le tableau 1 (granulométrie : 250-500 μτή) sont placés sur un fritté n°4 sur lequel est passé pendant 1 heure une solution de lavage. Le volume de solution utilisé représente environ 5 fois le volume occupé par la matrice oxyde mésoporeuse. Les solides lavés sont rincés avec un volume équivalent d’eau distillée pendant 1 heure supplémentaire puis sont placés en étuve à 115°C pendant au moins 4 heures.
    Les caractéristiques des matrices oxydes mésoporeuses après lavages sont récapitulées dans le tableau 2.
    Tabieau 2
    Le lavage acide décrit ci-dessus a permis de diminuer les teneurs en alcalins en dessous de 1000 ppm pour l’ensemble des supports siliciques et a légèrement modifié la texture des supports.
    Exemple 3 - Imprégnation à sec des supports pour le dépôt du tantale
    Le pentaéthoxyde de tantale (Ta(OCH2CH3)5) (dont la quantité est calculée à partir de la teneur en Ta à déposer sur le support) est dilué dans une solution d’éthanol (dont la quantité est proportionnelle au volume poreux du support silicique). Cette solution est rapidement ajoutée au goutte à goutte et mélangée au support silice jusqu’à observer une mouillabilité de la surface de ce dernier (imprégnation à sec). Le solide est alors placé dans une atmosphère saturée en éthanol durant 3 heures, séché à 100°C durant 24 heures. Le catalyseur est obtenu par calcination du solide séché sous air à 550°C pendant 4 heures.
    Exemple 4 - Imprégnation à sec pour le dépôt de niobium L’oxalate d’ammonium et de niobium pentahydraté (dont la quantité est calculée à partir de la teneur en Nb à déposer sur le support) est dilué dans une solution aqueuse (dont la quantité est proportionnelle au volume poreux du support silicique). Cette solution est rapidement ajoutée au goutte à goutte et mélangée à la silice jusqu’à observer une mouillabilité de la surface de ce dernier (imprégnation à sec). Le solide est alors placé dans une atmosphère saturée en eau durant 3 heures, séché à 100°C durant 24 heures. Le càtalyseUr est obtenu par calcination du sôlide séché sous air à 550°C pendant 4 heures.
    Exemple 5 - Imprégnation à sec pour le dépôt de zirconium
    Le chlorure de zirconyle (dont la quantité est calculée à partir de la teneur en Zr à déposer sur le support) est dilué dans une solution aqueuse (dont la quantité est proportionnelle au volume poreux du support silicique). Cette solution est rapidement ajoutée au goutte à goutte et mélangée à la silice jusqu’à observer une mouillabilité de la surface de ce dernier (imprégnation à sec). Le solide est alors placé dans une atmosphère saturée en eau durant 3 heures, séché à 100°C durant 24 heures. Le catalyseur est obtenu par calcination du solide séché sous air à 550°C pendant 4 heures.
    Le tableau 3 présente un récapitulatif des catalyseurs préparés.
    Tableau 3
    Description de l'unité de test catalytique
    Le réacteur utilisé dans les exemples qui suivent consiste en un tube en acier inoxydable de 20 cm de long et de 10 mm de diamètre. Le réacteur est d'abord chargé avec du carborundum puis avec le catalyseur dilué dans du carborundum et enfin avec du carborundum. Le carborundum est inerte vis-à-vis de la charge et n’influe pas sur les résultats catalytiques ; il permet de positionner le catalyseur dans la zone isotherme du réacteur et de limiter les risques de problèmes de transfert de chaleur et de matière. La température du réacteur est contrôlée avec un four tubulaire à trois zones de chauffe. La charge liquide (mélange d’éthanol et d’acétaldéhyde dans une proportion R) est injectée via une pompe HPLC à double piston. Le flux liquide est vaporisé dans les lignes chauffées par un traceur avant d'entrer dans le réacteur et est homogénéisé par le passage dans un mélangeur statique. Les produits formés lors de la réaction sont maintenus en phase vapeur pour être analysés en ligne par chromatographie gazeuse (colonnes capillaires PONA et Carboxen 1010) pour permettre l’identification la plus précise des centaines de produits formés. Le catalyseur est activé in situ sous azote à la température de test. Les conditions opératoires spécifiques sont décrites dans les exemples suivants.
    Exemple 6 - Impact du lavage acide sur des catalyseurs comprenant du tantale
    Dans ce test, le ratio Ethanol/Acétaldéhyde de la charge est fixé à 2,6 (mol/mol), la température à 350°C et la pression à 0,15 MPa. Pour chaque catalyseur, le débit de charge est ajusté pour obtenir une pph constante de 250g/gTa/h.
    Les valeurs de sélectivité et de productivité carbone sont mesurés au niveau de ce point de fonctionnement. L’impact du lavage acide sur des catalyseurs à base de tantale est démontré par les résultats récapitulés dans le tableau 4.
    Tableau 4
    Le lavage acide de la matrice oxyde mésoporeuse avant imprégnation de l’élément tantale permet une amélioration de la productivité en butadiène et de la sélectivité du catalyseur pour toutes les matrices oxydes mésoporeuses utilisées par rapport aux catalyseurs ayant des teneurs identiques en tantale mais dont la matrice oxyde mésoporeuse n’a pas subi de lavage acide, ou pour lesquels la matrice oxyde mésoporeuse n’a subit qu’un lavage à l’eau.
    Exemple 7 - Impact du lavage acide sur des catalyseurs à base de niobium ou zirconium ne contenant pas l’élément tantale
    Tableau 5
    Les catalyseurs M et N sont obtenus en imprégnant 2%Nb sur une silice Davisil 636. On constate que le lavage acide de la silice permet une amélioration de la productivité, mais que la sélectivité de ces catalyseurs ne contenant pas l’élément tantale est fortement dégradée.
    Les catalyseurs O et P sont obtenus en imprégnant 2%Zr sur une silice Davisil 636. On constate une amélioration de la productivité, mais une absence d’effet sur la sélectivité du lavage acide de la silice sur ces catalyseurs ne contenant pas l’élément tantale. C’est donc bien l’association du lavage acide et de la présence de l’élément tantale qui permet un gain de sélectivité, et également de productivité pour la production de 1,3-butadiène.
    Exemple 8 - Impact de l’ordre des étapes préparatoires sur des catalyseurs à base de tantale Impact de l’ordre des étapes préparatoires sur des catalyseurs à base de tantale
    Le lavage acide du solide après dépôt de la phase active à base de tantale pennet également d’obtenir de meilleures performances. Ce résultat est surprenant car on aurait pu s’attendre à une altération de la phase active.
    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 "SK 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 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 balance of the main reaction is as follows: 2 CH3CH2OH ^ CH2CHCHCH2 + H2 + 2H20
    Behind this global assessment are numerous chemical reactions including a dehydrogenation reaction to generate acetaldehyde (I), an aldolization / crotonization reaction of acetaldehyde to crotonaldehyde (II), a Merwein-Pondorff reaction. Verley (MPV) between ethanol and crotonaldehyde (III) and finally a dehydration step of crotyl alcohol into butadiene (IV). I: CH3CH2OH CH3CHO + H2 II: 2 CH3CHO CH3CHCH-CHO + H2O
    III: CH3CHCH-CHO + CH3CH2OH → CH3CHCH-CH2OH + CH3CHO IV: CH3CHCH-CH2OH → CH2CHCHCH2 + H2O
    This multiplicity of chemical reactions is at the origin of many by-products if the sequencing of the steps is not done in the order specified above, especially with 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 stage, it should be noted that, depending on 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 may 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 an industrial unit "Carbide" led to the formation of the following impurities (by-products): diethyl ether (23% weight of impurities), ethylene (11% weight of impurities) ), hexenes, hexadienes (11% weight of impurities), etc. (WJ Toussaint, JT Dunn, Jackson DR, Industrial and Engineering Chemistry, 1947, 39 (2), p 120-125). Despite the presence of by-products, their formation is limited by the relatively low acid-base 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 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. 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 specific ethanol / acetaldehyde 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 (US2374433, US2436125, US2438464, US237855, US2477181). More recently, most recent 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 a combination Zr, Zn, La, the application WO 2014/049158 (Lanxess) uses a mixed oxide Mg If doped with elements such as Ti, V, Mo, Mn, Cu, Ni, Zn or Cr, the application WO 2013/125389 (Daicel) claims the use of a mixed oxide Mg-Si doped with a metal belonging to the columns 4 at 13, the application WO 2012/015340 (Unisit) uses the combination of an element in the metallic state of the column 11 and a metal oxide selected from magnesium, titanium, zirconium, tantalum and niobium.
    Note that, regardless of the research axis chosen by those skilled in the art to improve the performance of the catalyst in question, the medium of choice for all the materials studied is a mesoporous silicic carrier. Some studies have therefore focused on improving support. Thus, 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 mesostracted silica) .
    Acid washing of silicas is a method known to those skilled in the art to modify the performance of chromatographic columns by eliminating certain undesirable impurities (J. Nawrocki, Chromatographia, 1991, 31 (3/4), "Silica Surface Controversies, Strong Adsorption Sites, their Blocking and Removal .I Part I "). In catalysis, this technique has been used in the case of metathesis of olefins (US2011196185A (UOP LLC)) in the presence of a catalyst comprising tungsten dispersed on a support comprising silica, making it possible to improve the activity of the catalyst without degrade their selectivity. However, this particular implementation is not easily transposable. Thus, for example, if the productivity of a Nb-Silica catalyst is improved when the support is washed with acid, its selectivity in the 1,3-butadiene production reaction is strongly degraded. Summary of the Invention The invention relates to a catalyst comprising, and preferably consisting of, at least the tantalum element, and at least one acid-treated silica-based mesoporous oxide matrix, said matrix before washing comprising at least 90% silica weight, the tantalum mass representing between 0.1 and 30% of the mass of said mesoporous oxide matrix. The invention also relates to a process for the preparation of a catalyst comprising at least the following steps: a) at least one acidic washing step of a mesoporous oxide matrix comprising, before washing, at least 90% by weight of silica, the weight percentages being expressed with respect to the total mass of the mesoporous oxide matrix, with at least one organic acid and / or one inorganic acid, at a temperature between 0 ° C and 120 ° C and a contact time of said acid solution with said matrix mesoporous oxide between 10 min and 10 h, b) at least one heat treatment step of said washed matrix from step a) so as to obtain a catalyst support, c) at least one deposition step of at least one metal precursor of at least the tantalum element on the surface of said support obtained at the end of step b) and d) at least one step of heat treatment of the solid resulting from step c). The invention also relates to a method for preparing a catalyst comprising at least the following steps: a ') at least one step of depositing at least one metal precursor of at least the tantalum element on the surface of a mesoporous oxide matrix comprising at least 90% by weight of silica before washing, the weight percentages being expressed relative to the total mass of the mesoporous oxide matrix, b ') at least one heat treatment step of the solid resulting from step a' ), c ') at least one acidic washing step of the solid resulting from step b'), with at least one organic acid and / or one inorganic acid, at a temperature of between 0 ° C. and 120 ° C. and contact time of said acid solution with said solid between 10 min and 10 h, d ') at least one heat treatment step of the solid from step c'). The invention also relates to the use of the catalyst according to the invention for converting a feedstock comprising at least ethanol into butadiene, at a temperature of between 300 and 400 ° C., at a pressure of between 0.15 and 0. , 5 MPa, at a space velocity of between 0.5 and 5 hr.
    Interest of the invention
    Compared to the state of the art mentioned above, the present invention proposes an original approach for improving the potential of a butadiene production catalyst from a mixture comprising at least ethanol, via a specific and adapted pretreatment of the commonly used silicic carrier: an acidic wash. The latter does not only involve the removal of some potential impurities from the support but also modifies its surface chemistry, which leads to a better activity of the tantalum catalyst as well as an improvement in its selectivity. Another effect of the invention is an improvement in the productivity and selectivity of butadiene at iso-charge rate.
    DESCRIPTION OF THE INVENTION The invention relates to a catalyst used for the production of butadiene from a feedstock comprising at least ethanol, comprising at least the tantalum element capable of carrying out at least the reactions II to IV. above, and at least one acid-treated silica-based mesoporous oxide matrix.
    The catalyst according to the invention comprises a mesoporous oxide matrix based on washed silica by contacting said matrix with at least one acid, in particular an organic acid and / or an inorganic acid. Preferably, the acid employed is an inorganic acid, optionally diluted in an aqueous solution. Particular inorganic acids include nitric acid, sulfuric acid and hydrochloric acid, with nitric acid and hydrochloric acid being preferred. The concentration of inorganic acid used is generally in the range of 0.05 molar (M) to 3 M and preferably in the range of 0.1 M to 1 M. Said acidic wash may be carried out under static conditions (For example in "batch") or continuous (for example circulation in a washing column with or without partial or total recycling of the effluent). According to the invention, the representative conditions of this acid washing are a temperature generally between 0 ° C. and 120 ° C., preferably between 15 ° and 80 ° C., and very preferably between 20 ° C. and 70 ° C. C. The contact time of the acidic solution with the mesoporous oxide matrix may vary between 10 minutes and 10 hours and preferably between 30 minutes and 3 hours. An optional water rinsing operation can then be set up to eliminate excess acidity. This can be carried out under the same conditions as described above.
    The catalyst according to the invention comprises a mass of Ta of between 0.1 and 30%, preferably between 0.3 and 10%, preferably between 0.5 and 5% and very preferably between 0.5 and 5%. 2% of the mass of said 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 advantageously also comprises at least one element selected from the group consisting of the elements of groups 2, 3, 4 and 5 of the periodic table and their mixtures, preferably chosen from the group constituted by the elements of groups 2 and more preferably at least one member selected from the group consisting of Group 2 Group 2 and Group 5 Ca and Ba in the periodic table and mixtures thereof, the mass of said element representing between 0.01 and 5%, preferably between 0.01 and 1%, preferably between 0.05 and 0.5% of the mass of the silica-based mesoporous oxide matrix.
    In a particular arrangement, the catalyst according to the invention advantageously also comprises at least one element selected from the group consisting 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 group 12 of the periodic table 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 predominantly ethanol, it is meant that the mass ratio of ethanol to acetaldehyde in said feed, when said feedstock comprises acetaldehyde, is at least greater than 1, preferably at least greater than 5, said feed also possibly not being include acetaldehyde.
    The silica-based mesoporous oxide matrix having undergone an acidic washing step of the catalyst according to the invention is referred to as a catalyst support in the following text of the present invention.
    By silica-based mesoporous oxide matrix is meant a mesoporous oxide matrix comprising, before washing according to the invention, at least 90% by weight relative to the total mass of the mesoporous silica matrix silica. Preferably, said matrix before washing comprises silica in an amount of at least 95% by weight (that is to say from 95% up to 100%) relative to the total mass of the mesoporous oxide matrix, more preferably at least 98% by weight (i.e. from 98% to 100%) and even more preferably at least 99.5% by weight (ie ie from 99.5% up to 100%).
    The silica-based mesoporous oxide matrix before washing used according to the invention advantageously contains, in addition to silica, at least oxides that are part of the following non-exhaustive list: zirconia, titanium oxide, boron oxide, lanthanum oxide , cerium oxide ,. Preferably, the preoperated mesoporous oxide matrix used according to the invention additionally contains silica of titanium oxide. Additionally, the silica-based mesoporous oxide matrix of the catalyst according to the invention optionally comprises at least one element that is part of the following non-exhaustive list: Na, K, Mg, Ca, Al, Cu, Zn, Fe, Ni , Co, S, P. Advantageously, the silica-based mesoporous oxide matrix of the catalyst according to the invention comprises at least one element belonging to the group consisting of Na, K, Mg, Ca, Al, Cu, Zn, Fe, Ni, Co, S and P and their mixtures.
    The mesoporous oxide matrix based on silica before washing the catalyst according to the invention 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 classification of the IUPAC (Sing KSW, Everett DH, Haul RA, Moscow L., Pierotti J., Rouquerol J., Sieinieniewska T., Pure Appl. Chem., 1985, 57, 603). In addition to being mesoporous, said matrix may be mesostracted (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). The use of well-known mesostructured silicas, such as silicas SBA15 and MCM41, makes it possible to benefit from the very high specific surface areas developed by this type of solid (between 600 and 1200 m 2 / g).
    Very preferably, the silica-based mesoporous oxide matrix before washing the catalyst according to the invention is a mesoporous amorphous silica with unorganized porosity without micropores. For example, Davisil Grade 636 or 646 silicas, sold by WR Grace Co., Columbia, Md., Also known as "silica gels" because they are obtained by precipitation at pH, can be used. <7, the so-called commercial precipitated silicas, obtained via a pH> 7, or the so-called pyrogenic commercial silicas obtained by hydrolysis of SiCl 4 at 1000 ° C. It is also possible to synthesize the silica according to methods known to those skilled in the art, in particular by using the "traditional" inorganic 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). Particularly advantageous results are thus obtained after acid washing of a silica-based mesoporous oxide matrix characterized, before washing, with a specific surface area of at least 250 m 2 / g, preferably with a specific surface area of between 250 m 2 / g and 700 m 2 / g and even more preferably by a specific surface area of between 400 m 2 / g and 600 m 2 / g. In addition, the average pore diameter (or pore size) of the silica-based mesoporous oxide matrix before washing used according to the invention is preferably at least 4 nm, preferably between 4.5 and 50 μm. nm and even more preferably between 4.5 and 20 nm.
    In general, the process for preparing the catalyst according to the invention comprising at least the tantalum element and at least one acid-treated silica-based mesoporous oxide matrix comprises a) the acidic washing of the mesoporous oxide matrix. based on silica, b) the heat treatment of said washed matrix resulting from step a) so as to obtain the support of the catalyst according to the invention, c) the deposition of at least one metal precursor of at least the tantalum element on the surface of said support obtained at the end of step b) and d) the heat treatment of the solid resulting from step c) so as to obtain the catalyst according to the invention.
    According to step a) or a) of the process for preparing the catalyst according to the invention, the silica-based mesoporous oxide matrix is as described in the present text of the invention. In particular, said matrix may be commercial or well synthesized according to the methods known to those skilled in the art. In addition, said silica-based mesoporous oxide matrix may be used directly in powder form or already shaped, in particular in the form of pelletized, crushed and sieved powder, beads, pellets, granules, or extruded (hollow cylinders or not, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted rolls), or rings, etc., these shaping operations being performed by conventional techniques known to man of career. Preferably, said silica-based mesoporous oxide matrix is obtained in the form of extrudates with a size of between 1 and 10 mm. However, it is not excluded that said silica-based mesoporous oxide matrix obtained is then, for example, introduced into a device for rounding the surface, such as a bezel or other equipment allowing their spheronization.
    According to step a) of the process for preparing the catalyst according to the invention, the silica-based mesoporous oxide matrix employed is washed by contacting said matrix with at least one acid, in particular an organic acid and / or an inorganic acid. Preferably, the acid employed is an inorganic acid, optionally diluted in an aqueous solution. Particular inorganic acids include nitric acid, sulfuric acid and hydrochloric acid, with nitric acid and hydrochloric acid being preferred. The concentration of inorganic acid used is generally in the range of 0.05 molar (M) to 3 M and preferably in the range of 0.1 M to 1 M. Said acidic wash may be carried out under static conditions (For example in "batch") or continuous (for example circulation in a washing column with or without partial recycling, or total effluent). According to the invention, the representative conditions of this acid wash are a temperature generally between 0 ° C. and 120 ° C., preferably between 15 ° and 80 ° C., and very preferably between 20 ° C. and 70 ° C. ° C. The contact time of the acidic solution with the mesoporous oxide matrix can vary between 10 minutes and 10 hours and preferably between 30 minutes and 3 hours. An optional operation of rinsing with water can then be implemented in a controlled manner. to eliminate excess acidity. This can be carried out under the same conditions as described above. This operation is necessary in cases where the acid can not be easily removed during steps b) and d) of the catalyst preparation process according to the invention, the latter then being likely to be present on the final catalyst. These conditions apply mutatis mutandis to the solid resulting from step b ') in step c') of the preparation process according to the invention.
    This acidic washing step is crucial for improving the potential of a butadiene production catalyst from a mixture comprising at least ethanol, in that it induces the elimination of certain potential impurities from the support and or modifies its surface chemistry, which leads to better catalyst activity and improved selectivity. At the end of this operation and before the impregnation of the active element (s), the catalyst contains low sodium contents of between 0 and 500 ppm, preferably between 0 and 300 ppm and preferably between 0 and 100 ppm.
    According to step b) of the process for preparing the catalyst according to the invention, the mesoporous oxide matrix based on washed silica from step a) of the process for preparing the catalyst according to the invention undergoes at least one heat treatment. in order to release the porosity of said matrix. This treatment corresponds to drying, calcination and / or steaming of said washed matrix, according to the methods well known to those skilled in the art. Preferably, said treatment is carried out in a temperature range from 50 to 800 ° C, preferably from 80 ° C to 800 ° C and very preferably from 80 ° C to 300 ° C for a period of less than 72 hours and preferably less than 24 hours. These conditions apply mutatis mutandis in step d ').
    According to step c) of the process for preparing the catalyst according to the invention, at least one step of depositing at least one metal precursor of at least the tantalum element on the surface of said support obtained at the end of step b) is carried out by any synthetic method known to those skilled in the art. 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. For example, in the case of a deposit made by the dry impregnation method, step c) of the catalyst preparation process according to the invention consists of the following unit operations: the dissolution of at least one precursor at least the tantalum element in a volume of solution corresponding to the pore volume of the support obtained at the end of step b) of the preparation process according to the invention, the impregnation of said solution at the surface of said support and 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 support.
    According to step c) of the process for preparing the catalyst according to the invention, the metal precursor of at least the tantalum element is any compound comprising at least the tantalum element and can release this element in solution in reactive form. Thus, the precursors of at least the tantalum 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, for example, the formula M (OR) - where M = Ta. and R = ethyl, isopropyl, n-butyl, sec-butyl, t-butyl, etc. or a chelated precursor such as X (C5H802) 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 conditions of step c) apply mutatis mutandis to step a ').
    According to step d) of the process for preparing the catalyst according to the invention, the solid resulting from stage c) of the process for preparing the catalyst according to the invention then undergoes at least one heat treatment stage so as to obtain the catalyst according to the invention. This treatment corresponds to drying, calcination and / or steaming of said washed matrix, according to the methods well known to those skilled in the art. Preferably the treatment is drying followed by calcination. The drying phase is carried out by circulating on the solid a gas at a temperature between 50 and 200 ° C and preferably between 80 and 150 ° C for a period of between 1 and 24 hours. Preferably, said drying step is carried out under air. The calcination phase is carried out by circulating on the dried solid a gas at a temperature of between 350 and 700 ° C., preferably between 450 and 600 ° C. for a period of between 1 and 6 hours and preferably between 2 and 4 hrs. Said calcination step is carried out under a gaseous flow comprising oxygen. The conditions of step d) apply mutatis mutandis to step b ').
    In the case where the silica-based mesoporous oxide matrix required in step a) or a ') of the catalyst preparation process according to the invention is used in the form of an unformed powder, the catalyst according to the invention, itself unformed at the end of step d) or d) of the preparation process according to the invention, can be shaped in the form of pelletized, crushed, sieved powder, balls, pellets, granules, or extrudates (hollow cylinders or not, multilobed cylinders with 2, 3, 4 or 5 lobes for example, twisted cylinders), or rings, etc., these operations of implementation form being made 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 said 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 type 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 from 5 to 60% by weight, and preferably from 10 to 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.
    In this particular case of a shaping of the catalyst according to the invention subsequent to step d) of heat treatment of the preparation process, said post-treatment step is repeated after shaping.
    Finally, the optional addition of at least one element from groups 2, 3, 4, 5, 11 and 12 of the periodic table can be carried out according to all the methods known to those skilled in the art and to whichever steps of synthesis and / or shaping of the silica-based mesoporous oxide matrix used or the catalyst according to the invention.
    The aforementioned textural parameters are determined by the so-called "nitrogen volumetric" analysis technique which corresponds to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in pressure at a constant temperature. Specific surface area is defined as the BET specific surface area (SBet in m 2 / g) determined by nitrogen adsorption according to ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the periodical "The Journal of the American Society, 1938, 60, 309. The representative porous distribution of a mesopore population 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. The pore volume V is defined as the value corresponding to the volume observed for the partial pressure P / P ° max of the nitrogen adsorption-desorption isotherm. In the following description, the diameter of the mesospores φ of the mixed oxide according to the invention is determined by the formula 4000.V / SBET. The use of a mesoporous oxide matrix based on washed silica as support for a catalyst comprising at least the tantalum element for converting a feedstock comprising at least ethanol into butadiene, results in advantages of significant performance in terms of catalytic activity, conversion level obtained at a given reaction temperature and / or selectivity. The representative conditions for this reaction 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 When the treated feed also comprises acetaldehyde, the mass ratio ethanol / acetaldehyde is between 1 and 30, preferably between 2 and 10. The space velocity is defined as the ratio of the mass flow rate of charge to the mass of catalyst The invention is illustrated by means of the examples which follow.
    Examples Definition of terms
    EXAMPLE 1 Preparation of 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 a solution of 68% nitric acid (volume). 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.
    The characteristics of the mesoporous oxide matrices used in the examples are summarized below.
    Table 1
    Example 2 - Washing of the mesoporous oxide matrix
    The various mesoporous oxide matrices described in Table 1 (particle size: 250-500 μτή) are placed on a sintered No. 4 on which a washing solution is passed for 1 hour. The volume of solution used represents approximately 5 times the volume occupied by the mesoporous oxide matrix. The washed solids are rinsed with an equivalent volume of distilled water for an additional hour and are then placed in an oven at 115 ° C. for at least 4 hours.
    The characteristics of the mesoporous oxide matrices after washes are summarized in Table 2.
    Tabieau 2
    The acid washing described above made it possible to reduce the alkaline contents below 1000 ppm for all silicic supports and slightly modified the texture of the supports.
    Example 3 - Dry impregnation of the supports for the deposit of tantalum
    Tantalum pentaethoxide (Ta (OCH2CH3) 5) (the amount of which is calculated from the content of Ta to be deposited on the support) is diluted in an ethanol solution (the amount of which is proportional to the pore volume of the silicic carrier ). This solution is rapidly added dropwise and mixed with the silica support 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. The catalyst is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.
    Example 4 - Dry impregnation for the deposition of niobium The ammonium oxalate and niobium pentahydrate (whose amount is calculated from the content of Nb to be deposited on the support) is diluted in an aqueous solution (the amount of is proportional to the pore volume of the silicic carrier). This solution is rapidly added dropwise and mixed with the 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. C.alysis was obtained by calcining the dried sodium in air at 550.degree. C. for 4 hours.
    EXAMPLE 5 Dry Impregnation for Zirconium Deposition
    Zirconyl chloride (the amount of which is calculated from the Zr content to be deposited on the support) is diluted in an aqueous solution (the amount of which is proportional to the pore volume of the silicic carrier). This solution is rapidly added dropwise and mixed with the 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. The catalyst is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.
    Table 3 presents a summary of the catalysts prepared.
    Table 3
    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.
    Example 6 Impact of acid washing on catalysts comprising tantalum
    In this test, the Ethanol / Acetaldehyde ratio of the feed is set at 2.6 (mol / mol), the temperature at 350 ° C. and the pressure at 0.15 MPa. For each catalyst, the feed rate is adjusted to obtain a constant pph of 250g / gTa / h.
    The selectivity and carbon productivity values are measured at this operating point. The impact of acid washing on tantalum catalysts is demonstrated by the results summarized in Table 4.
    Table 4
    The acid washing of the mesoporous oxide matrix before impregnation of the tantalum element makes it possible to improve the productivity of butadiene and the selectivity of the catalyst for all the mesoporous oxide matrices used compared to catalysts having identical contents of tantalum but whose matrix The mesoporous oxide has not undergone any acid wash, or for which the mesoporous oxide matrix has only been washed with water.
    Example 7 Impact of acid washing on niobium or zirconium catalysts not containing the tantalum element
    Table 5
    The catalysts M and N are obtained by impregnating 2% Nb on a Davisil 636 silica. It can be seen that the acidic washing of the silica makes it possible to improve the productivity, but that the selectivity of these catalysts not containing the tantalum element is strongly degraded.
    The catalysts O and P are obtained by impregnating 2% Zr on a Davisil 636 silica. An improvement in the productivity is observed, but an absence of an effect on the selectivity of the acidic washing of the silica on these catalysts not containing the element tantalum. It is therefore the combination of acid washing and the presence of the tantalum element that allows a gain in selectivity, and also productivity for the production of 1,3-butadiene.
    Example 8 - Impact of the order of preparatory steps on tantalum catalysts Impact of the order of preparatory steps on tantalum catalysts
    The acidic washing of the solid after deposition of the tantalum-based active phase also makes it possible to obtain better performances. This result is surprising because one could have expected an alteration of the active phase.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    A catalyst comprising at least the tantalum element, and at least one acid-washed silica-based oxide mesosporous matrix, said matrix before washing comprising at least 90% by weight of silica, the tantalum mass being between 0.1 and 30% of the mass of said mesopressus oxide matrix.
    [2" id="c-fr-0002]
    The catalyst according to claim 1 wherein said acidic wash is carried out by contacting said matrix with at least one organic acid and / or an inorganic acid, at a temperature between 0 ° C and 120 ° C, and a contact time of the acidic solution with the mesoporous oxide matrix of between 10 minutes and 10 hours.
    [3" id="c-fr-0003]
    3. Catalyst according to one of claims 1 to 2 wherein said silica-based mesoporous oxide matrix before washing also contains at least one oxide selected from the group consisting of zirconia, titanium oxide, boron oxide, lanthanum oxide, cerium oxide and mixtures thereof.
    [4" id="c-fr-0004]
    4. Catalyst according to one of claims 1 to 3 wherein said mesoporous oxide matrix comprises at least one element selected from the group consisting of elements Na, K, Mg, Ga, Al, Cu, Zn, Fe, Ni, Co , S, P and mixtures thereof.
    [5" id="c-fr-0005]
    5. Catalyst according to one of claims 1 to 4 wherein said mesoporous oxide matrix is a mesoporous amorphous silica with unorganized porosity without micropores.
    [6" id="c-fr-0006]
    6. Catalyst according to one of claims 1 to 5 wherein said mesoporous oxide matrix has, before washing, a specific surface area of between 250 mVg and 700 m 2 / g.
    [7" id="c-fr-0007]
    7. Catalyst according to one of claims 1 to 6 wherein said oxide matrix is mesostructured.
    [8" id="c-fr-0008]
    8. 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 2, 3, 4, 5 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.
    [9" id="c-fr-0009]
    9. Catalyst according to claim 8 comprising at least one element selected from the group consisting of the elements of groups 2 and 5 of the periodic table and mixtures thereof, the mass of said element representing between 0.01 and 5% of the mass of said matrix. mesoporous oxide.
    [10" id="c-fr-0010]
    10. Catalyst according to claim 9 comprising at least one element selected from the group consisting of elements Ca, Ba, Nb and mixtures thereof, the mass of said element representing between 0.01 and 5% of the mass of said mesoporous oxide matrix.
    [11" id="c-fr-0011]
    11. Catalyst according to one of claims 1 to 10 also comprising at least one element selected from the group consisting of groups II 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.
    [12" id="c-fr-0012]
    12. Catalyst according to claim 11 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.
    [13" id="c-fr-0013]
    13. Process for preparing a catalyst according to one of claims 1 to 12 comprising at least the following steps: a) at least one acidic washing step of a mesoporous oxide matrix comprising before washing at least 90% by weight of silica the weight percentages being expressed with respect to the total mass of the mesoporous oxide matrix, with at least one organic acid and / or one inorganic acid, at a temperature of between 0 ° C and 120 ° C and a contact time of said acid solution with said mesoporous oxide matrix of between 10 min and 10 h, b) at least one step of heat treatment of said washed matrix resulting from step a) so as to obtain a catalyst support, c) at least one step depositing at least one metal precursor of at least the tantalum element on the surface of said support obtained after step b) and d) at least one step of heat treatment of the solid resulting from the step c).
    [14" id="c-fr-0014]
    14. Process for the preparation of a catalyst according to one of claims 1 to 12 comprising at least the following steps: a ') at least one step of depositing at least one metal precursor of at least the tantalum element on the surface of a mesoporous oxide matrix comprising, before washing, at least 90% by weight of silica, the weight percentages being expressed relative to the total mass of the mesoporous oxide matrix, b ') at least one heat treatment stage of the solid resulting from the step a '), c') at least one acidic washing step of the solid resulting from step b '), with at least one organic acid and / or an inorganic acid, at a temperature between 0 ° C and 120 ° C ° C and a contact time of said acid solution with said solid included between 10 min and 10 h, d ') at least one heat treatment step of the solid from step c'),
    [15" id="c-fr-0015]
    15. Use of the catalyst according to one of claims 1 to 12 for the conversion of a feedstock comprising at least ethanol into butadiene, at a temperature between 300 and 400 ° C, at a pressure between 0.15 and 0.5 MPa, at a space velocity of between 0.5 and 5 h -1,
    [16" id="c-fr-0016]
    16. Use according to claim 15 wherein the temperature is between 320 ° C and 380 ° C.
    [17" id="c-fr-0017]
    17. Use according to one of claims 15 to 16 wherein the pressure is between 0.15 and 0.3 MPa.
    [18" id="c-fr-0018]
    18. Use according to one of claims 15 to 17 wherein the space velocity is between 1 and 4 h'1.
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    同族专利:
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    US11148983B2|2021-10-19|
    CN107921414B|2021-08-10|
    JP6865206B2|2021-04-28|
    EP3322524A1|2018-05-23|
    RU2726116C2|2020-07-09|
    PL3322524T3|2021-11-02|
    FR3038851B1|2019-11-08|
    RU2018105072A3|2019-11-29|
    JP2018521842A|2018-08-09|
    WO2017009107A1|2017-01-19|
    RU2018105072A|2019-08-13|
    ZA201800044B|2018-12-19|
    US20180208522A1|2018-07-26|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1556662|2015-07-13|
    FR1556662A|FR3038851B1|2015-07-13|2015-07-13|CATALYST BASED ON TANTALUM BASED ON SILICA FOR THE TRANSFORMATION OF ETHANOL TO BUTADIENE|FR1556662A| FR3038851B1|2015-07-13|2015-07-13|CATALYST BASED ON TANTALUM BASED ON SILICA FOR THE TRANSFORMATION OF ETHANOL TO BUTADIENE|
    PL16739054T| PL3322524T3|2015-07-13|2016-07-05|Preparation process of a silica supported catalyst comprising tantalum for the transformation of ethanol into butadiene|
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    EP16739054.1A| EP3322524B1|2015-07-13|2016-07-05|Preparation process of a silica supported catalyst comprising tantalum for the transformation of ethanol into butadiene|
    US15/745,292| US11148983B2|2015-07-13|2016-07-05|Tantalum-based catalyst deposited on silica for the transformation of ethanol into butadiene|
    JP2018500619A| JP6865206B2|2015-07-13|2016-07-05|Silica-supported tantalum-based catalyst for conversion of ethanol to butadiene|
    PCT/EP2016/065823| WO2017009107A1|2015-07-13|2016-07-05|Tantalum-based catalyst deposited on silica for the transformation of ethanol into butadiene|
    RU2018105072A| RU2726116C2|2015-07-13|2016-07-05|Catalyst based on tantalum deposited on silicon oxide for converting ethanol to butadiene|
    ZA2018/00044A| ZA201800044B|2015-07-13|2018-01-04|Tantalum¿based catalyst deposited on silica for the transformation of ethanol into butadiene|
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