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    • 专利摘要:
    The invention relates to a mesoporous mixed oxide catalyst comprising silicon and at least one metal M selected from the group consisting of the elements of groups 4 and 5 of the periodic table and mixtures thereof, the mass of metal M being between 0.1 and 20% of the mass of the mixed oxide.
    公开号:FR3038849A1
    申请号:FR1556664
    申请日:2015-07-13
    公开日:2017-01-20
    发明作者:Nicolas Cadran；Alexandra Chaumonnot；Arnold Lambert
    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:

    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 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 CH3CH2OH CH2CHCHCH2 + H2 + 2H20
    Behind this global balance sheet lie many chemical reactions including a dehydrogenation reaction to generate acetaldehyde (I), an aldolization / crotonization reaction of acetaldehyde in crotonaldehyde (II), a reaction of Meerwein-Ponndorf- Verley (MPV) between ethanol and crotonaldehyde (III) and finally a dehydration step of crotyl alcohol into butadiene (IV). I: CH3CH2OH ^ CH3CHO + H2 II: 2 CH3CHO3 CH3CHCH-CHO + H20
    III: CH3CHCH-CHO + CH3CH2OH → CH3CHCH-CH2OH + CH3CHO IV: CH3CHCH-CH2OH → CH2CHCHCH2 + H20
    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, in 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 amorphous silica (Ind. Eng Chem. 1949, 41, p 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. (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 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 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 $ 1 / 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 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 studies have sought to eliminate tantalum completely 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, the application WO 2013/125389 (Daicel) claims the use of a metal-doped Mg-Si mixed oxide belonging to columns 4 to 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. SUMMARY OF THE INVENTION The invention relates to a mixed mesoporous oxide catalyst comprising silicon and at least one metal M selected from the group consisting of the elements of groups 4 and 5 of the periodic table and their mixtures, the mass of metal M being included between 0.1 and 20% of the mass of the mixed oxide. The invention also relates to the use of this catalyst for the production of 1,3-butadiene from a filler comprising at least ethanol at a temperature between 300 and 400 ° C, a pressure of between 0, 15 and 0.5 MPa, a space velocity of between 0.5 and 5 hr -1.
    Interest of the invention
    The present invention describes a process for the production of butadiene with a single reactor or with a series of reactors using a catalyst comprising, and advantageously consisting of an amorphous mesoporous mixed oxide comprising the silicon element, at least one metal M selected from the group constituted by the elements of groups 4 and 5 of the periodic table and their mixtures, that is to say of the periodic table of the elements, and optionally at least one metal M 'chosen from the group constituted by the elements of the groups 11 and 12 of the periodic table and their mixtures, advantageously a binder, and advantageously an organic adjuvant. An advantage of the present invention using said catalyst is an improvement in the maintenance of catalytic performance over the life of the catalyst, i.e. from one catalytic cycle to another. Another aspect of the invention is an increase in the number of possible regenerations and therefore the lifetime of the catalyst.
    SUMMARY OF THE INVENTION The invention relates to a catalyst comprising, and preferably consisting of a mesoporous mixed oxide, advantageously amorphous, comprising silicon, at least one metal selected from the group consisting of the elements of groups 4 and 5 of the table. and mixtures thereof and optionally at least one metal selected from the group consisting of the elements of Groups 11 and 12 of the Periodic Table and mixtures thereof, advantageously a binder, and its use as a catalyst for the production of butadiene from a feedstock. comprising at least ethanol and its preparation process.
    By mixed oxide is meant a solid resulting from the combination of oxygen atoms with at least two other different elements of the latter. Said mixed oxide comprises at least the silicon element as the first additional element to oxygen. Said mixed oxide also comprises at least one metal M selected from the group consisting of the elements of groups 4 and 5 of the periodic table and mixtures thereof. The presence of silicon and metal M define mixed oxides called "binary" called, for example, Ta-Si, Nb-Si, Zr-Si, etc. in the following text of the present invention. It is also possible to combine at least two metals M as defined above so as to obtain mixed oxides with three elements (ternary), four elements, etc. Preferably, said metal M is selected from the group consisting of tantalum, niobium, zirconium and mixtures thereof. Even more preferably, said metal M is selected from the group consisting of tantalum and niobium alone or as a mixture.
    Said mixed oxide may also optionally comprise a metal M ', in addition to silicon and metal M. Said metal M' is a metal selected from the group consisting of the elements of groups 11 and 12 of the periodic table and mixtures thereof. The presence of silicon, metal M and optional metal M 'define so-called "ternary" mixed oxides called, for example, Ta-Si-Ag, Nb-Si-Zn, etc. in the following text of the present invention. It is also possible to combine at least two metals M 'as defined above so as to obtain mixed oxides with four elements, etc. Preferably, said metal M 'is selected from the group consisting of silver, copper, zinc and mixtures thereof.
    Said mixed oxide comprises at least one M, the mass of said metal M being between 0.1 and 20%, preferably between 0.3 and 10%, preferably between 0.5 and 5% and very preferably between 0.5 and 2% of the mass of the mixed oxide.
    Said mixed oxide advantageously comprises a metal M ', the mass of metal M', when this is present, being between 0.1 and 20%, preferably between 0.3 and 10%, preferably between 0, 5 and 5% and very preferably between 0.5 and 2% of the mass of the mixed oxide.
    By mixed oxide comprising an element A, the mass of the element A being comprised, or representing between, x and y% of the mass of the mixed oxide, is understood to mean that said mixed oxide comprises between x and y parts by weight of said element A per 100 parts by weight of said mixed oxide.
    Said mixed oxide 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 mixed oxide can be mesostructured (that is to say have mesopores of uniform size and periodically distributed in the matrix) or hierarchically porous (presence of micropores and / or macropores additional to the mesopores). Preferably, said mixed oxide is mesoporous with unorganized porosity without micropores. Particularly advantageous results are obtained via the use of a mixed oxide having a surface area of at least 250 m 2 / g, preferably a surface area of at least 400 m 2 / g and even more preferably a surface specific of at least 600 m2 / g. Similarly, the pore volume of said mixed oxide is preferably at least 1 ml / g and more preferably at least 1.3 ml / g. In addition, the average pore diameter (or pore size) of said mixed oxide is preferably at least 4 nm, preferably between 4.5 and 17 nm and even more preferably between 4.5 and 10 nm.
    The catalyst according to the invention may advantageously comprise at least one porous oxide material having the role of binder so as to generate the physical properties of the catalysts 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 mixtures 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, montmorillonite, 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.
    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. By specific surface is meant the specific surface B.E.T. (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 journal "The Journal of 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 E. P. Barrett, L. G. Joyner and P. Halenda. The pore volume V is defined as the value corresponding to the volume observed for the partial pressure P / P ° 11.0x of the nitrogen adsorption-desorption isotherm. In the following description, the diameter of the mesopores φ of the mixed oxide according to the invention is determined by the formula 4000. V / Sbet-
    In order to ensure the catalytic performance of the catalyst according to the invention, the textural properties of said mixed oxide (to ensure a good diffusion of the reagents and products of the reaction), as well as the surface reactivity (nature, strength and number of active sites) while simultaneously playing on the chemical composition and the degree of homogeneity of said mixed oxide (preferred formation of MO-Si bonds, with M = metal, 0 = oxygen and Si = silicon). Consequently, said catalyst can be prepared by any method known to those skilled in the art for the aforementioned control. In particular, the synthetic routes to obtain these solids can be "traditional" inorganic synthesis methods (precipitation / gelling from salts) or "modern" metallo-organic (precipitation / gelling from alkoxides), these methods which can be named in a simplified way "sol-gel" methods. These "sol-gel" methods are based on chemical reactions of hydrolysis (or even complexation) and condensation of molecular precursors (salts or alkoxides), operated most often at atmospheric pressure and ambient temperature in an aqueous or aquo-organic medium. . 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, etc. These methodologies of synthesis, compared to other conventional ways, make it possible to better control the purity, the chemical composition, the homogeneity and the texture of mesoporous oxides. Preferably, the preparation process used to synthesize the catalyst according to the invention is the metallo-organic modern ground-gel route by precipitation / gelling comprising at least the following stages: (a) dissolving at least one precursor of the element Si in an aqueous medium, organic or aquo-organic (preferably aqueous-alcoholic), optionally in the presence of an acid or a base, so as to form a solution, possibly colloidal, (b) addition to the solution obtained during the operation (a) of at least one precursor of the metal M, in the pure state or dissolved in a suitable medium compatible with said solution resulting from the operation (a). The operation (b) can be repeated as many times as necessary, in particular during the non-joint addition of distinct elements M (ternary, quaternary systems, etc.), (c) precipitation of the mixed oxide based on If, and at least the metal M 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), (e) at least one heat treatment, advantageously hydrothermal, of the mixed oxide obtained in step (d) (drying and / or calcination, and / or steaming, etc.) so as to obtain the catalyst used according to the invention. Preferably, the mixed oxide obtained at the end of step d) is dried and then calcined. The drying step may be carried out in an oven in a temperature range from 20 to 200 ° C, preferably from 50 ° C to 150 ° C and preferably from 100 ° C to 130 ° C for a period of less than 72 ° C. h and preferably less than 24 h. The calcination step can be carried out 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. C at T = 700 ° C for a period of less than 24 hours and preferably less than 12 hours.
    The precursors of the element Si and at least the metal M used during the operation (a) can be any compound comprising the element Si or M and can release this element in solution in reactive form. Thus, the precursor (s) of at least one of said metal M are advantageously an inorganic salt of said metal M of formula MZn, (n = 3 or 4), Z being a halogen, the NO 3 group, the sulphate group or a perchlorate. The precursor (s) of at least one of said metal M may also be an alkoxy precursor (s) of formula M (OR) n where R = ethyl, isopropyl, n-butyl, s-butyl, t-butyl, etc. or a chelated precursor such as M (C5H802) -, with n = 3 or 4. The precursor (s) of at least one of said metal M (s) may still be an oxide (s) or a hydroxide (s) of said metal M. The silicic precursor is, for its part, obtained from any source of silica and advantageously from a sodium silicate precursor of formula Na 2 SiO 3, of a chlorinated precursor of formula SiCl 4 of an alkoxide precursor of formula Si (OR) 4 where R = H, methyl, ethyl or a chloroalkoxide precursor of formula Si (OR) 4-aCla where R = H, methyl, ethyl, a being between 0 and 4 The silicic precursor may also advantageously be an alkoxide precursor of formula Si (OR) 4-aR'a where R = H, methyl, ethyl and R 'is an alkyl chain or a functionalized alkyl chain, for example by a thiol, amino group, β-diketone, sulphonic acid, a being between 0 and 4. A preferred silicic precursor is tetraethylorthosilicate ( TEOS).
    Preferably, said metal M is not impregnated. Very advantageously, said metal M is incorporated only in step b) of the process for preparing the catalyst according to the invention.
    The catalyst according to the invention can be used in powder form or advantageously shaped in a step f) in the form of beads, pellets, granules, or extrudates (hollow or non-hollow cylinders, multilobed cylinders with 2, 3 , 4 or 5 lobes for example, twisted cylinders), or rings, etc., these shaping operations being performed by conventional techniques known to those skilled in the art. Preferably, said catalyst according to the invention is obtained at the end of a shaping step f) 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 step f) of shaping, the catalyst according to the invention may optionally comprise, and therefore be mixed with, at least one porous oxide material having the role of binder so as to generate the physical properties of the catalysts suitable for process (mechanical strength, attrition resistance, 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 mixtures 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, montmorillonite, 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 forming step f). 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 shaping the catalyst according to the invention subsequent to the heat treatment step e) of the preparation process, said heat treatment step can be repeated after shaping. The optional addition of at least one metal M 'chosen from the group constituted by the elements of groups 11 and 12 of the periodic table and their mixtures can be carried out according to all the methods known to those skilled in the art and to any what steps of synthesis and / or shaping of said catalyst according to the invention. In addition, the use of at least two separate metals M and optionally M '(ternary, quaternary systems, etc.) makes it possible to incorporate at least the additional metals M or M' at any stage of the process. synthesis and / or shaping of said mixed oxide used as catalyst according to the invention and this by all methods known to those skilled in the art.
    Another object of the invention is the use of the catalyst according to the invention for the conversion of a feedstock comprising at least ethanol into butadiene, resulting in significant performance advantages, in particular by increased stability. 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 said 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 between the mass flow rate of the feed and the catalyst mass. The invention is illustrated by means of the following examples.
    Examples
    EXAMPLE 1 Preparation of catalyst A based on 2% Ta / SiC 2 (2% by weight relative to the weight of silica) obtained by dry impregnation of the tantalum precursor associated with the surface of a Davisil commercial silica 636 (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 m2 / g, Vp ~ 0.9 ml / g and φ = 7 nm, particle size: 200-500 microns) until 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 the Ta-Si B mixed oxide catalyst comprising 2% by weight of Ta metal relative to the mass of the silica, obtained by the modern metallo-organic sol-gel route (according to the invention) to a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH2CH3) 4) and 150 ml of ethanol are added 12.5 ml of a solution of 68% (volume) nitric acid at room temperature. The whole is left stirring for 30 min. 0.66 g of tantalum ethoxide (Ta (OCH 2 CH 3) 5) are 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 K is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. The catalyst B obtained is characterized by the following textural data: SBet = 710 m 2 / g, Vp = 1.42 ml / g and φ = 11.7 nm.
    Example 3 Preparation of Catalyst C Based on 2% Nb / SiC 2 (2% by weight relative to the weight of silica) obtained by dry impregnation of the niobium precursor associated with the commercial silica surface Davisil 636 (Comparative) 4.24 g of niobium and ammonium pentahydrate oxalate are diluted in 80 ml of water. This solution is rapidly added dropwise and mixed with 50 g of Davisil 636 silica (SBET ~ 500 m2 / g, Vp ~ 0.9 ml / g and φ = 7 nm, particle size: 200-500 microns) up to 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 C is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.
    EXAMPLE 4 Preparation of Nb-Si D mixed oxide catalyst comprising 2% by weight of Nb metal relative to the mass of silica obtained by the modern metallo-organic sol-gel route (according to the invention) to a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH2CH3) 4) and 150 ml of ethanol are added 12.5 ml of a solution of 68% (volume) nitric acid at room temperature. The whole is left stirring for 30 min. 0.96 g of niobium ethoxide (Nb (OCH2CH3) 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 under air at 550 ° C. for 4 hours. The catalyst obtained D is characterized by the following textural data: SBet = 790 m 2 / g, Vp = 1.02 ml / g and φ = 6.7 nm.
    EXAMPLE 5 Preparation of the Catalyst E Based on 1% Zn / 2% Ta / SiQ 2 (1% by weight in Zn and 2% by weight relative to the mass of the silica) obtained by dry impregnation of the tantalum and zinc precursors associated with the Davisil 636 commercial silica surface (comparative) 2.27 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 m2 / g, Vp ~ 0.9 ml / g and φ ~ 7 nm, particle size: 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. 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 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 E is obtained by calcining the dried solid under air at 550 ° C. for 4 hours.
    Example 6 Preparation of the mixed oxide catalyst Ta-Si-Zn F comprising 1% by weight of Zn metal and 2% by weight of Ta metal relative to the mass of the silica obtained synthesis of the Ta-Si mixed oxide by the metallo-organic modern sol-gel route and dry impregnation of said mixed oxide with the associated zinc precursor (according to the invention) to a solution containing 55 ml of tetraethylorthosilicate (TEOS, Si (OCH 2 CH 3) 4) and 150 ml of ethanol 12.5 ml of a solution of 68% (volume) nitric acid at room temperature are added. The whole is left stirring for 30 min. 0.66 g of tantalum ethoxide (Ta (OCH 2 CH 3) 5) are 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 K is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. 0.91 g of zinc nitrate hexahydrate are diluted in 56 ml of water. This solution is rapidly added dropwise and mixed with 20 g of the Ta-Si mixed oxide (SBET = 710 m2 / g, Vp = 1.42 ml / g and φ "11.7 nm), up 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 F is obtained by calcining the dried solid under air at 550 ° C. for 4 hours. Definition of terms
    Conversion (% wt):
    Productivity (gc / gM / h)
    Selectivity (% C):
    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 protocol
    For all the catalysts prepared according to the examples described below, the test conditions were as follows:
    The transformation test of the alcoholic charge was carried out at a temperature at a pressure of 0.15 MPa with a starting temperature of 340 ° C. The charge rate (and thus the pph) is adjusted for each catalyst so as to initially (at 340 ° C) achieve the desired conversion level. The temperature is gradually increased to compensate for deactivation of the catalyst and maintain a stable level of butadiene productivity. The test is stopped from the moment when the test temperature exceeds 375 ° C. At the end of each test, the catalyst is regenerated by calcination under air. Regeneration conditions have been chosen to be the most representative of industrial regeneration. The conditions of the regeneration step are described in detail in Table 1 and the regeneration is carried out according to the diagram shown in Figure 1 which illustrates the schematic representation of the flow flow during the various phases. After a first period under a stream of nitrogen to remove the remaining volatile compounds present in the reactor and on the catalyst, air is introduced into the unit to initiate the regeneration of the catalyst. This air is diluted thanks to partial recycling of the gas at the outlet (recycle rate = 5), gas composed of a mixture N 2, CO 2 and H 2 O as well as unreacted oxygen. During this phase (periods 1-4), the temperature is gradually increased to burn the coke while controlling the exotherm of the reaction. Finally, the residual coke is completely burned after a last step under pure air (period 5). The unit is then inerted under N2 to begin the next test.
    FIG. 1 schematically represents the mode of circulation of the fluids during the regeneration phase.
    Table 1: operating conditions of the catalyst regeneration step The catalytic test / regeneration assembly is repeated 20 times so as to be able to extrapolate the life of the catalyst. In the following examples, this will correspond to the number of cycles that the catalyst can undergo before its productivity level reaches a critical level set at half of its initial level, that is to say at the level of the catalyst. just been prepared.
    Example 7 Comparison of the Mixed Oxide Ta-Si Catalyst System and Ta / Si Impregnated Catalyst In this example, the Ethanol / acetaldehyde ratio of the feedstock is set at 2.5 mol / mol, the test start temperature at 340 ° C. and the pressure at 0.15 MPa. For each catalyst, the feed rate is set to achieve 45% conversion. The maintenance of butadiene productivity on the cycle is ensured by a regular increase in the temperature of the reactor. The productivity losses between each cycle reflect the rate of aging of the catalyst.
    EXAMPLE 8 Comparison of the Nb-Si Mixed Oxide Catalyst System and Nb / Si Impregnated Catalyst In this example, the Ethanol / acetaldehyde ratio of the feedstock is set at 2.5 mol / mol, the test start temperature at 340 ° C. and the pressure at 0.15 MPa. For each catalyst, the feed rate is set to achieve a conversion of 30%. The maintenance of butadiene productivity on the cycle is ensured by a regular increase in the temperature of the reactor. The productivity losses between each cycle reflect the rate of aging of the catalyst.
    Example 9 Comparison of the Ta-Si-Zn Mixed Oxide Catalyst System and Ta / Zn / Si Impregnated Catalyst In this example, the Ethanol / acetaldehyde ratio of the feed is set at 24 mol / mol, the test start temperature at 340 ° C and the pressure at 0.15 MPa. For each catalyst, the feed rate is set to achieve 55% conversion. The maintenance of butadiene productivity on the cycle is ensured by a regular increase in the temperature of the reactor. The productivity losses between each cycle reflect the rate of aging of the catalyst.
    In Examples 7 to 9, it is observed that the mixed oxide catalyst according to the invention has a better stability than the catalyst having a similar formulation, but for which the active phase has been deposited on the support.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    A mixed mesoporous oxide catalyst comprising silicon and at least one metal M selected from the group consisting of the elements of groups 4 and 5 of the periodic table and mixtures thereof, the mass of metal M being between 0.1 and 20% of the mass of the mixed oxide.
    [2" id="c-fr-0002]
    The catalyst of claim 1 wherein said metal M is selected from the group consisting of tantalum, niobium, zirconium, and mixtures thereof.
    [3" id="c-fr-0003]
    3. Catalyst according to one of claims 1 to 2 comprising a metal M ', said metal M' being a metal selected from the group consisting of the elements of groups 11 and 12 of the periodic table and mixtures thereof, the mass of metal M being between 0.1 and 20% of the mass of the mixed oxide.
    [4" id="c-fr-0004]
    The catalyst of claim 3 wherein said metal M 'is selected from the group consisting of silver, copper, zinc and mixtures thereof.
    [5" id="c-fr-0005]
    5. Catalyst according to one of claims 1 to 4 wherein said mixed oxide is mesostructured.
    [6" id="c-fr-0006]
    6. Catalyst according to one of claims 1 to 5 wherein the mixed oxide has a specific surface area of at least 250 m 2 / g, a pore volume of at least 1 ml / g and an average pore diameter of at least 4 nm.
    [7" id="c-fr-0007]
    7. Catalyst according to one of claims 1 or 6 shaped in the form of beads, pellets, granules, or extrudates, or rings.
    [8" id="c-fr-0008]
    8. Catalyst according to claim 7 comprising at least one porous oxide material having the role of binder, said porous oxide material being selected from the group formed by silica, magnesia, clays, titanium oxide, lanthanum, cerium oxide, boron phosphates and mixtures of at least two of the oxides mentioned above.
    [9" id="c-fr-0009]
    9. Process for the preparation of the catalyst according to one of claims 1 to 8 by the sol-gel modern metallo-organic precipitation / gelling process comprising at least the following steps: (a) dissolution of at least one precursor of the element Si in an aqueous, organic or aquo-organic medium, optionally in the presence of an acid or a base, so as to form a solution, possibly colloidal, (b) addition to the solution obtained during the operation (a ) at least one precursor of the metal M, in the pure state or dissolved in a suitable medium compatible with said solution resulting from the operation (a), (c) precipitation of the mixed oxide based on Si, d at least the metal M 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) , (e) at least one heat treatment of the oxide mix obtained in step (d) to obtain said catalyst.
    [10" id="c-fr-0010]
    10. Process for preparing the catalyst according to claim 9 wherein said heat treatment step (e) is a drying followed by a calcination, said drying being carried out in an oven in a temperature range of 20 to 200 ° C for a period less than 72 hours, said calcination step being carried out under air in an oven in a temperature range of 300 to 800 ° C for a period of less than 24 hours.
    [11" id="c-fr-0011]
    11. Use of the catalyst according to one of claims 1 to 8 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 of between 0.5 and 5 hr -1.
    [12" id="c-fr-0012]
    12. Use according to claim 11 wherein the temperature is between 320 ° C and 380 ° C.
    [13" id="c-fr-0013]
    13. Use according to one of claims 11 to 12 wherein the pressure is between 0.15 and 0.3 MPa.
    [14" id="c-fr-0014]
    14. Use according to one of claims 11 to 13 wherein the space velocity is between 1 and 4 h "1.
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    同族专利:
    公开号 | 公开日
    EP3322531A1|2018-05-23|
    US11213802B2|2022-01-04|
    WO2017009105A1|2017-01-19|
    RU2018105073A|2019-08-14|
    US20180200694A1|2018-07-19|
    RU2018105073A3|2019-12-31|
    RU2722158C2|2020-05-27|
    FR3038849B1|2019-11-29|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1556664A|FR3038849B1|2015-07-13|2015-07-13|MESOPOROUS MIXED OXIDE CATALYST COMPRISING SILICON|
    FR1556664|2015-07-13|FR1556664A| FR3038849B1|2015-07-13|2015-07-13|MESOPOROUS MIXED OXIDE CATALYST COMPRISING SILICON|
    PCT/EP2016/065821| WO2017009105A1|2015-07-13|2016-07-05|Mesoporous mixed-oxide catalyst including silicon|
    RU2018105073A| RU2722158C2|2015-07-13|2016-07-05|Mesoporous catalyst based on mixed oxide containing silicon|
    US15/744,106| US11213802B2|2015-07-13|2016-07-05|Mesoporous mixed oxide catalyst comprising silicon|
    EP16736075.9A| EP3322531A1|2015-07-13|2016-07-05|Mesoporous mixed-oxide catalyst including silicon|
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