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    • 专利摘要:
    The invention relates to a catalytic composition comprising a catalytically active metal and a solid support, in which said catalytically active is rhodium and said solid support is CeO
    公开号:ES2546118A2
    申请号:ES201590076
    申请日:2013-01-24
    公开日:2015-09-18
    发明作者:Ricardo Arjona Antolín；Agustín Martínez Feliu；Pedro Luis BURGUETE LLORENS；Juan Luis SANZ YAGÜE
    申请人:Abengoa Bioenergia Nuevas Technologias SA；
    IPC主号:
    专利说明:

    Rhodium catalyst promoted for the selective conversion of synthesis gas into ethanol. FIELD OF THE INVENTION The present invention falls within the catalytic systems comprising rhodium as a catalytically active metal element and certain metal compounds that act as promoters of rhodium, for use in processes where advantageously, oxygen-containing compounds, particularly ethanol, are obtained. , from synthesis gas. BACKGROUND It is well known in the state of the art that rhodium catalysts supported and conveniently promoted by one or more metal oxides show a high selectivity to ethanol during the catalytic conversion of synthesis gas (also called "hydrogenation of CO") in comparison to other catalytic systems. A particularity of rhodium-based catalytic systems is the so-called "promoter effect" whereby rhodium needs a suitable promotion to show good activity and high selectivity to ethanol in the conversion of synthesis gas. Finding the optimal combination (and relative concentration) of promoters for rhodium is a complicated task since the “promoter effect” depends on many variables, including the chemical nature and textural properties of the support on which the metal phases are deposited (Rh + promoters). As rhodium promoters, metal oxides are often used including those of transition metals (Fe, Mn, V, Zr, etc.), lanthanide oxides (La, Sm, Th, Ce, etc.) or alkaline (for example Li). In the patent literature, there are numerous documents that refer to the development of catalytic systems based on promoted rhodium. Thus, US 4,224,236, US 4,288,558 and US 4,351,908 describe the use of a rhodium catalyst promoted with magnesium salts or complexes or magnesium compounds with oxides of the elements of groups 3 to 6 of the periodic table and halide ions . US 4,442,228 describes a rhodium catalyst promoted by an element selected from Zr, Hf, La, Pt, Cr and Hg, supported on SiO2. US 4,344,868 and US 4,444,909 refer to rhodium catalytic systems 30 supported on a zeolite neutralized with alkali cations (Na). For its part, US Patent 4,415,749 describes a process for the selective production of ethanol and methyl acetate from synthesis gas through the use of a rhodium catalyst promoted with alumina-supported iron containing an alkali metal. US 6,346,555 refers to a rhodium-based catalyst which also contains other elements such as Zr, Ir, a transition metal (Cu. Co, Ni, Mn, Fe, Ru or Mo) and an alkali or alkaline earth metal. , located on a support of SiO2, Al2O3, TiO2, zeolite or activated carbon. International application WO2006 / 000733 describes a catalyst supported on SiO2 with formula Rh-Mn-Fe-M1-M2, where M1 is Li or Na and M2 is Ru or Ir. In the application WO2006 / 000734 40 that same support is specified and a combination of rhodium with a promoter selected from Ir, Ru, Co, Fe, Mn, Ti, Zr, V, Ce, Sm, La, Li, Na, Mg and Ba. Patents US 1,501,891 and US 4,235,801 describe a process for obtaining ethanol using a rhodium catalyst promoted with iron and supported on silica gel or alumina. In US 4,096,164 rhodium is promoted with Mo and / or W using different types of support. The combination of rhodium with alkaline elements is described in US 4,235,798, US 4,446,251 and US 4,471,075. European application EP 0030110 describes a rhodium and zirconium catalyst, which may also include a metal component selected from Fe, Mn, Mo, W, Ru, Cr, U, Th, Pd and Ir, located on a SiO2 support. These same metal components are described in GB 2078745 in a catalytic system based on a combination of rhodium and rhenium. On the other hand, there are also several scientific articles that describe the use of different rhodium promoters to develop catalytic systems useful in converting synthesis gas into ethanol. Thus, the Journal of Catalysis, 1978, 54, 120-128 and Studies in Surface Science and Catalysis, 1992, 73, 103-110, describe the promoter effect of iron oxide on rhodium in synthesis gas conversion reactions , whereby the presence of this oxide in the catalyst provides an increase in catalytic activity and ethanol selectivity. fifteen For their part, the Journal of Catalysis, 1986, 98, 522-529, Journal of Catalysis, 1992, 134, 1-12 and Topics in Catalysis, 2001, 14 (1-4), 25-33 also describe the effect vanadium oxide promoter on rhodium based catalyst systems. The use of zirconium oxide has been described as an additional component of a cerium oxide support on which rhodium is deposited as a catalytically active element, to increase the conversion of carbon monoxide and selectivity to ethanol (Catalysis Today, 2011, 164, 308-314). Some documents describing the use of lanthanide element oxides as promoters of rhodium in synthesis gas conversion reactions are Applied Catalysis, 1986, 28, 303-319, Applied Catalysis, 1987, 35, 77-92, Fresenius Journal Analytical Chemistry , 25 1991, 341, 387-394 and Journal of Catalysis, 2011, 280, 274-288. Although many of these documents describe the promoter effect of specific metal oxides, in general, the composition of the promoter phase is formed by the combination of at least two of these types of oxides as described in Catalysis Today, 2009, 147 (2), 139-149; Journal of Catalysis, 2009, 267 (2), 167-176 and WO2011 / 053953. 30 For its part, the most commonly used catalytic supports are silicon oxide (SiO2) with a wide variety of textural properties (specific area, pore size, etc.), aluminum oxide (Al2O3), titanium oxide (TiO2) and mixed oxides MxOy-M'zOw, such as CeO2-TiO2, CeO2-Al2O3, SiO2-Al2O3 and SiO2-TiO2, among others. Carbon materials such as activated carbon or carbon nanotubes have also been used as supports, although the latter type of materials are less convenient from the point of view of a potential application at the industrial level due to the difficulty of regeneration or high cost, such as the case of carbon nanotubes. There are very few examples in the state of the art that describe the use of cerium oxide (CeO2) as a component of the rhodium promoter phases (Journal of Physical 40 Chemistry, 1990, 94, 5941-5947) or as its own metal phase support (Journal of Molecular Catalysis A: Chemical, 2001, 165, 219-230; Journal of Chemical Society, Faraday Transactions, 1992, 88 (9), 1311-1319; Sekiyu Gakkaishi, 1999, 42 (3) , 178-179; Reac. Kinetics and Catalysis Letters, 2002, 76 (1), 141-150). However, despite the numerous rhodium-based catalytic compositions described in the state of the art, the activity shown in the production of ethanol from gas from Synthesis is not entirely satisfactory, so it is necessary to develop improved rhodium catalysts that allow obtaining ethanol with greater activity and / or selectivity. BRIEF DESCRIPTION OF THE INVENTION The authors of the present invention have surprisingly found that the use of an iron compound as a rhodium promoter, or a suitable combination of promoters comprising an iron compound, together with the use of CeO2 as a support, provides catalysts for Rhodium promoted with catalytic properties (activity and / or selectivity and / or productivity to ethanol) improved for the selective conversion of synthesis gas to ethanol compared to equivalent systems whose supports are based on other types of oxides more commonly used, such as SiO2, Al2O3 , TiO2 and mixed oxides MxOy-M'zOw, 10 as shown in example 2.2.3 of this document. From the studies carried out using CeO2 as a support, it has been possible to demonstrate that, in addition to iron, the most suitable combinations of rhodium promoters that lead to catalysts with a high activity and / or selectivity to ethanol and, therefore, to a high productivity of ethanol, comprise the following elements:
    - iron + zirconium and, optionally, a lanthanide
    - iron + a lanthanide
    - iron + zirconium + vanadium and, optionally, a lanthanide
    - iron + vanadium + a lanthanide. Another differentiating and advantageous aspect of these catalysts with respect to those based on the conventional supports, as derived from the typical compositions described in the literature, is that the catalysts supported in CeO2 do not require the addition of an alkaline element (Li and Na most commonly used) or alkaline earth (for example Mg) to achieve high selectivities to ethanol (see comparative example in section 2.1 of example 2). 25 Therefore, a first aspect of the present invention is directed to a catalytic composition comprising:
    - a rhodium compound; Y
    - a promoter of the rhodium compound, wherein said promoter comprises an iron compound,
    where the rhodium compound and the rhodium compound promoter are deposited on a cerium oxide support.
    In a particular embodiment, the rhodium compound promoter comprises a combination of metal compounds selected from:
    - iron + zirconium and, optionally, a lanthanide element; 35
    - iron + a lanthanide element;
    - iron + zirconium + vanadium and, optionally, a lanthanide element; Y
    - iron + vanadium + a lanthanide element. Another aspect of the present invention relates to a process for the preparation of a catalytic composition as previously defined, wherein said process 40 comprises:
    a) impregnating the cerium oxide support with a precursor of the rhodium compound and with a precursor or precursors of the rhodium compound promoter;
    b) subject the impregnated support to a drying stage;
    c) subject the impregnated and dried support to a calcination stage, and
    d) subject the calcined solid obtained in step c) to a reduction process. 5 Another aspect of the present invention relates to a catalytic composition obtainable according to the procedure described above. A further aspect of the invention is directed to a process for the preparation of oxygenated compounds of two or more carbon atoms, wherein said process comprises reacting a gaseous mixture comprising carbon monoxide and hydrogen with the catalytic composition described previously. In a particular embodiment, the oxygenated compound is ethanol. Finally, in another aspect the invention is directed to a process for the preparation of hydrocarbons of two or more carbon atoms, wherein said process comprises reacting a gaseous mixture comprising carbon monoxide and hydrogen with the catalytic composition previously described. DETAILED DESCRIPTION OF THE INVENTION The first aspect of the present invention is a catalytic composition comprising a rhodium compound as the main catalytic ingredient, and a rhodium compound promoter, wherein said promoter comprises an iron compound. Both rhodium compound and its promoter are deposited on a support of cerium oxide (CeO2). In the context of the present invention, the term "rhodium compound" may include rhodium in a metallic state or a mixture of rhodium metal and rhodium in an oxidation state greater than 0. The term "promoter" refers to one or more active catalyst ingredients, in particular one or more metal compounds, which have the ability to synergistically increase the catalytic activity and / or ethanol selectivity of the rhodium compound which is the main catalytic ingredient In a particular embodiment, the rhodium compound promoter comprises a combination of metal compounds selected from: a) iron + zirconium and, optionally, a lanthanide element; b) iron + a lanthanide element; c) iron + zirconium + vanadium and, optionally, a lanthanide element d) iron + vanadium + a lanthanide element, where the rhodium compound and the precursor combination thereof are deposited on a support of cerium oxide. "Metal compounds" should be understood as compounds that include in their composition the metal elements defined above, whether, for example, the element itself in a metallic state, in the form of metal oxide, in the form of metal carbide, or a combination thereof. , among others. Likewise, when the iron compound acts as the only 40 promoter, this can be in a metallic state, in the form of oxide, in the form of carbide, among others. In a particular embodiment, the catalytic composition of the invention contains rhodium in a proportion ranging from 0.1 to 20% by weight with respect to the total weight of the catalytic composition, preferably between 0.5 and 10% by weight, more preferably between 1 and 5 % in weigh. 5 In a particular embodiment, the atomic ratio between rhodium compound and total precursor compounds varies between 1/10 and 10/1, preferably between 1/5 and 5/1, more preferably between 1/3 and 3/1 . In another particular embodiment, when the promoter of the rhodium compound is iron, the atomic ratio rhodium / iron ranges between 2/1 and 1/2. Concrete examples of atomic relationships for the rhodium / iron combination are 1 / 0.5, 1/1 and 1/2. In another particular embodiment, when the combination of metal compounds comprises iron and zirconium, the atomic ratio rhodium / iron / zirconium ranges between 1 / 0.2 / 0.2 and 1/3/3, preferably between 1 / 0.5 / 0.5 and 1 / 1.5 / 1.5. Concrete examples of atomic ratios for the rhodium / iron / zirconium combination are 1/1/1, 1 / 1.5 / 1, 1/1 / 0.5, 1 / 0.5 / 1.5, 1/1 / 1.5, 1 / 0.5 / 1, 15 1 / 1.5 / 1.5 and 1 / 1.5 / 0.5. In another particular embodiment, the combination of iron and zirconium further comprises a lanthanide. Lanthanide means an element selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, tulio, ytterbium and 20 lutetium. In a preferred embodiment, the lanthanide element is selected from lanthanum, praseodymium and samarium. In a particular embodiment, the rhodium / lanthanide atomic ratio ranges between 1: 0.3 and 1: 3, more preferably between 1 / 0.5 and 1 / 1.5. Concrete examples of atomic relationships for the rhodium / iron / zirconium / lanthanide combination are 1/1/1/1; 1 / 0.5 / 1/1; 1 / 1.5 / 1/1; 1 / 0.5 / 0.5 / 1; 25 1 / 0.5 / 1.5 / 1; 1 / 1.5 / 0.5 / 1; 1/1/1 / 1.5; 1/1/1 / 0.5 and 1 / 1.5 / 1.5 / 1. In another particular embodiment, when the combination of metal compounds comprises iron and a lanthanide element, the atomic ratio rhodium / iron / lanthanide element ranges between 1 / 0.5 / 0.5 and 1/2/2. Preferably, the atomic ratio is 1/1/1. In another particular embodiment, when the combination of metal compounds comprises iron, zirconium and vanadium, the atomic ratio rhodium / iron / zirconium / vanadium ranges between 1 / 0.5 / 0.5 / 0.5 and 1/2/2/2. Concrete examples of atomic relationships for the rhodium / iron / zirconium / vanadium combination are 1/1/1/1; 1/1/1 / 0.5 and 1/1 / 0.5 / 1. In another particular embodiment, when the combination of metal compounds comprises iron, vanadium and a lanthanide element, the molar ratio rhodium / iron / vanadium / lanthanide element ranges between 1 / 0.2 / 0.2 / 0.2 and 1/3/3/3, preferably between 1 / 0.5 / 0.5 / 0.5 and 1 / 1.5 / 1.5 / 1.5. Concrete examples of molar ratios for the rhodium / iron / vanadium / lanthanide element combination are 1/1/1/1 /; 1 / 0.25 / 1/1; 1 / 0.5 / 1/1; 1 / 0.5 / 1.5 / 1; 1/1/1 / 1.5; 1/1/1 / 0.5; 1/1/1 / 2.5 and 1 / 1.5 / 0.5 / 1. In a preferred embodiment, the combination of metal compounds comprises iron and zirconium. The catalytic composition comprising this combination of metal compounds combines a high catalytic activity with a high selectivity to ethanol as evidenced by the examples provided. However, when high selectivity to ethanol is fundamentally required, the combination of metal compounds comprises iron, zirconium and a lanthanide compound. Four. Five In another particular embodiment, the catalytic composition of the invention lacks an alkali and / or alkaline earth metal. In a particular embodiment, the cerium oxide (CeO2) support where the rhodium compound is deposited and the iron compound or the combination of metal compounds has a specific surface area of at least 10 m2 / g, preferably between 10 and 150 m2 / g, plus 5 preferably between 25 and 75 m2 / g. In another particular embodiment, the cerium oxide support has a pore volume between 0.05 and 0.5 cm3 / g, preferably between 0.1 and 0.3 cm3 / g. In another particular embodiment, the cerium oxide support has an average pore diameter between 1 and 50 nm, preferably between 5 and 25 nm. 10 Said support may be in the form of dust, granules, pellets or irregularly shaped agglomerates. In order to obtain it, any process known to one skilled in the art can be carried out, such as, for example, a precipitation process, in which a soluble and / or colloidal precursor of cerium oxide is treated to produce the solid oxide. However, such support is also commercially available. fifteen The process for depositing the rhodium compound and the promoter on the cerium oxide (CeO2) support can be carried out by any conventional method of deposition of metal catalysts on solid supports known to one skilled in the art. Such procedures include the impregnation method, either sequential co-impregnation or impregnation, the immersion method, the ion exchange method or the co-precipitation method 20. In a preferred embodiment, the process for depositing the rhodium compound and the promoter thereof on the cerium oxide support is performed by impregnation. Thus, a further aspect of the present invention is a process for obtaining a catalytic composition as previously defined comprising:
    a) impregnating the cerium oxide support with a precursor of the rhodium compound and with a precursor or precursors of the rhodium compound promoter;
    b) subject the impregnated support to a drying stage;
    c) subject the impregnated and dried support to a calcination step; Y
    d) subject the calcined solid obtained in step c) to a reduction process. 30 The precursor of the rhodium compound is generally a rhodium salt or a rhodium complex. Specific examples of rhodium salts include inorganic rhodium salts such as chloride, bromide, iodide, nitrate and rhodium carbonate, as well as organic rhodium salts such as acetate or oxalate. As rhodium complexes, complexes including, together with rhodium and a halide, complex-forming ligands, for example ethylenediamine complexes (Rh (NH2C2H4NH2) 3Cl3), pyridine complexes (Rh (C4H4N) 4Cl3), acetylacetonate complexes, can be employed. cyclooctadiene, cyclopentadienyl complexes, π-allyl complexes, rhodium alene complexes, trialkylphosphine and triarylphosphine complexes. In a preferred embodiment, the precursor of the rhodium compound is a water-soluble salt, in particular, an inorganic salt of rhodium selected from chloride, nitrate and rhodium carbonate, the use of rhodium trihydrate chloride being even more preferred. (RhCl3 · 3H2O). The impregnation of the support with the rhodium compound precursor can be accomplished by previously dissolving the rhodium precursor in a suitable solvent, such as by for example, water, an alcohol (methanol or ethanol), an ether (tetrahydrofuran or dioxane) or a hydrocarbon (hexane). Preferably, the solvent used is water as long as the rhodium precursor is an inorganic salt as described above. Once the support is impregnated with this solution, it is subjected to a drying process to remove the solvent. This drying process can be carried out by subjecting the impregnated support 5 at a temperature close to the boiling point of the solvent used. In the particular case of using water as a solvent, the impregnated support can be subjected to a heating process at a temperature of approximately 100 ° C for at least 12 hours. Alternatively, the drying step can be carried out at a temperature lower than the boiling point of the solvent, for example, under conditions of reduced pressure (lower than atmospheric). The precursors of the metal compounds that act as promoter of the rhodium compound are also salts of metal elements. Examples of these salts include organic or inorganic salts such as chlorides, carbonates, hydroxides, acetates, formats, oxalates, silyl ether salts, acetylacetonates, polyhydroxystearates, alkoxides, dicylopentadienyl complexes, π-allyl complexes, benzyl complexes and iron alene complexes , zirconium, vanadium and lanthanide elements. In a particular embodiment, the iron compound precursor is selected from iron trichloride (FeCl3), ferric nitrate (Fe (NO3) 3), ferrous nitrate (Fe (NO3) 2), ferric hydroxide (Fe (OH) 3) , ferric carbonate (Fe2 (CO3) 3), ferric format (Fe (HCOO) 3), ferric oxalate 20 (Fe2 (C2O4) 3 · nH2O), ferric chlorate (Fe (ClO4) 3), ferric methoxide (Fe (OCH3 ) 3), ferric ethoxide (Fe (OC2H5) 3), ferric propoxide (Fe (OC3H7) 3), ferric butoxide (Fe (OC4H9) 3) and ferric methyl carbonate (Fe (CH3OCOO) 3). In another particular embodiment, the precursor of the zirconium compound is selected from zirconium oxynitrate (ZrO (NO3) 2 · 2H2O), zirconium nitrate (Zr (NO3) 3 · 6H2O), zirconium oxyacetate (ZrO (CH3COO) 3 ), zirconium oxychloride (ZrOCl2), zirconium tetrachloride (ZrCl4), zirconium acetate (Zr (CH3COO) 2), zirconium ethoxide (Zr (OC2H5) 4), zirconium isopropoxide (Zr (O-isoC3H7) 4) , Zirconium Butoxide (Zr (OC4H9) 4), Dicyclopentadienyl Zirconium Chloride ((π-C5H5) 2ZrCl2), Dicarbonyl Dicyclopentadienyl Zirconium ((π-C5H5) 2Zr (CO) 2), Zirconium Z2 (7) Zirconium Acetylacetonate ) and benzyl zirconium complex (Zr (CH2C6H5) 4. Preferably, the precursor of the zirconium compound is selected from zirconium oxynitrate (ZrO (NO3) 2 · 2H2O) and zirconium nitrate (Zr (NO3) 3 · 6H2O). In another particular embodiment, the vanadium compound precursor is selected from vanadium tetrachloride (VCl4), ammonium metavanadate (NH4VO3), vanadium ethoxide (VO (OC2H5) 3), vanadium butoxide (VO (OC4H9) 3), methoxide vanadium (VO (OCH3) 3), vanadium ethoxychloride (VO (OC2H5) 5), vanadium acetylacetonate (VO (C5H7O2) 3), vanadocene (π-C5H5) 2V) and π-allyl carbonyl vanadium complex ( π-C3H5) 2V (CO) 2). In a preferred embodiment, the precursor of the vanadium compound is ammonium metavanadate. In another particular embodiment, the lanthanide element compound is selected from a halide, a salt of an inorganic acid, a hydroxide, a salt of an organic acid, an alkoxide metal or the like. Examples of these precursors are chlorides, nitrates, oxalates, acetates, acetylacetonates and carbonates of the lanthanide element. The impregnation of the support with the precursors of the metal compounds that act as promoter of the rhodium compound can be carried out by previously dissolving them in a suitable solvent, such as, for example, water, an alcohol (methanol or ethanol), an ether (tetrahydrofuran). or dioxane) or a hydrocarbon (hexane). Preferably, the solvent used is water as long as the precursors of the metal compounds are inorganic salts as described above. Once the support is impregnated with this solution, it is subjected to a drying process to remove the solvent. This drying process can be carried out by subjecting the impregnated support at a temperature close to the boiling point of the solvent used. In the particular case of using water as a solvent, the impregnated support is subjected to a heating process at a temperature of approximately 100 ° C for at least 12 hours. Alternatively, the drying step can be carried out at a temperature lower than the boiling point of the solvent, for example, under reduced pressure conditions (lower than atmospheric). The impregnation of the rhodium precursor and the precursors of the metal compounds that act as a promoter of the rhodium compound can be carried out sequentially in any order, or it can be carried out simultaneously. In a preferred embodiment, the impregnation is carried out by dissolving simultaneously in the same solvent the rhodium precursor and the precursors of the metal compounds, subsequently adding this solution on the cerium oxide support. Therefore, in a preferred embodiment, the process of the invention comprises:
    a) co-impregnating the cerium oxide support with a solution comprising a rhodium compound precursor and a rhodium compound promoter precursor or precursors;
    b) subject the impregnated support to a drying stage to remove the solvent from the solution used in step a):
    c) subject the impregnated and dried support to a calcination step; Y
    d) subject the calcined solid obtained in step c) to a reduction process. However, due to the low solubility of some of the precursors of the zirconium and vanadium compounds, they can be incorporated into the support by impregnating the support with a solution comprising the precursor of the zirconium compound and / or vanadium and subsequent drying of the impregnated support, at a stage prior to the co-impregnation of the rhodium precursor and the precursors of the rest of the metal compounds. Therefore, in another particular embodiment, when the catalytic composition comprises a zirconium compound and / or a vanadium compound, the process of the invention comprises:
    a) impregnating the cerium oxide support with a solution comprising a precursor of the zirconium compound and / or a precursor of the vanadium compound;
    b) subjecting the impregnated support to a drying step to remove the solvent from the solution used in step a);
    c) co-impregnating the solid obtained in step b) with a solution comprising a precursor of the rhodium compound and a precursor or precursors of the rest of the metal compounds that act as a promoter of the rhodium compound not included in the solution of the stage a);
    d) subjecting the impregnated support obtained in step c) to a drying step to remove the solvent from the solution used in step c); 40
    e) subject the impregnated and dried support obtained in step d) to a calcination stage; Y
    f) subject the calcined solid obtained in step e) to a reduction process. In a particular embodiment, the calcination step is performed by subjecting the impregnated and dry support to a heating of between 250 and 600 ° C, preferably between 300 and 500 ° C, applying a heating ramp of between 1 and 10 ° C / min. Preferably, the time it remains at this temperature is at least one hour. In a preferred embodiment, the calcination is carried out under an atmosphere comprising an oxygen-containing gas, such as for example air, so that the metal salts or precursors of the metal compounds are converted into the corresponding metal oxides. After the calcination stage, the rhodium precursor used in the impregnation is no longer practically present, but most of the rhodium is as rust. So that the solid 10 obtained after the calcination step can be used as a catalytic composition in the reaction of conversion of the synthesis gas to oxygenated hydrocarbons, it must be activated by a reduction process. Said reduction step can be carried out by applying a temperature between 275 and 500 ° C, preferably between 300 and 400 ° C, and passing a gas 15 containing a reducing agent onto the catalytic composition. Examples of reducing agents include hydrogen, the synthesis gas itself, carbon monoxide, hydrazine, boron hydride or aluminum hydride. In a preferred embodiment, the reducing agent is hydrogen, synthesis gas or a mixture of both. Said reduction stage can be carried out in the same reactor where the conversion of synthesis gas is carried out or in an independent reactor. A further aspect of the invention is a process for the preparation of oxygenated compounds of two carbon atoms, wherein said process comprises reacting a gaseous mixture comprising carbon monoxide and hydrogen with the catalytic composition described previously. 25 In the context of the present invention, the term "oxygenated compounds of two carbon atoms" refers to compounds having two carbon atoms and one or more oxygen atoms, in addition to hydrogen, such as ethanol, acetaldehyde, or acetic acid. . The process for preparing the oxygenated compounds is carried out by passing the initial gas mixture over the catalytic composition of the invention. Said process 30 can be carried out by feeding the gaseous mixture comprising carbon monoxide and hydrogen in a suitable catalytic reactor, such as a closed circulation reactor, a fixed bed type reactor adapted for the circulation of an initial gaseous mixture to atmospheric pressure or high pressure, a reactor at discontinuous pressure or a pressure reactor with stirring of the discontinuous type, and bringing the initial gas mixture into contact with the catalyst composition. In a particular embodiment, the process is carried out at a temperature between about 50 ° C and about 450 ° C, more preferably between 100 and 350 ° C, The pressure at which the procedure is performed can range between about 0.5 and 40 about 350 bars, preferably between 10 and 300 bars. In a particular embodiment, the molar ratio between carbon monoxide and hydrogen in the gas mixture is between 10: 1 and 1:10, preferably between 5: 1 and 1: 5, more preferably between 2: 1 and 1 :2. In a preferred embodiment, the gas mixture used in the process is synthesis gas. The term "synthesis gas" means a gas mixture constituted in its all, or predominantly, by carbon monoxide and hydrogen. In some cases, said mixture may contain other components such as nitrogen, argon, carbon dioxide and / or methane. The synthesis gas can be prepared from a wide variety of substances, such as natural gas, liquid hydrocarbons, coal or biomass following methods known to a person skilled in the art. Following the process of the invention, oxygenated compounds with two carbon atoms, particularly ethanol, with high selectivity and / or productivity are obtained. The term "selectivity" denotes the percentage of said compound (carbon based) in the reaction products, including CO2, hydrocarbons and other oxygenated compounds. By "productivity" is meant the amount of oxygenated compound produced by mass of catalyst and unit of time. Ethanol, obtained as the main ingredient within the fraction of oxygenated compounds, can be easily separated from the rest of oxygenated compounds by conventional techniques known to a person skilled in the art. fifteen The present invention is further illustrated by the following examples, which are not intended to be limiting in scope. Examples Example 1. General procedure for the preparation of the promoted Rh catalyst supported on CeO2 and typical conditions used in catalytic synthesis tests for gas conversion
    1.1. General catalyst preparation procedure
    The CeO2 support used in the preparations of the catalysts studied is of commercial origin (Aldrich) and has the following textural properties: specific surface area (BET) = 62.7 m2 / g, pore volume = 0.20 cm3 / g, and average pore diameter = 13.1 nm. 25
    The catalysts were prepared by co-impregnating the wetness impregnation of the CeO2 support with an aqueous solution containing the Rh metal precursors (RhCl3 · 3H2O) and the promoter precursors at the appropriate concentrations to achieve 2.5% by weight of Rh and the desired promoter (s) / Rh atomic ratios in the calcined catalyst (before reducing). When 30 V and Zr compounds were used as Rh promoters, their incorporation into the support was performed by impregnating the support at pore volume and subsequently drying at 100 ° C for approx. 2-3 hours at a stage prior to the co-impregnation of Rh precursors and other metal promoters. Once all the metal precursors were incorporated into the support, the material was dried in an oven at 100 ° C for approx. 12 hours and then air flow was calcined at 400 ° C for 4 hours, using a heating ramp of 2 ° C / min. 1.2. General Nomenclature of Catalysts The nomenclature used for catalysts is Rh-xP1-yP2-zP3 / CeO2, where P1, P2 and P3 are the metals of the corresponding promoters (in the case, for example, of tri-promoted catalysts) where x, y , z the atomic relationships between promoters P1, P2 40 and P3, respectively, and Rh. As mentioned above, all catalysts have a nominal Rh content of 2.5% by weight (in the calcined material). 1.3. Preparation example of a catalyst of composition Rh-Fe-Zr / CeO2
    According to the established nomenclature, this catalyst contains 2.5% by weight of Rh and atomic ratios Fe / Rh = 1 and Zr / Rh = 1. For its preparation, they were impregnated at volume 45
    pore 94 grams of CeO2 with 93.5 cm3 of an aqueous solution in which 8.87 grams of ZrO (NO3) 3 · 6H2O (clear colorless solution) had previously dissolved. After the addition was completed (filling the pores of the support), the solid was dried in an oven at 100 ° C for 2-3 hours. Next, the CeO2 support impregnated with the Zr precursor and dried was again impregnated with pore volume with 93.5 cm3 of an aqueous solution in which 10.46 grams of RhCl3 · 3H2O and 6.57 grams of FeCl3 · 6H2O had previously been dissolved. After impregnation the solid was dried again in an oven at 100 ° C for approx. 12 hours, and finally it was calcined in air flow at 400 ° C for 4 hours.
    1.4. Conditions of catalytic tests The catalytic tests were carried out using a fixed bed catalytic reactor of 9.7 10 mm internal diameter and a length of 335 mm. The amount of catalyst (in its calcined form) used in the tests was approximately 1 g. In all cases, the reactor was charged with catalyst previously pressed and screened with a particle size of 0.25-0.45 mm and diluted with SiC (particle size 0.6-0.8 mm) until a total volume of catalytic bed of 6.5 cm3 was achieved. fifteen
    Before introducing the mixture of reactant gases into the reactor, the catalyst was subjected to an in situ reduction stage in H2 flow (100 cm3 / min · gcat) at 300 ° C for 6 hours (heating ramp of 1 ° C / min). Subsequently, the reactor was cooled to 100 ° C in H2 flow, this was replaced by synthesis gas with the volumetric composition 45% H2 / 45% CO / 10% Ar (ratio H2 / CO = 1, Ar used as internal standard for the chromatographic analysis) with the desired flow rate and the reactor was pressurized at 50 bar. Once pressurized, the reactor temperature was increased to 280 ° C using a heating ramp of 4 ° C / min. The start of the reaction (TOS = 0) is considered when the reaction temperature is reached (280 ° C). The spatial velocity was adjusted in each catalyst in order to achieve a constant CO conversion of approx. 10% and thus be able to compare selectivities under conditions of iso-25 conversion.
    The reaction products were separated and quantified by a gas chromatograph (Varian CP-3800 model) coupled in line to the reactor outlet after depressurization of the output stream. During the reaction, consecutive analyzes were performed at intervals of approx. 1 hour. Generally the catalyst was tested for a total time of approx. 8 30 hours, for which a pseudo-stationary behavior is already observed (little variation in activity and selectivity over time). The activity and selectivity data presented correspond to the values obtained in the pseudo-stationary state.
    Example 2. Results of catalytic tests for the conversion of synthesis gas to ethanol 35
    2.1. Results obtained using catalysts of the invention Table 1 shows examples of representative catalyst compositions of the invention, obtained according to the general preparation procedure described in example 1, exemplified in section 1.3 for the specific case of a catalyst of composition Rh-Fe-Zr / CeO2 of according to the established nomenclature (section 1.2). The nominal content of 40 rhodium in all catalysts is 2.5% by weight.
    Table 1. Chemical composition of catalysts representative of the invention.
     Catalyst  Support Composition of the metallic phase
     I-1  CeO2 Rh-Fe
     I-2  CeO2 Rh-Fe-Pr
     I-3  CeO2 Rh-Fe-Zr
     I-4  CeO2 Rh-Fe-0.5Zr
     I-5  CeO2 Rh-1.5Fe-0.5Zr
     I-6  CeO2 Rh-1.5Fe-Zr
     I-7  CeO2 Rh-1.5Fe-1.5Zr
     I-8  CeO2 Rh-Fe-Zr-Pr
     I-9  CeO2 Rh-Fe-Zr-Sm
     I-10  CeO2 Rh-Fe-Zr-0,5Sm
     I-11  CeO2 Rh-1.5Fe-1.5Zr-Sm
     I-12  CeO2 Rh-Fe-Zr-La
     I-13  CeO2 Rh-Fe-V-Pr
     I-14  CeO2 Rh-Fe-V-La
     I-15  CeO2 Rh-Fe-V-Sm
     I-16  CeO2 Rh-1.5Fe-0.5V-Sm
     I-17  CeO2 Rh-Fe-Zr-V These catalysts were tested in the catalytic conversion of synthesis gas under the conditions detailed in section 1.4 (T = 280 ° C, P = 50 bar). The results of activity (given as millimoles of CO converted per gram of catalyst and hour), selectivity to the 5 main reaction products (at a constant CO conversion of approx. 10%), and productivity to ethanol (given as grams of EtOH obtained per kg of catalyst and hour) are shown in Table 2.Table 2. Results obtained in the conversion of synthesis gas with the catalysts of the invention mentioned in Table 1.
     Catalyst  Activity (mmol / gh) Selectivity (% C) a Productivity to EtOH (g / kgcath)
     HC’s  Oxig CO2 EtOH
     I-1  13.5 41.0 40.2 18.8 24.9 77.3
     I-2  12.4 42.6 40.9 16.5 24.4 69.6
     I-3  10.6 41.2 47.3 11.5 31.5 76.8
     I-4  11.0 35.3 49.6 15.1 27.6 69.8
     I-5  13.5 49.4 37.7 12.9 24.1 74.8
     I-6  11.6 37.9 44.1 18.0 27.6 73.6
     I-7  11.4 40.6 46.5 12.9 30.6 80.2
     I-8  10.7 49.5 42.0 8.5 27.1 66.7
     I-9  8.8 40.6 47.3 12.1 31.3 63.4
     I-10  8.7 38.0 47.4 14.6 30.3 60.6
     I-11  10.2 42.1 46.0 11.9 29.6 69.4
     I-12  8.1 40.3 45.7 14.0 29.2 54.4
     I-13  7.8 45.3 42.9 11.8 29.1 52.2
     I-14  10.5 40.1 42.9 17.0 26.8 64.7
     I-15  7.6 40.0 44.4 15.6 29.3 51.2
     I-16  11.8 42.4 41.3 16.3 25.6 69.5
     I-17  6.9 48.3 45.0 6.7 28.5 45.2 at HC’s = hydrocarbons; Oxig. = Total oxygenates. All catalysts included in Table 2 are characterized by their high activity and / or selectivity to ethanol under the conditions of the tests. It should be taken into account that the 5 tests were carried out under fixed temperature and pressure conditions (280ºC and 50 bar, respectively) and at a spatial velocity such that a CO conversion was obtained. close to 10%, and therefore, the productivity values obtained are not optimal in each case. However, the conditions of these tests are appropriate to establish comparisons between different catalytic systems. Among the selected catalysts, I-7 stands out (metallic composition: Rh-1.5Fe-1.5Zr) since it combines a high catalytic activity with a high selectivity to ethanol (30.6%), 5 leading to the higher productivity of this alcohol (80.2 g / kgcath) of all the catalysts supported in CeO2. It should also be noted that when CeO2 is used as a support, the vast majority of metal compositions that give rise to the best catalysts contain combinations of Fe and Zr in different proportions (catalysts I-3 to I-7). 10 On the other hand, unlike what happens in the majority of catalysts supported in SiO2, the addition of an alkaline (generally Li) as a co-promoter has a negative effect on the behavior of the catalysts of the invention supported on CeO2, such as shown in Table 3, by way of example, for the catalysts I-8 (Rh-Fe-Zr-Pr) and I-9 (Rh-Fe-Zr-Sm). It is clearly observed that the addition of Li (atomic ratio Li / Rh = 0.5) to these catalytic systems significantly increases the selectivity to CO2, reducing the selectivity to oxygenates in general and to ethanol in particular. Table 3. Effect of the addition of Li on representative catalysts of the invention.
     Catalyst  Conversion of CO (%) Activity (mmol / gh) Selectivity (% C) Productivity to EtOH (g / kgcath)
     HC’s  Oxig CO2 EtOH
     I-8 + Lia  11.5 10.1 35.4 28.0 36.6 17.6 40.9
     I-9 + Lia  10.8 12.2 29.8 27.1 43.1 15.5 43.5 a Atomic ratio Li / Rh = 0.5.
    2.2. Comparative examples using supports representative of the state of the art 20 2.2.1. Catalysts supported in SiO2 Table 4 shows the textural properties of different types of silica of commercial origin used as supports representative of the state of the art. Table 5 shows examples of promoted Rh catalysts supported in the different types of commercial SiO2. The catalysts were prepared following the same general methodology described in section 2.2.1 for those supported in CeO2.
    Table 4. Properties of different types of commercial silica (Aldrich) used in the preparation of catalysts representative of the state of the art.
     Textural properties
     Commercial silicas  Abbreviated name SBET (m2 / g) Pore volume (cm3 / g) Pore diameter (nm)
     Silica Spherical gel  SiO2-Spher. 430-530 0.7-1 6-8
     Silica gel (Davisil) grade 12  SiO2-G12 0.43 2.2
     Silica gel (Davisil) grade 635  SiO2-G635 0.75 6.0
     Silica gel (Davisil) grade 643  SiO2-G643 1.15 Table 5. Composition of promoted Rh catalysts supported on silica materials of commercial origin. 5
     Catalyst  Support Composition of the metallic phase
     C-1  SiO2-Spher. Rh-Fe-V-Pr
     C-2  SiO2-G12 Rh-Fe-V-Pr
     C-3  SiO2-G643 Rh-Fe-V-Pr
     C-4  SiO2-G635 Rh-Fe-V-Pr These catalysts were tested in the synthesis gas conversion process under the same reaction conditions used for the catalysts of the invention (supported on CeO2), as described in section 1.4. The results obtained are shown in Table 6. 10
    Table 6. Results obtained in the conversion of synthesis gas with the catalysts supported in SiO2 (Table 5) representative of the state of the art.
     Catalyst  Conversion of CO (%) Activity (mmol / gh) Selectivity (% C) Productivity to EtOH (g / kgcath)
     HC’s  Oxig CO2 EtOH
     C-1  9.9 6.6 59.9 34.2 5.9 20.6 31.3
     C-2  7.9 3.9 45.5 46.7 7.8 22.3 20.0
     C-3  8.8 4.4 58.3 36.7 5.0 23.1 23.4
     C-4  10.3 5.0 45.5 47.8 6.7 28.5 32.8 2.2.2. Catalysts supported in TiO2 Tables 7 and 8 show the catalytic compositions and results of catalysts prepared using commercial titanium oxide (P25, Degussa) as support.Table 7. Rh promoted catalysts supported on commercial TiO2.
     Catalyst  Support Composition of the metallic phase
     C-5  TiO2 (P25, Degussa) Rh-Fe-Zr-Pr
     C-6  TiO2 (P25, Degussa) Rh-Fe-V-Pr Table 8. Results obtained in the conversion of synthesis gas with the catalysts 10 supported in TiO2.
     Catalyst  Conversion of CO (%) Activity (mmol / gh) Selectivity (% C) Productivity to EtOH (g / kgcath)
     HC’s  Oxig CO2 EtOH
     C-5  10.2 8.2 56.1 38.2 5.7 27.1 51.1
     C-6  10.2 6.8 54.4 39.9 6.0 23.9 37.4 2.2.3. Catalysts supported in mixed oxides Table 9 shows Rh catalysts with metallic compositions of the promoter phases similar to the previous ones, but supported on two mixed oxides, CeO2-SiO2 and 15 CeO2-ZrO2. The catalytic results obtained with these catalysts are shown in Table 10. Table 9. Rh promoted catalysts supported on mixed oxides.
     Catalyst  Support Composition of the metallic phase
     C-7  CeO2-SiO2 (atomic relay Ce / Si = 4) Rh-Fe-V-Pr
     C-8  CeO2-ZrO2 (atomic rel. Ce / Zr = 4) Rh-Fe-V-Pr Table 10. Results obtained in the conversion of synthesis gas with catalysts 5 supported in mixed oxides.
     Catalyst  Conversion of CO (%) Activity (mmol / gh) Selectivity (% C) Productivity to EtOH (g / kgh)
     HC’s  Oxig CO2 EtOH
     C-7  8.3 3.3 64.2 29.8 6.0 17.1 13.0
     C-8  9.9 6.7 47.9 41.5 10.6 27.2 41.9 The results of the comparative examples presented above demonstrate that, for equivalent promoter metal phase compositions, the catalysts of the invention supported on CeO2 are more productive to ethanol under the same operating conditions. 10
    权利要求:
    Claims (21)
    [1]

    [1]
    1. A catalytic composition comprising:
    - a rhodium compound;
    - a promoter of the rhodium compound, wherein said promoter comprises an iron compound,
    where the rhodium compound and the promoter thereof are deposited on a support of cerium oxide.
    [2]
    2. Catalytic composition according to claim 1, wherein the rhodium compound promoter comprises a combination of metal compounds selected from:
      iron + zirconium and, optionally, a lanthanide; 10
      iron + a lanthanide;
      iron + zirconium + vanadium and, optionally, a lanthanide; Y
      iron + vanadium + a lanthanide.
    [3]
    3. Catalytic composition according to claim 1 or 2, wherein the rhodium compound is in a proportion ranging from 0.1 to 20% by weight with respect to the total weight of the catalytic composition.
    [4]
    4. Catalytic composition according to any of claims 1 to 3, wherein the molar ratio between the rhodium compound and the promoter thereof ranges between 1:10 and 10: 1.
    [5]
    5. Catalytic composition according to any of claims 1 to 4, wherein the lanthanide compound is selected from lanthanum, praseodymium and samarium. twenty
    [6]
    6. Catalytic composition according to any one of claims 1 to 4, wherein the combination of metal compounds comprises iron and zirconium.
    [7]
    7. Catalytic composition according to claim 6, wherein the combination of metal compounds further comprises a lanthanide.
    [8]
    8. Catalytic composition according to any of claims 1 to 7, characterized in that it lacks an alkali metal.
    [9]
    9. A process for the preparation of a catalytic composition as defined in any one of claims 1 to 8, wherein said process comprises:
    a) impregnating the cerium oxide support with a precursor of the rhodium compound and with a precursor or precursors of the promoters of the rhodium compound; 30
    b) subject the impregnated support to a drying stage;
    c) subject the impregnated and dried support to a calcination step; Y.
    d) subject the calcined solid obtained in step c) to a reduction process.
    [10]
    10. The method according to claim 9, wherein the precursor of the rhodium compound is an inorganic salt selected from chloride, bromide, iodide, nitrate and rhodium carbonate; An organic salt selected from acetate and rhodium oxalate; or a rhodium complex selected from ethylenediamine complexes, pyridine complexes, cyclooctadiene complexes, cyclopentadienyl complexes, π-allyl complexes, rhodium aleno complexes and trialkylphosphine and triarylphosphine complexes.
    [11]
    11. Process according to any of claims 9 to 10, wherein the rhodium compound promoter precursors are inorganic salts selected from chlorides, nitrates, carbonates and hydroxides; organic salts selected from acetates, formats, oxalates, silyl ether salts, acetylacetonates, polyhydroxystearates and alkoxides; or dicylopentadienyl complexes, π-allyl complexes, benzyl complexes and aleno complexes of iron, zirconium, vanadium and lanthanide elements.
    [12]
    12. Method according to any of claims 9 to 11, wherein the impregnation of the rhodium compound precursor and the rhodium compound promoter precursors is carried out sequentially in any order, or simultaneously.
    [13]
    13. Method according to any of claims 9 to 12, wherein the impregnation of the rhodium compound precursor and the rhodium compound promoter precursors is carried out simultaneously, and comprises:
    a) co-impregnating the cerium oxide support with a solution comprising a rhodium compound precursor and the rhodium compound promoter precursor or precursors; fifteen
    b) subject the impregnated support to a drying stage;
    c) subject the impregnated and dried support to a calcination step; Y
    d) subject the calcined solid obtained in step c) to a reduction process.
    [14]
    14. Method according to any of claims 9 to 12, comprising:
    a) impregnating the cerium oxide support with a solution comprising a precursor of the zirconium compound or a precursor of the vanadium compound;
    b) subjecting the impregnated support to a drying step to remove the solvent from the solution used in step a);
    c) co-impregnating the support obtained in step b) with a solution comprising a precursor of the metal rhodium compound and precursors of the remaining metal compounds that act as a promoter of the rhodium compound not included in the solution of step a );
    d) subjecting the impregnated support obtained in step c) to a drying step to remove the solvent from the solution used in step c).
    e) subject the impregnated and dried support obtained in step d) to a stage of calcination; Y
    f) subject the calcined solid obtained in step e) to a reduction process.
    [15]
    15. Method according to any of claims 9 to 14, wherein the calcination step is performed by subjecting the impregnated and dry support to a heating of between 250 and 600 ° C, applying a heating ramp of between 1 and 10 ° C / min. 35
    [16]
    16. Method according to any of claims 9 to 15, wherein the reduction step is carried out by applying a temperature between 275 and 500 ° C on the calcined solid, and passing a gas containing a reducing agent.
    [17]
    17. A catalytic composition obtainable according to a method as defined in any of claims 9 to 16. 40
    [18]
    18. A process for the preparation of oxygenated compounds of two carbon atoms, wherein said process comprises reacting a gaseous mixture comprising carbon monoxide and hydrogen with the catalytic composition defined in any one of claims 1 to 8 and 17.
    [19]
    19. Process according to claim 18, wherein the oxygenated compound is ethanol. 5
    [20]
    20. A process for the preparation of hydrocarbons of two carbon atoms, wherein said process comprises reacting a gaseous mixture comprising carbon monoxide and hydrogen with the catalytic composition defined in any one of claims 1 to 8 and 17.
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    同族专利:
    公开号 | 公开日
    WO2014114822A1|2014-07-31|
    ES2546118R1|2015-11-02|
    ES2546118B1|2016-08-09|
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