CATALYTIC PROCESS FOR THE PRODUCTION OF HYDROCARBONS AND AROMATIC COMPOUNDS FROM OXYGEN COMPOUNDS PR

专利摘要:
Catalytic process for the production of hydrocarbons and aromatic compounds from oxygenated compounds present in aqueous mixtures. Process for the production of mixtures of hydrocarbons and aromatic compounds, for use as fuel components (preferably in the C5-C16 range), by catalytic transformation of oxygenated organic compounds present in aqueous fractions derived from biomass treatments, which may comprise at least the following steps: i) contacting the aqueous mixture containing the oxygenated organic compounds derived from biomass with a catalyst comprising at least Sn and Nb, Sn and Ti, and combinations of Sn, Ti and Nb ii) reacting the mixture with the catalyst in a catalytic reactor at temperatures between 100 and 350ºC and pressures of 1 to 80 bar in the absence of hydrogen: and iii) recover the products obtained by a liquid/liquid separation process of the aqueous and organic phases. (Machine-translation by Google Translate, not legally binding)
公开号:ES2732747A1
申请号:ES201830508
申请日:2018-05-25
公开日:2019-11-25
发明作者:Marcelo Eduardo Domine；Naranjo Alberto Fernández-Arroyo；Nieto José Manuel López
申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
IPC主号:

专利说明:

[0001] Catalytic process for the production of hydrocarbons and aromatic compounds from oxygenated compounds present in aqueous mixtures
[0002]
[0003] FIELD OF THE INVENTION
[0004]
[0005] This invention belongs to the field of the synthesis and application of solid catalysts for the conversion of biomass mainly of the lignocellulosic type and its derivatives into liquid fuels for transport.
[0006]
[0007] STATE OF THE ART PRIOR TO THE INVENTION
[0008]
[0009] Biomass, together with CO2, is one of the primary and renewable sources of coal. The valorization of biomass (mainly vegetable or lignocellulosic type) and its derivatives is a sustainable alternative to the use of fossil sources for the production of fuels and chemical products, thus reducing the obvious problems of depletion of non-renewable resources and the environmental issues associated with them [GW Huber, S. Iborra, A. Corma. Chemical Reviews, 106 (2006) 4044]. In this sense, in the new concept of biorefinery and bio-economy, it is essential to co-produce biofuels together with other chemical products of interest. Likewise, in the new innovative strategies for the treatment of biomass of 2nd generation (not competitive with food), it is also necessary to valorise the residual currents and aqueous effluents obtained during biorefinery processes [F. Cherubini et al., Biofuels, Bioproducts and Biorefining, 3 (2009) 534].
[0010]
[0011] In this context, and after a primary treatment of lignocellulosic biomass (for example, by processes of pyrolysis, liquefaction and thermal or catalytic hydrolysis, as well as fermentation processes), aqueous fractions containing mixtures of oxygenated organic compounds can be obtained ( ie acids, aldehydes, alcohols, polyols, sugars, furans, phenols, etc.) that are not currently being used [A. Corma, S. Iborra, A. Velty, Chemical Reviews, (2007) 2411]. Thus, by means of thermal or catalytic pyrolysis processes, so-called pyrolysis oils or bio-liquids can be obtained mostly. These bioliquids are complex mixtures of more than 200 components, containing different proportions of water and fundamentally oxygenated organic compounds (ie alcohols, ketones, acids, polyalcohols, furans, phenols, among others) of different molecular size that are characterized by their high content in oxygen and its great reactivity. The bio-liquids also have a high acidity due to the presence of short chain carboxylic acids (C1-C4), which makes storage and direct use difficult. These properties added to its instability against temperature make it necessary to have an improvement or “upgrading” stage prior to storage and use. Due to the complexity of these mixtures, difficult to treat as a whole, one of the most used strategies is the separation of the different components of the bio-liquid to facilitate its subsequent treatment [documents US 2014/0288338, US 2013 / 0079566, WO 2015/08110].
[0012]
[0013] After a liquid-liquid separation process by adding water or organic solvents to the bio-liquid, an organic phase can be obtained, on the one hand, containing various organic compounds of interest for later use as fuels; and on the other hand aqueous fractions and effluents containing C1-C4 short chain carboxylic acids (mainly acetic acid) together with other compounds such as aldehydes, ketones or alcohols and small amounts of furanic compounds and / or heavier compounds, which are not being currently used and constitute residual currents in bio-refineries [M. Asadieraghi et al., Renewable and Sustainable Energy Reviews, 36 (2014) 286, EE lojoiu et al., Applied Catalysis A: Gen. 323 (2007) 147].
[0014]
[0015] These oxygenated organic compounds, mostly short chain (<C5) have little value in themselves, but can be efficiently transformed to generate mixtures of longer chain hydrocarbons and aromatic compounds that are very useful as precursors, components and / or additives in automotive liquid fuels. These compounds (hydrocarbons and aromatics) are produced by the formation of carbon-carbon bonds through reactions of condensation, ketoneization, alkylation with alcohols, which occur consecutively [CA Gaertner et al. Journal of Catalysis, 266 (2009) 71]. In addition, given the diversity of Organic molecules present in the system, other reactions such as decarboxylations, dehydrations or esterifications can occur when treating these complex aqueous mixtures.
[0016]
[0017] For this, it is necessary to develop new catalysts and catalytic processes that are capable of carrying out the desired reactions in the fewest possible stages and with high efficiency. In this context, the study of solid catalysts of the mixed oxides type of Ce-Zr [A. Gangadharan et al., Applied Catalysis A: Gen. 385 (2010) 80-91], which allow the conversion in gas phase and high temperatures (> 300 ° C) of low molecular weight aldehydes (for example, propanal) in the presence of carboxylic acids and water, mainly through aldol condensation and ketone processes. The activity of these materials is due to their multifunctional properties possessing isolated and well-distributed active sites that can work cooperatively (for example, acid-base and redox sites). However, the stability of the catalyst in the reaction conditions (presence of water and high temperatures) is a point to be improved in the new materials to be developed for this type of applications.
[0018]
[0019] More recently, materials based on Nb oxides (A. Fernández-Arroyo et al., Catalysis Science & Technology 7 (2017) 5495-5499) and Nb-W mixed oxides (WO 2017162900) have been synthesized using hydrothermal synthesis. pseudo-crystalline structures (and arranged in a single crystallographic axis) and improved acidic properties. These materials have turned out to be active catalysts in consecutive condensation reactions of oxygenated compounds in water, with yields of products of interest similar to those presented by the catalysts of the type mixed oxides of Ce-Zr, also demonstrating a certain resistance and stability in the conditions of reaction. However, both the catalytic activity and the stability of the catalysts working at high temperatures and pressures in aqueous media must be improved in order to efficiently develop this type of applications.
[0020] DESCRIPTION OF THE INVENTION
[0021]
[0022] The present invention relates to a catalytic process for the production of mixtures of hydrocarbons and aromatic compounds, which may comprise at least the following steps:
[0023] (a) contacting an aqueous mixture containing oxygenated organic compounds derived from primary treatments of the biomass with a catalyst, which may contain in its composition at least
[0024] - Sn and Nb, and combinations of Sn-Nb with other transition metals, rare earths or lanthanides,
[0025] - Sn and Ti, and combinations of Sn-Ti with other transition metals, rare earths or lanthanides,
[0026] - Sn, Nb and Ti, and combinations of Sn-Nb-Ti with other transition metals, rare earths or lanthanides,
[0027] and that, in its calcined form, it is mostly formed (more than 65% by weight) by the rutile-like crystalline phase of SnO2.
[0028] (b) reacting the mixture with the catalyst in a catalytic reactor at temperatures between 100 and 350 ° C and pressures of 1 to 80 bar in the absence of hydrogen;
[0029] (c) recover the products obtained in step (b) by a process of liquid / liquid separation of the aqueous and organic phases.
[0030]
[0031] According to a particular embodiment, the process of the present invention for the catalytic condensation of oxygenated organic compounds present in aqueous fractions derived from biomass in mixtures of hydrocarbons and aromatic compounds (preferably C5-C16), can use a catalyst having the empirical formula :
[0032] Sn ^a Nb ^b Ti ^c M ^d O ^e
[0033] in which:
[0034] - M is a chemical element of the group of transition metals, rare earths or lanthanides,
[0035] - a is between 0.05 and 10.0
[0036] - b and c are between 0 and 10.0, with c + b other than zero (c + b + 0)
[0037] - d is between 0 and 4.0 and
[0038] - e has a value that depends on the oxidation state of the elements Sn, Nb, Ti and the element M.
[0039]
[0040] According to this embodiment, the catalyst must comply with the condition that the catalyst comprises at least Sn and Nb and / or Ti, and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of the SnO2 in which at least Nb and / or Ti are incorporated.
[0041]
[0042] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, solutions of the same pure elements, or mixing thereof, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0043]
[0044] According to another particular embodiment of the present invention, the catalyst is obtained by a process comprising at least:
[0045] a) a first stage, of mixing of compounds of the different elements, of pure elements, or of mixing thereof,
[0046] b) a second stage, of drying the solid obtained in the first stage and
[0047] c) a third stage, for calcining the dry solid obtained in the second stage.
[0048]
[0049] The mixing step can be carried out from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0050]
[0051] The elements Sn, Nb, Ti and the metal M can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0052]
[0053] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0054] The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
[0055]
[0056] The Ti may be incorporated into the mixing step preferably as titanium dioxide, titanium oxychloride, titanium oxy sulfate, titanium nitrate, titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium butoxide or Ti metal.
[0057]
[0058] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0059]
[0060] The mixing step can be carried out in solution or by hydrothermal treatment.
[0061]
[0062] The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
[0063]
[0064] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0065]
[0066] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0067]
[0068] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn, Nb, Ti and the element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The coprecipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0069]
[0070] In an alternative embodiment, the catalyst is obtained using hydrothermal methods (containing two or more elements in the synthesis, especially containing Sn, Nb, Ti and element M) in which the temperature and synthesis time can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0071]
[0072] In an alternative embodiment, the catalyst is obtained by impregnating the precursors containing the elements Nb, Ti and the metal M on an SnO2 material, mostly presenting the rutile crystalline phase. As precursor compounds containing elements Nb, Ti and element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the elements in the SnO2 material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is subjected to the activation of the material prior to its use in reaction.
[0073]
[0074] The catalyst described can be used for the inventive process as it is obtained once calcined.
[0075]
[0076] In an alternative embodiment, the catalyst described above can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0077]
[0078] According to another particular embodiment of the process of the present invention, a catalyst can be used that starting from the formula with the composition Sn ^a Nb ^b Ti ^c M ^d O ^e , where d is zero, has the following empirical formula:
[0079] Sn ^a Nb ^b Ti ^c O ^e
[0080] in which:
[0081] - a is between 0.05 and 10.0
[0082] - b and c are between 0.0001 and 10.0, and
[0083] - e has a value that depends on the oxidation state of the elements Sn, Nb and Ti.
[0084]
[0085] According to this embodiment, the catalyst must comply with the condition that the catalyst comprises at least Sn, Nb and Ti, and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of SnO2 in which are incorporated at least Nb and / or Ti.
[0086]
[0087] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, solutions of the same pure elements, or mixing thereof, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0088]
[0089] According to another particular embodiment of the present invention, the catalyst is obtained by a process comprising at least:
[0090] a) a first stage, of mixing compounds of the different elements, of pure elements, or mixture thereof,
[0091] b) a second stage, of drying the solid obtained in the first stage and
[0092] c) a third stage, for calcining the dry solid obtained in the second stage.
[0093]
[0094] The mixing step can be carried out from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0095]
[0096] The elements Sn, Nb and Ti can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0097]
[0098] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0099]
[0100] The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
[0101]
[0102] The Ti may be incorporated into the mixing step preferably as titanium dioxide, titanium oxychloride, titanium oxy sulfate, titanium nitrate, titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium butoxide or Ti metal.
[0103]
[0104] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0105]
[0106] The mixing step can be carried out in solution or by hydrothermal treatment.
[0107]
[0108] The drying stage can be carried out by conventional methods in the oven, evaporation with stirring, evaporation in rotary evaporator, or vacuum drying.
[0109]
[0110] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0111]
[0112] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0113]
[0114] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn, Nb and Ti, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The co-precipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, Without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0115]
[0116] In an alternative embodiment, the catalyst is obtained using methods hydrothermal (containing two or more elements in the synthesis, especially containing Sn, Nb and Ti) in which the temperature and time of synthesis can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0117]
[0118] In an alternative embodiment, the catalyst is obtained by impregnating the precursors containing the elements Nb and Ti on an SnO2 material, mostly presenting the rutile crystalline phase. As precursor compounds containing the elements Nb and Ti, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the elements in the SnO2 material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0119]
[0120] The catalyst described can be used for the inventive process as it is obtained once calcined.
[0121]
[0122] In an alternative embodiment, the catalyst described above can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0123]
[0124] According to another particular embodiment of the process of the present invention, a catalyst can be used that starting from the formula with the composition Sn ^a Nb ^b Ti ^c M ^d O ^e , in which c is zero, has the following empirical formula:
[0125] Sn ^a Nb ^b M ^d O ^e
[0126] in which:
[0127] - M is a chemical element of the group of transition metals, rare earths or lanthanides,
[0128] - a and b are between 0.05 and 10,
[0129] - d is between 0 and 4.0 and
[0130] - e has a value that depends on the oxidation state of the elements Sn, Nb and M.
[0131]
[0132] Again, the above formula must comply with the condition that the catalyst comprises at least Sn and Nb and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of SnO2 in which the Nb It is incorporated into the structure of the rutile phase.
[0133]
[0134] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, solutions of the same pure elements, or mixing thereof, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0135]
[0136] The catalyst described in this embodiment can be obtained by a process comprising at least:
[0137] a) a first stage, of mixing of compounds of the different elements, of pure elements, or of mixing thereof,
[0138] b) a second stage, of drying the solid obtained in the first stage and
[0139] c) a third stage, for calcining the dry solid obtained in the second stage.
[0140]
[0141] The mixing step can be carried out from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0142]
[0143] The elements Sn, Nb and the metal M can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0144] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0145]
[0146] The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
[0147]
[0148] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0149]
[0150] The mixing step can be carried out in solution or by hydrothermal treatment.
[0151]
[0152] The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
[0153]
[0154] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0155]
[0156] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0157]
[0158] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn, Nb and the element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The coprecipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0159]
[0160] In an alternative embodiment, the catalyst is obtained using hydrothermal methods (containing two or more elements in the synthesis, especially containing Sn, Nb and element M) in which the temperature and synthesis time can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0161]
[0162] In an alternative embodiment, the catalyst is obtained by impregnating the precursors containing Nb and the metal M on an SnO2 material, mostly presenting the rutile crystalline phase. As precursor compounds containing Nb and element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the elements in the SnO2 material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0163]
[0164] The catalyst described can be used for the inventive process as it is obtained once calcined.
[0165]
[0166] In an alternative embodiment the catalyst described above in this invention can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0167]
[0168] According to another particular embodiment of the process of the present invention, a catalyst can be used that starting from the formula with the composition Sn ^a Nb ^b Ti ^c M ^d O ^e , in which c and d are zero, has the following empirical formula:
[0169] Sn ^a Nb ^b O ^e
[0170] where:
[0171] - a and b are between 0.05 and 10.0, and
[0172] - e has a value that depends on the oxidation state of the elements Sn and Nb.
[0173]
[0174] Again with the proviso that the catalyst comprises at least Sn and Nb and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of SnO2 in which Nb is incorporated into the structure of the rutile phase.
[0175]
[0176] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, solutions of the same pure elements, or mixing thereof, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0177]
[0178] The catalyst is obtained by a process comprising at least:
[0179] a) a first stage, of mixing of compounds of the different elements, of pure elements, or of mixing thereof,
[0180] b) a second stage, of drying the solid obtained in the first stage and
[0181] c) a third stage, for calcining the dry solid obtained in the second stage.
[0182]
[0183] The mixing step can be carried out from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0184]
[0185] The elements Sn and Nb can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0186]
[0187] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0188]
[0189] The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
[0190]
[0191] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0192]
[0193] The mixing step can be carried out in solution or by hydrothermal treatment.
[0194]
[0195] The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
[0196]
[0197] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0198] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0199]
[0200] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn and Nb, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The co-precipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, Without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0201]
[0202] In an alternative embodiment, the catalyst is obtained using hydrothermal methods (containing at least two elements in the synthesis, especially Sn and Nb) in which the temperature and time of synthesis can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0203] In an alternative embodiment, the catalyst is obtained by impregnating precursors containing Nb on an SnO2 material, mostly presenting the rutile crystalline phase. As precursor compounds containing Nb, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the Nb in the SnO2 material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0204]
[0205] The catalyst described can be used for the inventive process as it is obtained once calcined.
[0206]
[0207] According to an alternative embodiment, the catalyst described above in this invention can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0208]
[0209] According to another particular embodiment of the process of the present invention, a catalyst can be used that starting from the formula with the composition Sn ^a Nb ^b Ti ^c M ^d O ^e , in which b is zero, has the following empirical formula:
[0210] Sn ^a Ti ^c M ^d O ^e
[0211] in which:
[0212] - M is a chemical element of the group of transition metals, rare earths or lanthanides,
[0213] - a and c are between 0.05 and 10,
[0214] - d is between 0 and 4.0 and
[0215] - e has a value that depends on the oxidation state of the elements Sn, Ti and M.
[0216] Again, the above formula must comply with the condition that the catalyst comprises at least Sn and Ti and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of SnO2 in which the Ti It is incorporated into the structure of the rutile phase.
[0217]
[0218] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, solutions of the same pure elements, or mixing thereof, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0219]
[0220] The catalyst described in this embodiment can be obtained by a process comprising at least:
[0221] a) a first stage, of mixing of compounds of the different elements, of pure elements, or of mixing thereof,
[0222] b) a second stage, of drying the solid obtained in the first stage and
[0223] c) a third stage, for calcining the dry solid obtained in the second stage.
[0224]
[0225] The mixing step can be carried out from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0226]
[0227] The elements Sn, Ti and the metal M can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0228]
[0229] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0230]
[0231] The Ti can be incorporated into the mixing stage preferably as titanium dioxide, titanium oxychloride, titanium oxy sulfate, titanium nitrate, tetrachloride titanium, titanium ethoxide, titanium isopropoxide, titanium butoxide or Ti metal.
[0232]
[0233] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0234]
[0235] The mixing step can be carried out in solution or by hydrothermal treatment.
[0236]
[0237] The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
[0238]
[0239] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0240]
[0241] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0242]
[0243] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn, Ti and the element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. As salts, sulfates, nitrates, oxalates or halides As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The coprecipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0244]
[0245] In an alternative embodiment, the catalyst is obtained using hydrothermal methods (containing two or more elements in the synthesis, especially containing Sn, Ti and element M) in which the temperature and synthesis time can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0246]
[0247] In an alternative embodiment, the catalyst is obtained by impregnating the precursors containing Ti and the metal M onto an SnO ² material, mostly presenting the rutile crystalline phase. As precursor compounds containing Ti and element M, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the elements in the SnO ² material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0248]
[0249] The catalyst described can be used for the inventive process as it is obtained once calcined.
[0250] In an alternative embodiment the catalyst described above in this invention can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0251]
[0252] According to another particular embodiment of the process of the present invention, a catalyst can be used that starting from the formula with the composition Sn ^a Nb ^b Ti ^c M ^d O ^e , in which b and d are zero, has the following empirical formula:
[0253] Sn ^a Ti ^c O ^e
[0254] where:
[0255] - a and c are between 0.05 and 10, and
[0256] - e has a value that depends on the oxidation state of the elements Sn and Ti.
[0257]
[0258] With the proviso that the catalyst comprises at least Sn and Ti and that, in its calcined form, it is presented as a mixed metal oxide formed mostly by the rutile-like crystalline phase of SnO2 in which the Ti is incorporated into the structure of the rutile phase
[0259]
[0260] Said catalyst can be prepared by conventional methods from solutions of compounds of the different elements, from solutions of the same pure elements, or from mixing of both, with the desired atomic ratios. Said solutions are preferably aqueous solutions.
[0261]
[0262] According to this embodiment, the catalyst can be obtained by a process comprising at least:
[0263] a) a first stage, of mixing of compounds of the different elements, of pure elements, or of mixing of both,
[0264] b) a second stage, of drying the solid obtained in the first stage and
[0265] c) a third stage, for calcining the dry solid obtained in the second stage.
[0266]
[0267] The mixing stage can be performed from the compounds of the different elements, from the pure elements themselves in solution, using co-precipitation methods or by hydrothermal methods.
[0268]
[0269] The elements Sn and Ti can be incorporated into the mixing stage as pure metal elements, as salts, as oxides, as hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. As salts, sulfates, nitrates, oxalates or halides are preferably used, without these limiting examples.
[0270]
[0271] The Sn can be incorporated into the mixing stage preferably as tin oxide, tin acetate, tin nitrate, tin chloride, tin fluoride, tin isopropoxide, tin oxalate or tin sulfate.
[0272]
[0273] The Ti may be incorporated into the mixing step preferably as titanium dioxide, titanium oxychloride, titanium oxy sulfate, titanium nitrate, titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium butoxide or Ti metal.
[0274]
[0275] The mixing step can be followed by a period of static permanence in the reactor, or the mixing can be carried out with stirring. Both static permanence and agitation can be performed in a normal reactor or in an autoclave.
[0276]
[0277] The mixing step can be carried out in solution or by hydrothermal treatment.
[0278]
[0279] The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
[0280]
[0281] The step of calcining the dry solid can be carried out under an inert gas atmosphere, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
[0282]
[0283] This calcination stage can be carried out by passing a flow of inert gas (with space velocities between 1 and 400 h-1) or in static. The temperature is preferably in a range between 250 and 850 ° C and more preferably between 400 and 600 ° C. The calcination time is not decisive, but it is preferred that it is in a range between 0.5 hours and 20 hours. The heating rate is not decisive, but is preferred in a range between 0.1 ° C / minute and 10 ° C / minute. The catalyst may also be initially calcined in an oxidizing atmosphere to a temperature between 200 and 350 ° C, and more preferably between 240 and 290 ° C, and subsequently subjected to calcination in an inert atmosphere.
[0284]
[0285] According to this embodiment, the catalyst is obtained, as indicated above, by co-precipitation of the elements, either from precursor compounds containing the different elements or from the pure elements themselves in solution. As precursor compounds containing the elements Sn and Ti, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The co-precipitation of the elements in the solution is carried out by controlled change of pH by the addition of a basic compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide or ammonia water, and alkali metal hypochlorites, Without being these limiting examples. Once the pH is controlled, the solution is allowed to age and subsequently the solid obtained is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0286]
[0287] In an alternative embodiment, the catalyst is obtained using hydrothermal methods (containing at least two elements in the synthesis, especially Sn and Ti) in which the temperature and synthesis time can be decisive. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more preferably, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more preferably between 24 and 200 hours.
[0288]
[0289] In an alternative embodiment, the catalyst is obtained by impregnating Ti precursors onto an SnO2 material, mostly presenting the phase. Rutile crystalline As precursor compounds containing Ti e they can use salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms. Sulfates, nitrates, oxalates or halides are preferably used as salts. As solvents, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. The impregnation of the elements in the SnO2 material can be carried out by wet impregnation, impregnation at incipient volume or pore volume, without being these limiting examples. Once the impregnated solid is obtained, it is washed, dried and a calcination process is submitted for the activation of the material prior to its use in reaction.
[0290]
[0291] The catalyst described according to this embodiment can be used for the inventive process as it is obtained once calcined.
[0292]
[0293] In an alternative embodiment the catalyst described above in this invention can be supported and / or diluted on a solid such as: silica, alumina, titanium oxide or mixtures thereof, as well as silicon carbide. In these cases the fixing of the different catalyst elements on the support can be carried out by conventional impregnation methods, such as pore volume, excess solution, or simply by precipitation on the support of a solution containing the active elements.
[0294]
[0295] The process of the present invention has the following advantages over the state of the art:
[0296]
[0297] - catalysts comprising Sn and Nb, Sn and Ti, and combinations of Sn-Nb or Sn-Ti with other elements, in which at least Sn and Nb or Sn and Ti are present in the form of a mixed oxide, provide yields to C5-C8 hydrocarbons greater than those reported with Ce-Zr-based catalysts, with total yields (“20%) comparable to those observed for these Ce-Zr materials;
[0298]
[0299] - they are more stable and resistant under reaction conditions than other reported catalytic materials;
[0300]
[0301] - they require a lower temperature to perform the procedure when they are compare with data reported in literature for other catalytic materials.
[0302]
[0303] According to the present invention, the metal M may be selected from the group of transition metals, preferably V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ta, Tl, Re and combinations thereof; as well as rare earths and lanthanides, preferably La.
[0304] According to a particular embodiment, the metal M is selected from among V, Mn, Cu, Zn, La and combinations thereof.
[0305]
[0306] According to the process of the present invention, at the end of the same, mixtures of hydrocarbons and aromatic compounds of between 5 and 16 C atoms can be obtained.
[0307]
[0308] According to a particular embodiment, the product obtained can be selected from linear, branched, cyclic aliphatic hydrocarbons of between 5 and 16 C atoms, and may also contain between 0 and 4 O atoms, and more preferably between 0 and 2 atoms from O.
[0309]
[0310] According to another particular embodiment, the product obtained may be selected from among aromatic compounds of between 5 and 16 C atoms, and may also contain between 0 and 4 O atoms.
[0311]
[0312] In the process of the present invention, the aqueous mixture derived from the biomass that is introduced in the first step may contain oxygenated organic compounds having between 1 and 12 carbon atoms, preferably between 1 and 9 carbon atoms, and also , may have between 1 and 9 oxygen atoms, preferably between 1 and 6 oxygen atoms.
[0313]
[0314] According to the present invention, the total concentration of the oxygenated organic compounds present in the aqueous mixture derived from the biomass are preferably in a range of between 0.5 and 99.5% by weight, and more preferably between 1.0 and 70.0% by weight.
[0315]
[0316] In the process described according to the present invention, the contact between the aqueous mixture and the catalyst is carried out in a reactor preferably selected from between a discontinuous reactor, a continuous stirred tank reactor, a continuous fixed bed reactor and a continuous fluidized bed reactor.
[0317]
[0318] According to a particular embodiment, the reactor is a discontinuous reactor and the reaction is carried out in a liquid phase at a pressure preferably selected from 1 to 80 bars, and more preferably at a pressure between 1 and 50 bars. In addition, the reaction can be carried out at a temperature between 100 ° C and 350 ° C, preferably between 140 ° C and 280 ° C. The contact time between the aqueous mixture containing the oxygenated organic compounds derived from the biomass and the catalyst may range from 2 minutes to 200 hours, preferably from 1 hour to 100 hours. According to this particular embodiment, the weight ratio between the aqueous mixture containing the oxygenated compounds derived from the biomass and the catalyst can be preferably between 1 and 200, and more preferably between 2.5 and 100.
[0319]
[0320] According to another particular embodiment, the reactor that is used in the process of the present invention can be a fixed bed reactor or a fluidized bed reactor. In this case, the reaction temperature is preferably in a range between 100 ° C and 350 ° C and more preferably between 150 ° C and 300 ° C; the contact time (W / F) is between 0.001 and 200 s; and the working pressure of between 1 and 100 bars and more preferably between 1 and 60 bars.
[0321]
[0322] According to the procedure described above, the contact between the aqueous fraction containing the oxygenated organic compounds and the catalyst can be carried out under nitrogen, argon, air atmosphere, nitrogen enriched air, argon enriched air, or combinations of the same.
[0323]
[0324] According to a particular embodiment, the process is preferably carried out in a nitrogen atmosphere.
[0325]
[0326] According to another particular embodiment, the process is preferably carried out in an atmosphere of air or air enriched with nitrogen.
[0327] As already mentioned, the present invention describes the use of the catalyst obtained as described above to obtain mixtures of hydrocarbons and aromatic compounds, preferably between 5 and 16 C (C5-C16) atoms useful in liquid fuels, a from the catalytic transformation of oxygenated organic compounds present in aqueous fractions derived from biomass.
[0328]
[0329] The aqueous fractions derived from the biomass containing different oxygenated organic compounds to be treated by the process of the present invention may be selected from among aqueous fractions obtained by liquid-liquid separation of the bio-liquids produced by thermal pyrolysis and / or catalytic biomass , aqueous fractions obtained by chemical and / or enzymatic biomass hydrolysis, aqueous fractions obtained by liquefaction under sub-or supercritical biomass conditions, and aqueous fractions obtained from biomass fermentation for the selective production of ethanol, butanol, succinic acid, and lactic acid, without being these limiting examples.
[0330]
[0331] The aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds having between 1 and 12 Carbon atoms, preferably between 1 and 9 Carbon atoms.
[0332]
[0333] In addition, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds possessing between 1 and 9 Oxygen atoms, preferably between 1 and 6 O atoms.
[0334]
[0335] The aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds in concentrations ranging between 0.5 and 99.5% by weight with respect to the amount of water, preferably of between 1.0 and 70.0% by weight with respect to the amount of water.
[0336]
[0337] According to a particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds, including alcohols, aldehydes, ketones, acids and carboxylic acids, esters, ethers, diols, triols and polyols in general, sugars, furanic derivatives, and phenolic derivatives , without being these limiting examples.
[0338]
[0339] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the alcohol type, including methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, iso-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, and furfuryl alcohol, without being these limiting examples. According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated compounds of the aldehyde type, including formaldehyde, acetaldehyde, propanal, butanal, 2-butenal, pentanal, 2-pentenal , 3-pentenal, hexanal, 2-hexenal, 3-hexenal, 2-methyl-2-pentenal, 2-methyl-3-pentenal, 3-methyl-2-pentenal, furfural, and 5-hydroxymethyl-furfural, without being these limiting examples.
[0340]
[0341] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the ketone type, including acetone, 2-butanone, 2-pentanone, penten-2-one, 3-pentanone, penten-3-one, 2-hexanone, hexen-2-one, 3-hexanone, hexen-3-one, iso-forone, vanillin, aceto-vanillin, syringone, and acetosyringone, without being these limiting examples .
[0342]
[0343] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the acid and di-acid type, including acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, lactic acid, pyruvic acid, levulinic acid, tartronic acid, tartaric acid, glycolic acid, succinic acid, gluconic acid, and glucaric acid, without being these limiting examples.
[0344]
[0345] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the ester type, including methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate, without being these limiting examples .
[0346]
[0347] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the ether type, including di-methyl ether, di-ethyl ether, di-propyl ether, di -iso-propyl ether, di-butyl ether, di-sec-butyl ether, methyl-ethyl ether, methyl-propyl ether, methyl-iso-propyl ether, methyl-butyl ether, methyl-sec-butyl ether, ethyl-propyl ether, ethyl-isopropyl ether, ethyl-butyl ether, ethyl-sec-butyl ether, propyl-butyl ether, and propyl-sec-butyl ether, without being these limiting examples.
[0348]
[0349] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the diols type, including ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3- pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,3-hexane-diol, 2,4-hexanediol; triols, including glycerol, 1,2,3-butanedriol, 1,2,4-butanedriol, 1,2,3-pentanotriol, 1,2,4-pentanotriol, 1,2,3-hexanotriol, 1,2, 4-hexanotriol, 1,2,5-hexanotriol, 1,2,6-hexanotriol, 2,3,4-hexanotriol, 2,3,5-hexanotriol, 2,3,6-hexanotriol, 1,3,6- hexanotriol, 1,4,6-hexanotriol; and polyols, among them, mono-sugars of the glucose, fructose, and arabinose type, without being these limiting examples.
[0350]
[0351] According to another particular embodiment, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated organic compounds of the Furyne derivatives type, including furan, 2-methyl-furan, 5-methyl-furan, 2 , 5-dimethyl-furan, 2-ethyl-furan, 5-ethyl-furan, 2,5-diethylfuran, benzofuran, methyl benzofuran, ethyl benzofuran, without being these limiting examples.
[0352] The aqueous fractions derived from biomass to be treated by the process of the present invention may contain different oxygenated compounds of the phenolic derivatives type, including phenol, benzyl alcohol, acetol, o-cresol, m-cresol, pcresol, guaiacol, vanillin alcohol, siringol, and aceto-siringol, without being these limiting examples.
[0353]
[0354] The mixtures of organic compounds of between 5 and 16 C atoms (C5-C16) obtained as a result of the transformation of the oxygenated compounds present in aqueous fractions derived from biomass, may contain linear, branched, cyclic linear aliphatic hydrocarbon compounds of 5 and 16 C atoms, and may also contain between 0 and 4 O atoms, preferably between 0 and 2 O atoms.
[0355]
[0356] Mixtures of organic compounds of between 5 and 16 C atoms (C5-C16) obtained as a result of the transformation of oxygenated compounds present in aqueous fractions derived from biomass, may contain aromatic compounds of between 5 and 16 C atoms , may also contain between 0 and 4 O atoms, preferably between 0 and 2 O atoms. These aromatic compounds may possess one, two, or more substituents in the ring, these substituents being able to be of the linear, branched and branched alkyl type / or cyclic, linear, branched and / or cyclic alkoxide, acetyl, tetrahydrofuran, fury, and aromatic, without being these limiting examples.
[0357]
[0358] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which the present invention belongs. Procedures and materials similar or equivalent to those described herein may be used in the practice of the present invention. Throughout the description and claims, the word "comprises" and its variations are not intended to exclude other technical characteristics, additives, components or steps. Additional objects, advantages and features of the invention will be apparent to those skilled in the art after examination of the description or can be learned by the practice of the invention The following graphic examples are provided by way of illustration and are not intended to be limiting of the present invention.
[0359] BRIEF DESCRIPTION OF THE GRAPHICS
[0360]
[0361] Fig. 1 . It shows X-ray diffractograms of catalysts based on Sn [SnO2], Nb [Nb2O5] and Ti [TiO2-Anatase] and [TiO2-Rutile] oxides.
[0362]
[0363] Fig. 2 . It shows X-ray diffractograms of catalysts based on oxides of Sn (a) [SnO2], Nb (b) [Nb2O5] and Ti (c) [TiO2] prepared by co-precipitation described in examples 1, 2 and 3, respectively .
[0364]
[0365] Fig. 3 . It shows X-ray diffractograms of catalysts based on tin and niobium oxides [Sn-Nb-O] described in Examples 4 to 7.
[0366]
[0367] Fig. 4 . It shows X-ray diffractograms of catalysts based on tin and titanium oxides [Sn-Ti-O] described in Examples 8 to 11.
[0368]
[0369] Fig. 5 . It shows X-ray diffractograms of catalysts based on tin, titanium and niobium oxides [Sn-Nb-Ti-O] described in Examples 12 to 15.
[0370]
[0371] Fig. 6 . It shows the X-ray diffractogram of a Ce-Zr-O based catalyst (Example 16).
[0372]
[0373] Fig. 7 . It shows X-ray diffractograms of Nb and Ti-based catalysts supported by impregnation over tin oxide [Nb / SnO2 and Ti / SnO2] described in Examples 17 and 18, respectively.
[0374]
[0375] Fig. 8 . It shows a scheme with the chemical structures of reagents and main reaction products, together with the reactions that take place during the process.
[0376]
[0377] Fig. 9. Shows a comparison of the stability and maintenance of the catalytic activity with the re-uses of the catalysts Sn-Nb-O (Example 5), Sn-Ti-O (Example 10) and Ce-Zr-O (Example 16).
[0378] E J E M P L O S
[0379]
[0380] Next, the inventors will illustrate the invention by means of various tests demonstrating the preparation of the catalysts and their application in the process of the invention.
[0381]
[0382] E j e m p l o 1. P r e p a r a c i o n d e u n c a t a l i z a d o r p o r m é t o d o d e c o - p r e c i p i t a c i o n,
[0383] b a s a d o e n o x i d o d e e s t a ñ o [S n O 2]
[0384]
[0385] In 200.0 ml of water, 14.72 g of tin (IV) pentahydrate chloride are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 2a.
[0386]
[0387] E j e m p l o 2. P r e p a r a c i o n d e u n c a t a l i z a d o r p o r m é t o d o d e c o - p r e c i p i t a c i o n,
[0388] b a s a d o e n o x i d o d e n i o b i o [N b 2O 5]
[0389]
[0390] In 200.0 ml of water, 12.73 g of niobium oxalate are added, which is kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 2b.
[0391]
[0392] E j e m p l o 3. P r e p a r a c i o n d e u n c a t a l i z a d o r p o r m é t o d o d e c o - p r e c i p i t a c i o n,
[0393] b a s a d o e n o x i d o d e t i t a n i o [T i O 2]
[0394]
[0395] In 200.0 ml of water, 8.48 ml of an aqueous solution of oxychloride of titanium with hydrochloric acid, which are kept under stirring until completely homogenized. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 hours at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 2c.
[0396]
[0397] Example 4. Preparation of a catalyst by co-precipitation method, based on tin and niobium oxides with a molar ratio Sn / Nb = 0.77 [Sn-Nb-O (0.77)]
[0398]
[0399] In 200.0 ml of water, 9.82 g of tin (IV) pentahydrate chloride and 4.24 g of niobium oxalate are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 3a.
[0400]
[0401] Example 5. Preparation of a catalyst by co-precipitation method, based on tin and niobium oxides with a molar ratio Sn / Nb = 0.58 [Sn-Nb-O (0.58)]
[0402]
[0403] In 200.0 ml of water, 7.01 g of tin (IV) pentahydrate chloride and 6.06 g of niobium oxalate are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 hours at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. East The catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 3b.
[0404]
[0405] Example 6. Preparation of a catalyst by co-precipitation method, based on tin and niobium oxides with a molar ratio Sn / Nb = 0.43 [Sn-Nb-O (0.43)]
[0406]
[0407] In 200.0 ml of water, 4.91 g of tin (IV) pentahydrate chloride and 8.48 g of niobium oxalate are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 3c.
[0408]
[0409] Example 7. Preparation of a catalyst by co-precipitation method, based on tin and niobium oxides with a molar ratio Sn / Nb = 0.29 [Sn-Nb-O (0.29)]
[0410]
[0411] In 200.0 ml of water, 3.51 g of tin (IV) pentahydrate chloride and 12.12 g of niobium oxalate are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 3d.
[0412]
[0413] Example 8. Preparation of a catalyst by co-precipitation method, based on tin and titanium oxides with a molar ratio Sn / Ti = 0.74 [Sn-Ti-O (0.74)]
[0414] In 200.0 ml of water, 14.02 g of tin (IV) pentahydrate chloride and 2.02 ml of an aqueous solution of titanium oxychloride with hydrochloric acid are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 4a.
[0415]
[0416] Example 9. Preparation of a catalyst by co-precipitation method, based on tin and titanium oxides with a molar ratio Sn / Ti = 0.64 [Sn-Ti-O (0.64)]
[0417]
[0418] In 200.0 ml of water, 9.82 g of tin (IV) pentahydrate chloride and 2.84 ml of an aqueous solution of titanium oxychloride with hydrochloric acid are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 4b.
[0419]
[0420] Example 10. Preparation of a catalyst by co-precipitation method, based on tin and titanium oxides with a molar ratio Sn / Ti = 0.33 [Sn-Ti-O (0.33)]
[0421]
[0422] In 200.0 ml of water, 4.91 g of tin (IV) pentahydrate chloride and 5.68 ml of an aqueous solution of titanium oxychloride with hydrochloric acid are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 hours at a temperature. environment. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 4c.
[0423]
[0424] Example 11. Preparation of a catalyst by co-precipitation method, based on tin and titanium oxides with a molar ratio Sn / Ti = 0.18 [Sn-Ti-O (0.18)]
[0425]
[0426] In 200.0 ml of water, 3.51 g of tin (IV) pentahydrate chloride and 8.08 ml of an aqueous solution of titanium oxychloride with hydrochloric acid are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 4d.
[0427]
[0428] Example 12. Preparation of a catalyst by co-precipitation method, based on tin, niobium and titanium oxides with a molar ratio Sn / (Ti + Nb) = 0.60 [Sn-Nb-Ti-O (0.60 )]
[0429]
[0430] In 200.0 ml of water, 9.35 g of tin (IV) pentahydrate chloride, 1.33 ml of an aqueous solution of titanium oxychloride with hydrochloric acid and 5.05 g of niobium oxalate are added, which are maintained stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 hours at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 5a.
[0431] Example 13. Preparation of a catalyst by co-precipitation method, based on tin, niobium and titanium oxides with a molar ratio Sn / (Ti + Nb) = 0.35 [Sn-Nb-Ti-O (0.35 )]
[0432]
[0433] In 200.0 ml of water 5.84 g of tin (IV) pentahydrate chloride, 3.37 ml of an aqueous solution of titanium oxychloride with hydrochloric acid and 5.05 g of niobium oxalate are added, which are maintained stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 5b.
[0434]
[0435] Example 14. Preparation of a catalyst by co-precipitation method, based on tin, niobium and titanium oxides with a molar ratio Sn / (Ti + Nb) = 0.29 [Sn-Nb-Ti-O (0.29 )]
[0436]
[0437] In 200.0 ml of water 4.67 g of tin (IV) pentahydrate chloride, 2.70 ml of an aqueous solution of titanium oxychloride with hydrochloric acid and 8.08 g of niobium oxalate are added, which are maintained stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 5c.
[0438]
[0439] Example 15. Preparation of a catalyst by co-precipitation method, based on tin, niobium and titanium oxides with a molar ratio Sn / (Ti + Nb) = 0.16 [Sn-Nb-Ti-O (0.16 )]
[0440] In 200.0 ml of water, 2.34 g of tin (IV) pentahydrate chloride, 5.40 ml of an aqueous solution of titanium oxychloride with hydrochloric acid and 5.05 g of niobium oxalate are added, which are maintained. stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 9 is reached. The resulting gel is transferred to a container where it is allowed to age for 24 h at room temperature. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 5d.
[0441]
[0442] Example 16. Preparation of a catalyst based on mixed oxides of Ce and Zr [Ce-Zr-O] by the co-precipitation method
[0443]
[0444] This catalyst was synthesized to illustrate catalysts of the type Ce-Zr mixed oxides commonly used in literature for this type of condensation reactions [A. Gangadharan et al., Appl. Catal. A: Gral., 385 (2010) 80]. Various catalysts with different Ce-Zr ratios were synthesized, and the catalyst that provided the best results, in terms of yield to organic and conversion was selected to be compared with the catalysts of the present invention.
[0445]
[0446] The catalyst was prepared by the synthesis method by co-precipitation of the mixed oxide Ce-Zr adapting the procedure published by Serrano-Ruiz et al. [J. Catal., 241 (2006) 45-55]. To synthesize the Ce05Zr05O2 catalyst, an aqueous solution of the salts of both metals is prepared in equimolar proportion. In 150 ml of water, 11.76 g of Ce (NO3) 36H2O and 6.70 g of ZrO (NO3) 2 H2O are added, which are kept under stirring until completely dissolved. Then, a 28% solution of NH4OH is added dropwise until a pH = 10 is reached. Subsequently, the solution is transferred to a balloon where it is allowed to age under stirring and at room temperature for 65 h. After a washing and filtering step, the solid is dried at 100 ° C overnight. Finally, the solid obtained is heated at 450 ° C for 2 h in a stream of air to obtain the catalyst. The amounts of Ce and Zr measured by ICP coincide with the formula Ce05Zr05O2, and the X-ray diffractogram obtained for this sample indicates the presence of mixed oxides of Ce and Zr (Fig. 6)
[0447] E j e m p l o 17. P r e p a r a c i o n d e u n c a t a l i z a d o r b a s a d o e n o x i d o s m i x t o s d e e t t y y
[0448] n i o b i o [N b - S n O 2 i m p r e g. ] e m p l e a n d o u n m é t o d o d e i m p r e g n a c i o n
[0449]
[0450] A mixed oxide type catalyst with an Sn-Nb ratio similar to that used for the catalyst of Example 4 was synthesized, in order to be compared in terms of catalytic activity with the catalysts of the present invention.
[0451]
[0452] The catalyst was prepared by the pore volume impregnation synthesis method. To synthesize the Nb-SnO2 catalyst, an aqueous solution is prepared containing 1.86g of niobium oxalate in a volume of water previously calculated to impregnate about 1.5 g of commercial SnO2. The solution is added dropwise onto said support until a homogeneous gel is obtained. After a drying step at a temperature of 100 ° C, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 7a.
[0453]
[0454] E j e m p l o 18. P r e p a r a c i o n d e u n c a t a l i z a d o r b a s a d o e n o x i d o s m i x t o s d e S n y T i
[0455] [T i - S n O 2 i m p r e g. ] e m p l e a n d o u n m é t o d o d e i m p r e g n a c i o n
[0456]
[0457] A mixed oxide type catalyst was synthesized with an Sn-Ti ratio similar to that used for the catalyst of Example 8, in order to be compared in terms of catalytic activity with the catalysts of the present invention.
[0458] The catalyst was prepared by the pore volume impregnation synthesis method. To synthesize the Ti-SnO2 catalyst, an aqueous solution containing 0.7 ml of an aqueous solution of titanium oxychloride with hydrochloric acid is prepared in a volume of water previously calculated to impregnate about 1.5 g of commercial SnO2. The solution is added dropwise onto said support until a homogeneous gel is obtained. After a drying step at a temperature of 100 ° C, the solid obtained is heated at 600 ° C for 2 h in a stream of air to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 7b.
[0459] Example 19. Comparative catalytic activity of the catalysts of the Sn-Nb series of Examples 1, 2, 4, 5, 6 and 7.
[0460]
[0461] The catalytic activity experiments were carried out in liquid phase using 12 ml stainless steel autoclave type reactors with a reinforced PEEK (polyether-ethyl ketone) coated interior and equipped with magnetic stirrer, pressure gauge and inlet valve / output of gases and liquid samples. The reactors are located on an individual steel jacket support with closed loop temperature control.
[0462]
[0463] The initial feed consists of a model aqueous mixture containing oxygenated compounds simulating the residual aqueous currents that are obtained after a phase separation process, after the pyrolysis of the biomass. The composition of the model aqueous mixture is detailed below (Table 1):
[0464]
[0465]
[0466]
[0467]
[0468] Table 1. Composition of the model aqueous mixture used as initial feed in the autoclave type reactor.
[0469]
[0470] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 1, 2, 4-7 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50 100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m The identification of the products is carried out by means of a gas chromatograph Agilent 6890 N coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with a 30 m long HP-5 MS capillary column.
[0471]
[0472] The quantification of the products is carried out from the response factors calculated by internal standard (2% by weight solution of chlorobenzene in methanol) and organic compounds obtained from more than 5 carbon atoms are classified and quantified in ranges or intervals of compounds, whose response factors have been calculated from representative molecules thereof. In addition to the main primary condensation reaction products, such as acetone, ethyl acetate, 3-pentanone and 2-methyl-2-pentenal, groups of molecules with 5, 6, 7, 8, 9, 10 or more are distinguished of 10 carbon atoms, produced by consecutive condensation reactions of reagents and primary products. To simplify the quantification of these reaction products, these molecules are grouped into two large groups of compounds, namely: Products C5-C8 and Products C9-C10 +. The chemical structures of the reagents and the main reaction products, together with the most significant reactions that take place during the process, are detailed in Figure 8.
[0473]
[0474] In the examples of catalytic activity illustrated, the following parameters are used to analyze the results obtained:
[0475]
[0476] The conversion (in mole percent) for each of the oxygenated compounds present in the model aqueous mixture, was calculated from the following formula:
[0477]
[0478] Conversion (%) = (initial moles of oxygenated comp - final moles of comp.
[0479] oxygenated / initial moles of comp. oxygenated) * 100
[0480]
[0481] The final yield (in percentage by weight) to each of the products obtained, was calculated from the following formula:
[0482]
[0483] Product yield (%) = grams product i in the reactor / total grams in the reactor
[0484] The Total Organic Yield (in percentage by weight), was calculated from the following formula:
[0485]
[0486] Total Organic (%) = (RendAcetone Rend3-pentanone Rend2-methyl-2-pentenal RendC5-C8
[0487] Yield C9-C10 +)
[0488]
[0489] In addition, taking into account the composition of the model aqueous mixture used, the maximum total organic products that could be obtained are calculated, assuming that:
[0490] - 100% conversion of all reagents is reached.
[0491] - Acetic acid can be transformed into ethyl acetate (esterification product) and acetone (ketone product).
[0492] - The final products are compounds of type C9 (there are no intermediate or longer chain products in the final mixture).
[0493]
[0494] With these assumptions, the composition of the final mixture would be:
[0495] 51.3% water, 19.1% ethyl acetate and 29.6% C9 products.
[0496]
[0497] Therefore, the catalytic results (expressed as yield to total products) are calculated considering «30% as the maximum possible.
[0498]
[0499] Thus, the following results were obtained for the catalytic activity experiments with the catalysts based on Sn and Nb of Ex. 1,2, 4, 5, 6 and 7:
[0500]
[0501]
[0502]
[0503] Table 2. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and / or Nb of Examples 1, 2, 4, 5, 6 and 7.
[0504]
[0505] From the comparison of the results in Table 2, it is observed that the conversion of hydroxy-acetone is 100% in all cases, while the conversion of propionaldehyde reaches a maximum ("96%) for catalysts with a Sn molar ratio. / Nb close to 0.6. Acetone (acetic acid condensation product) is present in the final mixture in amounts below 1.5%, because most of the acetic acid reacts with ethanol via esterification to give ethyl acetate. In addition, acetone is a very reactive compound that can lead to condensation products of higher molecular weight.
[0506]
[0507] In addition, it is observed how for molar ratios Sn / Nb «0.4-0.6; intermediate condensation products (C5-C8) are decreasing to give rise to products of greater molecular weight in later stages of condensation. Likewise, the increase in the conversion of propionaldehyde causes the amount of 2-methyl-2-pentenal (product of the first self-condensation of propionaldehyde) to grow and be transformed successively into condensation products in the range of C9-C10 +. Therefore, the Total Organic Yield is maximized to those catalyst compositions.
[0508] These results show that the combination of Sn and Nb oxides in the structure of these catalysts produces higher yields of condensation products and, in general, higher yields to products in the range of C9-C10 + than their analog catalyst SnO2 without niobium (example one). On the other hand, the Nb2O5 non-tin catalyst (example 2) shows even worse catalytic activity (both in conversion of oxygenated compounds and in yield to total organic, <52%). On the other hand, even when there are small amounts of Sn present in the catalyst (See result with low concentrations of Sn, catalyst of Ex. 7), a mixed oxide with rutile structure is formed which implies an improvement in the catalytic results. All this would indicate that there is an optimal range in the Sn / Nb ratio (between Examples 4, 5 and 6) in the catalyst structure to achieve maximum yields in the transformation of oxygenated compounds present in aqueous mixtures derived from biomass.
[0509]
[0510] Example 20. Comparative catalytic activity of the Sn-Ti series catalysts of Examples 1, 3, 8, 9, 10 and 11.
[0511]
[0512] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 1, 3, 8-11 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50 100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0513]
[0514] Thus, the following results were obtained for the catalytic activity experiments with the Sn and Ti based catalysts of Ex. 1, 3, 8, 9, 10 and 11:
[0515]
[0516]
[0517]
[0518] Table 3. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and / or Ti of Examples 1, 3, 8, 9, 10 and 11.
[0519]
[0520] From the comparison of the results in Table 3, it is observed that the conversion of hydroxy-acetone is 100% in all cases, while the conversion of propionaldehyde reaches a maximum («88%) for all oxide-based catalysts mixed where there is a rutile phase Sn-Ti, regardless of the molar ratio Sn / Ti. Acetone (condensation product of acetic acid) is present in the final mixture in amounts less than 1.0%, because most of the acetic acid reacts to ethyl acetate. In addition, acetone is a very reactive compound that can lead to condensation products of higher molecular weight.
[0521]
[0522] It is appreciated that by having a mixed Sn-Ti phase, the conversion of propionaldehyde increases and causes the amount of 2-methyl-2-pentenal (product of the first self-condensation of propionaldehyde) and, above all, the products of second stages of condensation in the interval C9-C10 +, grow.
[0523]
[0524] Therefore, the Total Organic Performance exhibits the same behavior. This means that the yield to Total Organic, and particularly the production of compounds C9-C10, can be increased by synthesizing the materials in the appropriate Sn-Ti-O compositions.
[0525]
[0526] These results show that the combination of Sn and Ti oxides in the structure of these catalysts produces higher yields of condensation products and, in general, higher yields to products in the range of C9-C10 + than their SnO2 analog catalyst without titanium (Example one). In addition, the tin-free catalyst, TiO2 (Example 3) shows an acceptable catalytic activity (yield at total organic, "57%), although the result is not fully comparable, since by synthesizing this oxide by co-precipitation, the resulting phase It is TiO2-anatase. All this would indicate that the synthesis of mixed oxides based on Sn / Ti with rutile structure (Examples 8 to 11) in the catalyst structure implies an improvement in the transformation of oxygenated compounds present in aqueous mixtures derived from biomass.
[0527]
[0528] Example 21. Comparative catalytic activity of the Sn-Ti-Nb series catalysts of Examples 1, 2, 12, 13, 14 and 15.
[0529]
[0530] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 1, 2, 12-15 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50-100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0531]
[0532] Thus, the following results were obtained for catalytic activity experiments with the Sn-Ti-Nb based catalysts of Ex. 1, 2, 12, 13, 14 and 15:
[0533]
[0534]
[0535]
[0536] Table 4. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and / or Ti and / or Nb of Examples 1,2, 12, 13, 14 and 15.
[0537]
[0538] From the comparison of the results in Table 4, it is observed that the conversion of hydroxy-acetone is in all cases 100%, while the propionaldehyde conversion increases dramatically when a mixed oxide of Sn is formed with Ti and Nb in the catalysts used.
[0539]
[0540] Acetone (acetic acid condensation product) is present in the final mixture in amounts less than 1.5%, because most of the acetic acid reacts by esterification to produce ethyl acetate. In addition, acetone is a very reactive compound that can lead to condensation products of higher molecular weight.
[0541]
[0542] The increase in the conversion of propionaldehyde causes the amount of 2-methyl-2-pentenal (product of the first self-condensation of propionaldehyde) to grow and therefore be able to continue reacting to give rise to condensation products in the C9-C10 + interval (fruit of subsequent condensation stages). Both C9-C10 + products and Total Organic Yields exhibit the same behavior.
[0543] These results show that the combination of Sn, Ti and Nb oxides in the structure of these catalysts produces higher yields of condensation products and, in general, greater yield to products in the range of C9-C10 + than their simple oxides catalyst: SnO2 (Example 1), Nb2O5 (Example 2) or TiO2 (Example 3). All this would confirm that the formation of a mixed oxide phase with rutile phase with an Sn / (Ti + Nb) ratio (between Examples 12 and 15) in the catalyst structure allows to achieve maximum yields in the transformation of present oxygenated compounds in aqueous mixtures derived from biomass.
[0544]
[0545] E j e m p l o 22. A c t i v i d a d c a t a l í t i c a c o m p a r a t i v a d e l o s c a t a l i z a d o r e s d e l a s e r i e d e
[0546] S n - N b (E j e m p l o s 4 y 5) f r e n t e a o x i d o d e N b - S n O 2 p r e p a r a d o p o r i m p r e g n a c i o n
[0547] (E j e m p l o 17) and N b 2O 5 c o m e r c i a l (S i g m a - A l d r i c h, C A S 1313 - 96 - 8)
[0548]
[0549] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 4, 5, 17 and commercial Nb2O5 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50-100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0550]
[0551] The following results were obtained:
[0552]
[0553]
[0554] Table 5. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and Nb, Examples 4 and 5, against the results of the Nb-SnO2 catalyst prepared by impregnation (Example 17) or commercial Nb2O5.
[0555]
[0556] In Table 5, the catalytic results of the catalysts based on Sn-Nb-O structures prepared by co-precipitation and described above (Examples 4 and 5) are compared with another catalyst based on mixed oxides of both metals and prepared by the impregnation method, the preparation of which is described in Example 17. In addition, a commercial Nb2O5 catalyst purchased from Sigma-Aldrich is also used, which is activated analogously prior to use.
[0557]
[0558] From the results in Table 5, the total conversion of hydroxy-acetone is observed in all cases, while the conversion of acetic acid is quite similar in all cases studied (close to 15%).
[0559]
[0560] The conversion of propionaldehyde is the biggest difference between one type of catalyst and others. While catalysts based on combined Sn-Nb structures show conversions> 90%, the commercial niobium catalyst and the Nb-SnO2 catalyst (Example 17), have much lower conversions (67-70%). This causes the decrease in the formation of first condensation products such as 2-methyl-2-pentenal and some C5-C8 products, as well as products of greater molecular weight originated by second condensation reactions. In these cases, the Total Organic Yield decreases to 49-56%, which means that the use of catalysts based on specific Sn-Nb structures such as Examples 4 and 5 increases the products by 15-25% obtained in the final reaction mixture of the condensation of oxygenated compounds present in aqueous mixtures derived from biomass. These products are potentially usable as additives in gasoline and refining fractions in general.
[0561]
[0562] These results show that the catalysts of the process of the present invention show results in activity and yields to products superior to those obtained with catalysts prepared by conventional methods or with similar commercial materials.
[0563]
[0564] E j e m p l o 23. A c t i v i d a d c a t a l í t i c a c o m p a r a t i v a d e l o s c a t a l i z a d o r e s d e l a s e r i e d e
[0565] S n - T i (E j e m p l o s 10 and 11) f r e n t e a o x i d o d e T i - S n O 2 p r e p a r a d o p o r i m p r e g n a c i o n
[0566] (E j e m p l o 18) and m u e s t r a s d e T i O 2 c o m e r c i a l a n a t a s a (S i g m a - A l d r i c h, C A S 13 17 - 70
[0567] 0) y T i O 2 c o m e r c i a l r u t i l o (S i g m a - A l d r i c h, C A S 1317 - 80 - 2)
[0568]
[0569] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 10, 11, 18 and commercial TiO2 samples were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50-100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0570]
[0571] The following results were obtained:
[0572]
[0573]
[0574]
[0575] Table 6. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and Ti, Examples 10 and 11, against the results of the Ti-SnO2 catalyst prepared by impregnation (Example 18) or TiO2 samples commercial.
[0576]
[0577] In Table 6, the catalytic results of the catalysts based on Sn-Ti-O structures prepared by co-precipitation and described above (Examples 10 and 11) are compared with another catalyst based on mixed oxides of both metals and prepared by the impregnation method, the preparation of which is described in Example 18. In addition, samples of commercial TiO2 purchased from Sigma-Aldrich are also used, which is activated analogously prior to use.
[0578]
[0579] From the results in Table 6, the total conversion of hydroxy-acetone is observed in all cases, while the conversion of acetic acid is quite similar in all cases studied (close to 10-15%).
[0580]
[0581] The conversion of propionaldehyde is the biggest difference between one type of catalyst and others. While the catalysts based on combined Sn-Ti structures show conversions> 87%, the commercial titanium oxide samples and the Ti-SnO2 catalyst (Example 18) show much lower conversions (58-68%). This causes the decrease in the formation of first products condensations such as 2-methyl-2-pentenal and some C5-C8 products, as well as higher molecular weight products originated by second condensation reactions. In these cases, the Total Organic Yield decreases to 48-51%, which means that the use of catalysts based on specific Sn-Ti structures such as Examples 10 and 11 increases the products obtained by 20% in the final reaction mixture of the condensation of oxygenated compounds present in aqueous mixtures derived from biomass. These products are potentially usable as additives in gasoline and refining fractions in general.
[0582]
[0583] These results show that the catalysts of the process of the present invention show results in activity and yields to products superior to those obtained with catalysts prepared by conventional methods or with similar commercial materials.
[0584]
[0585] Example 24. Comparative catalytic activity of the Sn-Nb-O, Sn-Ti-O and Sn-Ti-Nb-O series catalysts prepared by co-precipitation method (Examples 4, 5, 10, 11, 12 and 13)
[0586]
[0587] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 4, 5, 10, 11, 12 and 13 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples («50-100 pl) were taken at different time intervals up to 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0588]
[0589] The following results were obtained:
[0590]
[0591]
[0592]
[0593] Table 7. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on Sn and / or Nb and / or Ti, prepared by co-precipitation, Examples 4, 5, 10, 11, 12 and 13.
[0594]
[0595] In Table 7, the catalytic results of the catalysts based on structures containing Sn-Nb-O, Sn-Ti-O and Sn-Nb-Ti-O prepared by coprecipitation and then heat treated in an air atmosphere at 600 ° are compared C as described above (Examples 4, 5, 10, 11, 12 and 13).
[0596]
[0597] From the results in Table 7, the total conversion of hydroxy-acetone in all cases is 100%, while the conversion of acetic acid is quite similar in the catalysts shown here (Examples 4, 10, 11, 12, 13); being somewhat smaller in the material of example 5.
[0598]
[0599] The yield to 2-methyl-2-pentenal, C9-C10 products and in general yield to Total Organic products, can be increased by synthesizing the materials in the appropriate compositions, thus achieving catalysts based on specific Sn-Nb-O structures. , Sn-Ti-O and Sn-Ti-Nb-O as in Examples 4, 5, 10, 11, 12 and 13.
[0600]
[0601] Example 25. Comparative catalytic activity of the catalysts of the series of Sn-Nb-O, Sn-Ti-O and Sn-Ti-Nb-O, prepared by co-precipitation (Examples 5, 10 and 13) against a conventional Ce-Zr catalyst (Example 16)
[0602]
[0603] 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 5, 10, 13 and 16 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50-100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0604]
[0605] The following results were obtained:
[0606]
[0607]
[0608]
[0609]
[0610] Table 8. Comparative catalytic activity of catalysts based on Sn, Nb and / or Ti of Examples 5, 10 and 13 in the transformation of oxygenated compounds present in a model aqueous mixture against a conventional Ce-Zr catalyst (Example 16).
[0611] The conversions of propionaldehyde and hydroxy acetone are very similar in the catalysts of Examples 5, 10, 13 and 16, while the Ce-Zr-O catalyst exhibits a greater conversion of acetic acid (results in Table 7). However, both the overall reagent conversion and the Total Organic Yield observed are very similar in the three examples studied (64-68%). The only observable difference between the catalysts based on oxides of Sn, Nb and / or Ti (Ex. 5, 10 and 13) and the mixed oxide of Ce-Zr (Ex. 16) is that the first three have a higher production of organic compounds in the C5-C8 range, while the mixed oxide prepared in Example 16 is able to more easily catalyze second condensation reactions, increasing the amount of compounds in the C9-C10 + range.
[0612]
[0613] In general, catalysts based on structures that combine Sn, Nb and / or Ti have results similar to those demonstrated by a catalyst such as Ce05Zr05O2 traditionally used in literature for reactions of this type.
[0614]
[0615] The catalysts of Examples 5, 10, 13 and 16 once used are recovered after the reaction, subjected to a methanol wash and dried at 100 ° C overnight. Subsequently, they are characterized by Elemental Analysis (AE) and Thermogravimetry (TG).
[0616]
[0617] The AE study shows that the Ce-Zr type catalyst of Example 16 has 3.5% by weight of carbon (organic products deposited in the catalyst) after washing. The Sn-Nb-based catalyst of Example 5 only has 0.5% by weight of carbon, demonstrating that a lower deposition of carbonaceous substances occurs during the reactive process, and is therefore less sensitive to deactivation caused by the coke deposition
[0618]
[0619] These characterization data are confirmed by TG analyzes. The Ce-Zr catalyst of Example 16 exhibits a mass loss of 11.5% at a temperature close to 300 ° C corresponding to the desorption of the absorbed organic products. On the other hand, the catalyst of Example 5 only shows a mass loss of 1.5% at said temperature. This catalyst also has a mass loss of 1.8% at a temperature close to 100 ° C corresponding to absorbed water This amount of absorbed water is also observed in the TG analysis of the catalyst before being used, so the presence of water in the reaction medium does not cause damage to the activity of the catalyst or its stability.
[0620]
[0621] Example 26. Comparative catalytic activity during reuse of Sn-Nb-O (Ex. 5), Sn-Ti-O (Ex. 10), and Ce-Zr-O (Ex. 16) catalysts
[0622]
[0623] A series of consecutive reactions with the catalysts prepared in Examples 5, 10 and 16 were carried out to compare their activity after several uses. For this, the initial reaction (R0) and three subsequent reuses (R1, R2 and R3) were performed, all under the same reaction conditions. The catalysts used are recovered after each reaction, subjected to a methanol wash and dried at 100 ° C overnight. Subsequently, they are characterized by Elemental Analysis (AE) and Thermogravimetry (TG).
[0624]
[0625] In each case (R0, R1, R2 and R3), 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 5, 10, and 16 (fresh or already used) were introduced into the autoclave reactor before described The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 200 ° C under continuous stirring. Liquid samples ( ~ 50-100 pl) were taken at different time intervals until 7 hours of reaction. The samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in methanol, and analyzed by gas chromatography on a GC-Bruker 430 equipped with an FID detector and a TRB-624 capillary column. 60 m Products are identified by an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with an HP-5 MS capillary column 30 m long.
[0626]
[0627] The results obtained are shown in Tables 9, 10 and 11, and in Figure 9.
[0628]
[0629]
[0630] Table 9. Catalytic activity during reuse of the Sn-Nb-O catalyst (0.58) of Example 5.
[0631]
[0632]
[0633]
[0634]
[0635] Table 10. Catalytic activity during reuse of the Sn-Ti-O catalyst (0.33) of Example 10.
[0636]
[0637]
[0638] Table 11. Catalytic activity during reuse of the Ce-Zr-O catalyst of Example 16.
[0639]
[0640] In general, the same behavior is observed for all catalysts in the conversion of the reagents present in the initial aqueous mixture. The conversion of propionaldehyde decreases with the number of reactions performed. On the other hand, the conversion of acetic acid decreases in the case of Ce-Zr-O, while it remains constant or even increases for materials based on Sn-Nb and Sn-Ti. On the other hand, the conversion of ethanol increases in the case of the catalyst based on Ce-Zr-O (Ex. 16) and decreases slightly in the rest of catalysts containing Sn and / or Nb and / or Ti (Ex. 5 and 10 ). Consequently, the Total Organic Yield is decreasing slightly with the number of re-uses in said catalysts, but the drop is more pronounced in the case of the Ce-Zr-O catalyst of Example 16 with a percentage loss of catalytic activity with respect to the initial 16%, while the Sn-Nb-O catalyst prepared in Example 5 exhibits excellent stability with a percentage drop in catalytic activity of only 1% (see Figure 8). This means that the activity of the Sn-Nb-O catalyst prepared in Example 5 remains practically constant after at least 3 consecutive reuses. On the other hand, the Sn-Ti-O based catalyst of Example 10 exhibits a fall in intermediate catalytic activity (10%) between the Ce-Zr-O material (Ex. 16) and the Sn-Nb-O catalyst (Ex . 5).
[0641] It should be noted that in the case of the Ce-Zr-O catalyst of Example 16, at the end of reuse only 80 mg of the 150 mg initially added is recovered, while 130 mg is recovered in the case of the Sn catalyst -Nb-O of Example 5. The lower amount of solid catalyst recovered may be due to a lower stability of the Ce-Zr-O catalyst and the possible formation of cerium acetate, which causes the extraction of cerium oxide from the catalyst structure. This also explains the drastic drop in acetic acid conversion with re-uses (Table 11).
[0642]
[0643] At the same time, the analyzes performed by AE and TG confirm the greater stability of the Sn-Nb-based catalyst of Example 5 and the Sn-Ti-based catalyst of Example 10 compared to the mixed Ce-Zr oxide prepared in Example 16. Thus, in the Sn-Nb material (Ex. 5), only 0.5% by weight of carbon is determined by AE after the third reuse (R3); 2.8% in the case of Sn-Ti (Ex. 10), while the amount of carbon detected in the Ce-Zr catalyst (Ex. 16) after the same number of re-uses reached 4.8 % in weigh. Likewise, it is observed by TG analysis that the Sn-Nb catalyst (Ex. 5) undergoes a mass loss of 1.5% at temperatures close to 300-350 ° C corresponding to the absorbed organic products, while the oxide Mixed Ce-Zr (Ex. 16) has a mass loss of 9.5% at these temperatures, plus an additional 3.3% at temperatures close to 450 ° C, the latter corresponding to heavier reaction products absorbed in the catalyst.

权利要求:
Claims (20)
[1]
1. A process for the production of mixtures of hydrocarbons and aromatic compounds, characterized in that it comprises at least the following steps:
(a) contacting an aqueous mixture containing oxygenated organic compounds derived from primary treatments of the biomass with a catalyst, comprising at least one mixed metal oxide of Sn and Nb, Sn and Ti, and combinations of Sn, Ti and Nb and which, in its calcined form, is made up of at least 65% by weight by the rutile crystalline phase of SnO2.
(b) reacting the mixture with the catalyst in a catalytic reactor at temperatures between 50 and 450 ° C and pressures of 1 to 120 bars in the absence of hydrogen;
(c) recover the products obtained in step (b) by a process of liquid / liquid separation of the aqueous and organic phases.
[2]
2. A process according to claim 1, characterized in that the catalyst has the empirical formula:
S n a N b b T ic M d O e
in which:
- M is a chemical element of the group of transition metals, rare earths or lanthanides,
- a is between 0.05 and 10.0
- b and c are between 0 and 10.0, with c + b other than zero (c + b + 0)
- d is between 0 and 4.0 and
- e has a value that depends on the oxidation state of the elements Sn, Nb, Ti and the element M.
[3]
3. A process according to claim 2, characterized in that d is zero and the catalyst has the empirical formula:
S n a N b bT i cO e
in which:
- a is between 0.05 and 10.0
- b and c are between 0.05 and 10.0, and
- e has a value that depends on the oxidation state of the elements Sn, Nb and Ti.
[4]
4. A process according to claim 2, characterized in that c is zero and the catalyst has the empirical formula:
Sn ^a Nb ^b M ^d O ^e
in which:
- M is a chemical element of the group of transition metals, rare earths or lanthanides,
- a and b are between 0.05 and 10,
- d is between 0 and 4.0 and
- e has a value that depends on the oxidation state of the elements Sn, Nb and M.
[5]
5. A process according to claim 2, characterized in that b is zero and the catalyst has the empirical formula:
Sn ^a Ti ^c M ^d O ^e
in which:
- M is a chemical element of the group of transition metals, rare earths or lanthanides,
- a and c are between 0.05 and 10,
- d is between 0 and 4.0 and
- e has a value that depends on the oxidation state of the elements Sn, Ti and M.
[6]
6. A method according to any of claims 1, 2, 4 and 5, characterized in that the element M is selected from the group of transition metals, rare earths, or lanthanides.
[7]
7. A method according to claim 6, characterized in that the element M is a transition metal, lanthanide or rare earth selected from V, Cr, Fe, Co, Ni, Cu, Zn, Mo, Ta, Tl, Re, The and combinations thereof.
[8]
8. A process according to any of the preceding claims, characterized in that the aqueous mixture derived from biomass contains oxygenated organic compounds having between 1 and 12 carbon atoms, and also having between 1 and 9 oxygen atoms.
[9]
9. A process according to any of the preceding claims, characterized in that the total concentration of the oxygenated organic compounds present in the aqueous mixture derived from the biomass is in a range of between 0.5 and 99.5% by weight.
[10]
10. A process according to claim 9, characterized in that the total concentration of the oxygenated organic compounds present in the aqueous mixture derived from the biomass is in a range of between 1.0 and 70.0% by weight.
[11]
A method according to any of the preceding claims, characterized in that the contact between the aqueous mixture and the catalyst is carried out in a reactor selected from a discontinuous reactor, a continuous stirred tank reactor, a continuous fixed bed reactor and a continuous fluidized bed reactor.
[12]
12. A process according to claim 11, characterized in that the reactor is a discontinuous reactor and the reaction is carried out in the liquid phase.
[13]
13. A method according to claim 12, characterized in that the process is carried out at a pressure of between 1 to 80 bar.
[14]
14. A process according to any of claims 12 or 13, characterized in that the process is carried out at a temperature between 100 ° C and 350 ° C.
[15]
15. A process according to any of claims 12 to 14, characterized in that the contact between the aqueous mixture containing the oxygenated organic compounds derived from the biomass and the catalyst is carried out in a time ranging from 2 minutes to 200 hours.
[16]
16. A process according to any of claims 12 to 15, characterized in that the weight ratio between the aqueous mixture containing the oxygenated organic compounds derived from the biomass and the catalyst is between 1 and 200.
[17]
17. A method according to claim 11, characterized in that the reactor is a fixed bed reactor or a fluidized bed reactor.
[18]
18. A process according to claim 17, characterized in that the reaction temperature is between 100 ° C and 350 ° C; the contact time is between 0.001 and 200 s; and the working pressure of between 1 and 100 bars.
[19]
19. A process according to any of the preceding claims, characterized in that the contact between the aqueous fraction containing the oxygenated organic compounds and the catalyst is carried out under nitrogen, argon, air atmosphere, nitrogen enriched air, argon enriched air , or combinations thereof.
[20]
20. A process according to claim 19, characterized in that it is carried out in a nitrogen atmosphere.

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同族专利:

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公开号 | 公开日

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WO2019224412A1|2019-11-28|

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EP3804848A4|2022-02-23|

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JP2021525303A|2021-09-24|

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EP3804848A1|2021-04-14|

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ES2732747B2|2020-07-02|

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US20210379564A1|2021-12-09|

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BR112020023948A2|2021-02-23|

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ES201830508A|ES2732747B2|2018-05-25|2018-05-25|CATALYTIC PROCESS FOR THE PRODUCTION OF HYDROCARBONS AND AROMATIC COMPOUNDS FROM OXYGENATED COMPOUNDS PRESENT IN AQUEOUS MIXTURES|ES201830508A| ES2732747B2|2018-05-25|2018-05-25|CATALYTIC PROCESS FOR THE PRODUCTION OF HYDROCARBONS AND AROMATIC COMPOUNDS FROM OXYGENATED COMPOUNDS PRESENT IN AQUEOUS MIXTURES|

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EP19806718.3A| EP3804848A4|2018-05-25|2019-05-23|Catalytic method for the production of hydrocarbons and aromatic compounds from oxygenated compounds contained in aqueous mixtures|

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PCT/ES2019/070340| WO2019224412A1|2018-05-25|2019-05-23|Catalytic method for the production of hydrocarbons and aromatic compounds from oxygenated compounds contained in aqueous mixtures|

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US17/058,395| US20210379564A1|2018-05-25|2019-05-23|Catalytic method for the production of hydrocarbons and aromatic compounds from oxygenated compounds contained in aqueous mixtures|

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JP2020565950A| JP2021525303A|2018-05-25|2019-05-23|Catalytic method for producing hydrocarbons and aromatic compounds from oxygen-containing compounds contained in aqueous mixtures|

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BR112020023948-8A| BR112020023948A2|2018-05-25|2019-05-23|catalytic method for the production of hydrocarbons and aromatic compounds from oxygenated compounds contained in aqueous mixtures|