Procedure for the valorization of oxygenated compounds present in aqueous fractions derived from bio

专利摘要:
Procedure for the valorization of oxygenated compounds present in aqueous fractions derived from biomass. The present invention relates to a process for the production of mixtures of hydrocarbons and aromatics, for later use as fuel components (preferably in the range c5-c16), by the catalytic transformation of oxygenated compounds present in aqueous fractions derived from primary treatments of the biomass, which may comprise at least the following steps: i) contacting the aqueous mixture containing the oxygenated compounds derived from the biomass with a catalyst comprising at least w and/or nb, and combinations of nb and w with other elements, ii) reacting the mixture with the catalyst in a catalytic reactor at temperatures between 50 and 450ºC and pressures of 1 to 120 bar; 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:ES2638719A1
申请号:ES201630339
申请日:2016-03-22
公开日:2017-10-23
发明作者:Marcelo Eduardo Domine；Jose Manuel Lopez Nieto；Daniel DELGADO MUÑOZ；Alberto FERNANDEZ-ARROYO NARANJO
申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
IPC主号:

专利说明:

FIELD OF THE INVENTION
This invention belongs to the field of synthesis and application of catalysts for the conversion of biomass mainly of the lignocellulosic type and its derivatives into liquid fuels for transport. STATE OF THE ART PRIOR TO THE INVENTION
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 the 2nd generation (not competitive with food), it is also necessary to recover the residual currents and aqueous effluents obtained during the process [F. Cherubini et al., Biofuels, Bioproducts and Biorefining, 3 (2009) 534].
In this context, and after a primary treatment of biomass (mainly vegetable or lignocellulosic type), for example by thermal or catalytic pyrolysis processes, so-called pyrolysis oils or bioliquids can be obtained mostly. These bio-liquids are complex mixtures of more than 200 components, containing different proportions of water and fundamentally oxygenated organic compounds (i.e. alcohols, ketones, acids, polyalcohols, furans, phenols, among others) of different molecular size that are characterized by their high


oxygen content 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].
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, E.
AND.  Iojoiu et al., Applied Catalysis A: Gen. 323 (2007) 147].
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 [C.A. 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.
For this, it is necessary to develop new catalysts and catalytic processes that


are able to carry out the desired reactions in the least possible number of 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 ºC) 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. DESCRIPTION OF THE INVENTION
The present invention relates to a process for the production of mixtures of hydrocarbons and aromatic compounds, which may comprise at least the following steps:
(to) contacting an aqueous mixture containing oxygenated compounds derived from primary treatments of the biomass with a catalyst, comprising at least W and / or Nb and which, in its calcined form, has at least one material arranged along one of the crystallographic axes and an X-ray diffractogram in which at least diffraction lines corresponding to angles 2 to 22.70.4 and 46.60.4 are observed;
(b) react the mixture with the catalyst in a catalytic reactor at temperatures between 50 and 450 ° C and pressures of 1 to 120 bar;
(C) recover the products obtained in step (b) by means of a liquid / liquid separation process from the aqueous and organic phases.
According to a particular embodiment, the process of the present invention for the catalytic transformation of oxygenated 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: WaNbbAcBdOe


in which:-A is a metal of the group of alkali and alkaline earth metals,-B is a chemical element of the group of transition metals, rare earths orelements of groups III, IV and V.-a and b are between 0 and 12.0, with a + b other than zero (a + b ≠ 0)-c is between 0 and 2.0,-d is between 0 and 4.0 and-e has a value that depends on the oxidation state of the elements W, Nb and theitem B.
According to this embodiment, the catalyst must comply with the condition that thecatalyst comprises at least W and / or Nb and which, in its calcined form, presents theless an ordered material along one of the crystallographic axes and aX-ray diffractogram in which at least diffraction lines are observedcorresponding to angles 2 to 22.70.4 and 46.60.4.
Said catalyst can be prepared by conventional methods from solutionsof compounds of the different elements, of solutions of the same elementspure, or mixture thereof, with the desired atomic relationships. TheseSolutions are preferably aqueous solutions.
According to another particular embodiment of the present invention, the catalyst is obtainedthrough a procedure comprising at least:a) a first stage, of mixing compounds of the different elements, ofpure elements, or mixture thereof,b) a second stage, of drying the solid obtained in the first stage andc) a third stage, for calcining the dry solid obtained in the second stage.
The mixing stage can be performed from the compounds of the differentelements, from the pure elements themselves in solution, or by methodshydrothermal
The elements W, Nb and metals A and B can be incorporated into the stage ofmixed as pure metal elements, as salts, as oxides, as


hydroxides, as alkoxides, or as mixtures of two or more of the aforementioned forms. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts.
The W may be incorporated into the mixing stage preferably as tungsamic acid, ammonium tungsten, ammonium metawolframto, ammonium parawolframto or tungsten oxide.
The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
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.
The mixing step can be carried out in solution or by hydrothermal treatment.
The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
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.
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 450 and 650 ° 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.
According to this embodiment, the catalyst is obtained, as indicated above, using hydrothermal methods (containing two or more elements in the synthesis, especially containing W, Nb, and elements A and B). The temperature and time of synthesis can be decisive using hydrothermal methods. 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.
In an alternative embodiment, the catalyst is obtained 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 elements W, Nb and elements A and B, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts. As solvent, water, methanol, ethanol, isopropanol, acetonitrile, dioxane, or mixtures thereof, preferably water, can be used. 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.
The catalyst described can be used for the inventive process as it is obtained once calcined.
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 fixation of the different elements of the


Catalyst 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.
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 WaNbbAcBdOe, in which d is zero, has the following empirical formula:
WaNbbAcOe
in which:-A is a metal of the group of alkali or alkaline earth metals-a and b are between 0 and 12, with a + b other than zero (a + b ≠ 0)-c is between 0.0001 and 2.0 and-e has a value that depends on the oxidation state of the elements W and Nb.
Again the above formula must meet the condition that the catalystcomprise at least W and / or Nb and that, in its calcined form, has at least oneordered material along one of the crystallographic axes and a diffractogram ofX-rays in which at least diffraction lines corresponding toangles 2 to 22.70.4 and 46.60.4.
Said catalyst can be prepared by conventional methods from solutionsof compounds of the different elements, of solutions of the same elementspure, or mixture thereof, with the desired atomic relationships. TheseSolutions are preferably aqueous solutions.
The catalyst described in this embodiment can be obtained by aprocedure comprising at least:a) a first stage, of mixing compounds of the different elements, ofpure elements, or mixture thereof,b) a second stage, of drying the solid obtained in the first stage andc) a third stage, for calcining the dry solid obtained in the second stage.
The mixing stage can be performed from the compounds of the differentelements, from the pure elements themselves in solution, or by methods


hydrothermal
The elements W, Nb and the metal A 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. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts.
The W may be incorporated into the mixing stage preferably as tungsamic acid, ammonium tungsten, ammonium metawolframto, ammonium parawolframto or tungsten oxide.
The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
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.
The mixing step can be carried out in solution or by hydrothermal treatment.
The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
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.
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 450 and 650 ° 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.
According to this embodiment, the catalyst is obtained, as indicated above, using hydrothermal methods (containing two or more elements in the synthesis, especially containing W, Nb and metal A). The temperature and time of synthesis can be decisive using hydrothermal methods. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more specifically, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more specifically between 24 and 200 hours.
It is also possible that the catalyst is obtained 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 elements W, Nb and element A, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts. As solvent, water, methanol, ethanol, isopropanol, acetonitrile, dioxane and 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, alkali metal hypochlorites, without these examples being limiting 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.
The catalyst described can be used for the inventive process as it is obtained once calcined.
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.
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 WaNbbAcBdOe, in which c is zero, has the following empirical formula:
WaNbbBdOe where: -B is a chemical element of the group of transition metals, rare earths or elements of groups III, IV and V -ayb are between 0 and 12.0, with a + b other than zero (a + b ≠ 0) -d is between 0.0001 and 4.0 and -e has a value that depends on the oxidation state of elements W, Nb and element B.
Again on condition that the catalyst comprises at least W and / or Nb and that,in its calcined form, it has at least one material arranged along one ofthe crystallographic axes and an X-ray diffractogram in which at least they are observeddiffraction lines corresponding to angles 2 to 22.70.4 and 46.60.4.
Said catalyst can be prepared by conventional methods from solutionsof compounds of the different elements, of solutions of the same elementspure, or mixture thereof, with the desired atomic relationships. TheseSolutions are preferably aqueous solutions.
The catalyst is obtained by a process comprising at least:a) a first stage, of mixing compounds of the different elements, ofpure elements, or mixture thereof,b) a second stage, of drying the solid obtained in the first stage andc) a third stage, for calcining the dry solid obtained in the second stage.


The mixing stage can be carried out from the compounds of the different elements, from the pure elements themselves in solution, or by hydrothermal methods.
The elements W, Nb and the metal B 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. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts.
The W may be incorporated into the mixing stage preferably as tungsamic acid, ammonium tungsten, ammonium metawolframto, ammonium parawolframto or tungsten oxide.
The Nb can be incorporated into the mixing step preferably as niobium pentoxide, niobium oxalate, niobium chloride or Nb metal.
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.
The mixing step can be carried out in solution or by hydrothermal treatment.
The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
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.
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


it preferably ranges between 250 and 850 ° C and more preferably between 450 and 650 ° 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.
According to this embodiment, the catalyst is obtained, as indicated above, using hydrothermal methods (containing two or more elements in the synthesis, especially containing W, Nb and element B). The temperature and time of synthesis can be decisive using hydrothermal methods. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more specifically, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more specifically between 24 and 200 hours.
It is also possible that the catalyst is obtained 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 elements W, Nb and element B, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts. As solvent, water, methanol, ethanol, isopropanol, acetonitrile, dioxane and 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, alkali metal hypochlorites, without these examples being limiting 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.
In another alternative embodiment of the present invention, other elements, such as


an alkali metal or alkaline earth metal, can also be incorporated after the calcination step by impregnation or precipitation. In this case, the resulting solid will be subjected to a second calcination stage.
The catalyst described can be used for the inventive process as it is obtained once calcined.
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.
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 WaNbbAcBdOe, in which c and d are zero, has the following empirical formula:
WaNbbOe where: -a and b are between 0 and 12, with a + b other than zero (a + b ≠ 0) -e has a value that depends on the oxidation state of the elements W and Nb.
With the proviso that the catalyst comprises at least W and / or Nb and that, in its calcined form, it has at least one material arranged along one of the crystallographic axes and an X-ray diffractogram in which at least they observe diffraction lines corresponding to angles 2 to 22.70.4 and 46.60.4.
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.
According to this embodiment, the catalyst can be obtained by a process


which comprises at least:a) a first stage, of mixing compounds of the different elements, of
pure elements, or mixture of both, b) a second stage, for drying the solid obtained in the first stage and c) a third stage, for calcining the dry solid obtained in the second stage.
The mixing stage can be carried out from the compounds of the different elements, from the pure elements themselves in solution, or by hydrothermal methods.
The elements W 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. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts.
The W may be incorporated into the mixing stage preferably as tungsamic acid, ammonium tungsten, ammonium metawolframto, ammonium parawolframto or tungsten oxide.
The Nb can be incorporated into the mixing step preferably as niobium oxalate, niobium pentoxide, niobium chloride or Nb metal.
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.
The mixing step can be carried out in solution or by hydrothermal treatment.
The drying step can be carried out by conventional methods in an oven, evaporation with stirring, evaporation in a rotary evaporator, or vacuum drying.
The step of calcining the dry solid can be carried out under a gas atmosphere


inert, such as nitrogen, helium, argon or mixtures thereof, as well as air or mixtures of air with other gases.
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 450 and 650 ° 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.
According to this particular embodiment, the catalyst can be obtained, as indicated above, using hydrothermal methods (containing two or more elements in the synthesis, especially containing W and Nb). The temperature and time of synthesis can be decisive using hydrothermal methods. Thus, the synthesis temperature is preferably between 100 and 250 ° C and, more specifically, between 150 and 180 ° C. The synthesis time is preferably between 6 and 500 hours, and more specifically between 24 and 200 hours.
In addition, the catalyst can be obtained 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 W and Nb, salts, oxides, hydroxides, alkoxides or mixtures of two or more of the aforementioned forms can be used. Sulfates, nitrates, oxalates or halides, and more preferably sulfates are preferably used as salts. As solvent, water, methanol, ethanol, iso-propanol, acetonitrile, dioxane and 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, alkali metal hypochlorites, without being these limiting examples. Once the pH is controlled, the solution is


let it 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.
According to the particular embodiment, other elements, such as an alkali metal or alkaline earth metal, can also be incorporated after the calcination step by impregnation or precipitation. In this case, the resulting solid will be subjected to a second calcination stage.
The catalyst described according to this embodiment can be used for the inventive process as it is obtained once calcined.
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.
The process of the present invention has the following advantages over the state of the art:
- Catalysts comprising W and / or Nb, and combinations of Nb and / or W with other elements, in which at least W and / or Nb are present in the form of at least one oxide, provide higher C5-C8 hydrocarbon yields. that those reported with Ce-Zr-based catalysts, with total yields (≈20%) comparable to those observed for these Ce-Zr materials;
- they are more stable and resistant in reaction conditions than other reported catalytic materials;
- they require a lower temperature to perform the procedure when compared with data reported in literature for other catalytic materials.


According to the present invention, the catalyst metal A may be selected from the group of alkali and alkaline earth metals, preferably Li, Na, K, Cs, Be, Mg, Ca, Sr, Ba, and combinations thereof and more preferably Na, K, Cs, Mg, Ca and combinations thereof.
In addition, element B may be selected from the group of transition metals, preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ta, Tl, Re and combinations of the themselves; rare earths, preferably La, Ce and combinations thereof; and elements of group III, IV and V, preferably B, Al, Ga, Si, Sn, and Sb.
According to a particular embodiment, element B is selected from Ti, V, Mn, Cu, Zn, Zr, La, Ce, Al, Si and combinations thereof.
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.
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.
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.
In the process of the present invention, the aqueous mixture derived from the biomass that is introduced in the first step may contain oxygenated compounds having between 1 and 12 carbon atoms, preferably between 1 and 9 carbon atoms, and in addition, they can have between 1 and 9 oxygen atoms, preferably between 1 and 6 oxygen atoms.
According to the present invention, the total concentration of the oxygenated 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.
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 a discontinuous reactor, a continuous stirred tank reactor, a continuous fixed bed reactor and a continuous reactor of fluidized bed
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 120 bars, and more preferably at a pressure between 1 and 80 bars. In addition, the reaction can be carried out at a temperature between 50 ° C and 350 ° C, preferably between 120 ° C and 280 ° C. The contact time between the aqueous mixture containing the oxygenated 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.
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 of between 50 ° C and 450 ° C and more preferably between 150 ° C and 350 ° 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.
According to the procedure described above, the contact between the aqueous fraction containing the oxygenated compounds and the catalyst can be carried out under an atmosphere of nitrogen, argon, hydrogen, air atmosphere, nitrogen enriched air, argon enriched air, or combinations of the same.


According to a particular embodiment, the process is preferably carried out in a nitrogen atmosphere.
According to another particular embodiment, the process is preferably carried out in an atmosphere of air or air enriched with nitrogen.
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 compounds present in aqueous fractions derived from biomass.
The aqueous fractions derived from the biomass containing different oxygenated compounds to be treated by the process of the present invention may be selected from among the 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 super-critical biomass conditions, and aqueous fractions obtained from biomass fermentation for the selective production of ethanol, butanol, succinic acid, and lactic acid, without this being limiting examples.
The aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated compounds possessing between 1 and 12 Carbon atoms, preferably between 1 and 9 Carbon atoms.
In addition, the aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated compounds possessing between 1 and 9 Oxygen atoms, preferably between 1 and 6 O atoms.
The aqueous fractions derived from the biomass to be treated by the process of the present invention may contain different oxygenated compounds in


concentrations in a range of between 0.5 and 99.5% by weight with respect to the amount of water, preferably between 1.0 and 70.0% by weight with respect to the amount of water.
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 compounds, including alcohols, aldehydes, ketones, carboxylic acids and di-acids, esters, ethers, diols, triols. and polyalcohols in general, sugars, furanic derivatives, and phenolic derivatives, 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 alcohol type, including methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol , 1-pentanol, 2-pentanol, iso-pentanol, 1-hexanol, 2hexanol, 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, 3hexenal, 2-methyl-2-pentenal, 2-methyl-3-pentenal, 3-methyl-2-pentenal, furfural, and 5-hydroxymethyl-furfural, without being these examples limiting
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 ketone type, including acetone, 2-butanone, 2pentanone, penten-2-one, 3-pentanone , penten-3-one, 2-hexanone, hexen-2-one, 3hexanone, hexen-3-one, iso-forone, vanillin, aceto-vanillin, syringone, and acetosyringone, 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 acid and di-acid type, including acetic acid, propionic acid, butyric acid, pentanoic acid, acid hexanoic acid, lactic acid, acid


pyruvic, levulinic acid, tartronic acid, tartaric acid, glycolic acid, succinic acid, gluconic acid, and glucaric acid, 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 ester type, including methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propionate of methyl, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate, but these are not 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 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-iso-propyl ether, ethyl-butyl ether, ethyl-sec-butyl ether, propyl-butyl ether, and propyl-sec-butyl ether, 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 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, 2,4pentanediol , 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-butanethriol, 1,2,4butanotriol, 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, 2,3,6hexanotriol, 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.
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 Furan derivatives type, including furan, 2-methyl-furan, 5-methyl-furan, 2, 5-dimethyl-furan, 2-ethyl-furan, 5-ethyl-furan, 2,5-diethyl-furan,


benzofuran, methyl benzofuran, ethyl benzofuran, without being these limiting examples. 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-syringol, without being these limiting examples.
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.
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.
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 graphical examples are provided by way of


illustration and are not intended to be limiting of the present invention. BRIEF DESCRIPTION OF THE GRAPHICS
Fig. 1. Shows an x-ray diffractogram of the tungsten oxide based catalyst [W-O hydrot.] Described in example 1.
Fig. 2. Shows an X-ray diffractogram of the tungsten oxide based catalyst [W-O hydrot.] Described in example 2.
Fig. 3. It shows an x-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (1,8)] described in example 3.
Fig. 4. Shows an x-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (1,8)] described in example 4.
Fig. 5. It shows an X-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (1,0)] described in example 5.
Fig. 6. Shows an x-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (0.7)] described in example 6.
Fig. 7. Shows an x-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (0.3)] described in example 7.
Fig. 8. Shows an x-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (1,0)] described in example 8.
Fig. 9. Shows an X-ray diffractogram of the catalyst based on tungsten and niobium oxides [W-Nb-O (1,0)] described in example 9.
Fig. 10. It shows an x-ray diffractogram of the niobium oxide-based catalyst [Nb-O hydrot.] Described in example 10.


Fig. 11. Shows an x-ray diffractogram of the niobium oxide-based catalyst [Nb-O hydrot.] Described in example 11.
Fig. 12. Shows the X-ray diffractogram obtained for the catalyst based on cerium and zirconium oxides [Ce-Zr-O] described in example 12.
Fig. 13. It shows the X-ray diffractogram obtained for the tungsten and niobium oxide [W-Nb-O impreg.] Catalyst described in example 13.
Fig. 14. Shows the X-ray diffractogram obtained for the catalyst based on tungsten and niobium oxides [W-Nb-O co-precip.] Described in example 14.
Fig. 15. Shows an x-ray diffractogram of the catalyst based on tungsten, niobium and potassium oxides [W-Nb-K-O] described in example 15.
Fig. 16. Shows an x-ray diffractogram of the catalyst based on tungsten, niobium and vanadium oxides [W-Nb-V-O (V / W = 0.33)] described in example 16.
Fig. 17. Shows an x-ray diffractogram of the catalyst based on tungsten, niobium and vanadium oxides [W-Nb-V-O (V / W = 0.17)] described in example 17.
Fig. 18. Shows an X-ray diffractogram of the catalyst based on tungsten, niobium and cerium oxides [W-Nb-Ce-O] described in example 18.
Fig. 19. Shows an x-ray diffractogram of the catalyst based on tungsten and zirconium oxides [W-Zr-O] described in example 19.
Fig. 20. Shows a comparison of the stability and maintenance of the catalytic activity with the re-uses of the Ce-Zr-O (Ex. 12) and W-Nb-O (0.7) catalysts (Ex. 6 ). EXAMPLES
Next, the inventors will illustrate the invention by means of various tests carried out by the inventors, which demonstrate the preparation of the catalysts and their


application in the process of the invention.
Example 1. Preparation of a catalyst by hydrothermal method, based on tungsten oxide [W-O] and treated with nitrogen
In 134.8 g of water at 80 ° C, 31.7 g of ammonium tungsten, 2.0 g of oxalic acid and 2.45 g of 37% hydrochloric acid are added, which are kept under stirring for 30 minutes. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is heated at 450 ° C for 2 h under a stream of nitrogen to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 1.
Example 2. Preparation of a catalyst similar to that of Example 1, but thermally activated in air
In 134.8 g of water at 80 ° C, 31.7 g of ammonium tungsten, 2.0 g of oxalic acid and 2.45 g of 37% hydrochloric acid are added, which are kept under stirring for 30 minutes. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is treated at 600 ° C for 2 h in a stream of air. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 2.
Example 3. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 1.8 [W-Nb-O (1.8)] and treated with nitrogen
In 235.7 g of water at 80 ° C, 44.0 g of ammonium metawolframate and 5.88 g of 96% sulfuric acid are added. On the other hand, and after heating at 40 ° C, a solution is prepared with 65.9 g of deionized water and 27.2 g of niobium oxalate, which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is heated at 550 ° C for 2 h in a stream of


nitrogen to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 3.
Example 4. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 1.8 [W-Nb-O (1.8)] and treated in air
In 136.5 g of water at 80 ° C, 25.7 g of ammonium metawolframide and 2.5 g of 37% hydrochloric acid are added. On the other hand, and after heating at 40 ° C, a solution is prepared with 38.7 g of deionized water and 26.2 g of niobium oxalate, which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static for 2 days and the solid obtained is treated at 100 ° C for 16 h. Finally, the material is thermally treated at 550 ° C for 2 hours in a stream of air. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 4.
Example 5. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 1.0 [W-Nb-O (1.0)] and treated with nitrogen
In 134.5 g of water at 80 ° C, 25.87 g of ammonium metawolframate and 1.90 g of 96% sulfuric acid are added. On the other hand, and after heating at 80 ° C, a solution is prepared with 71.5 g of deionized water and 48.5 g of niobium oxalate which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days and the solid obtained is dried at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 5. Example 6. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 0.7 [W-Nb-O (0.7)] and treated with nitrogen


In 53.8 g of water at 80 ° C, 10.35 g of ammonium metawolframide and 0.76 g of 96% sulfuric acid are added. On the other hand, and after heating at 40 ° C, a solution is prepared with 28.6 g of deionized water and 19.26 g of niobium oxalate which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is heated at 550 ° C for 2 h under a stream of nitrogen to obtain the catalyst. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 6.
Example 7. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 0.3 [W-Nb-O (0.3)] and treated with nitrogen
In 54.9 g of water at 80 ° C, 4.07 g of ammonium metawolframate and 1.1 g of 37% hydrochloric acid are added and kept under stirring for 30 minutes. In parallel, a solution of 30.6 g of niobium oxalate in 29.9 g of water is prepared, which is added slowly to the first. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is treated at 100 ° C for 16 h and finally heated at 550 ° C for 2 h in a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 7.
Example 8. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 1.0 [W-Nb-O (1.0)] and treated in nitrogen at 300 ° C
In 134.5 g of water at 80 ° C, 25.87 g of ammonium metawolframate and 1.90 g of 96% sulfuric acid are added. On the other hand, and after heating at 80 ° C, a solution is prepared with 71.5 g of deionized water and 48.5 g of niobium oxalate which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days and the solid obtained is dried at 100 ° C for 16 h. Finally the material is


heats at 300 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 8.
Example 9. Preparation of a catalyst by hydrothermal method, based on tungsten and niobium oxides with a molar ratio W / Nb = 1.0 [W-Nb-O (1.0)] and treated in nitrogen at 800 ° C
In 134.5 g of water at 80 ° C, 25.87 g of ammonium metawolframate and 1.90 g of 96% sulfuric acid are added. On the other hand, and after heating at 80 ° C, a solution is prepared with 71.5 g of deionized water and 48.5 g of niobium oxalate which was added to the previous solution. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days and the solid obtained is dried at 100 ° C for 16 h. Finally, it is treated at 800 ° C for 2 hours in a nitrogen stream. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 9.
Example 10. Preparation of a catalyst by hydrothermal method, based on niobium oxide [Nb-O hydrot.] And treated with nitrogen
30.6 g of niobium oxalate are dissolved in 63.2 g of deionized water at 80 ° C under stirring. Stirring is maintained for 10 minutes. The mixture is transferred to a Teflon coated steel autoclave. The autoclave is kept at 175 ° C in static for 2 days, and the solid obtained is treated at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 10.
Example 11. Preparation of a catalyst similar to that of Example 10, but thermally activated in air
30.6 g of niobium oxalate are dissolved in 63.2 g of deionized water at 80 ° C under stirring. Stirring is maintained for 10 minutes. The mixture is transferred to a Teflon coated steel autoclave. The autoclave is maintained at 175 ° C in static


for 2 days, and the solid obtained is treated at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 11.
Example 12. Preparation of a catalyst based on mixed oxides of Ce and Zr [Ce-Zr-O] by the co-precipitation method
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.
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 Ce0.5Zr0.5O2 catalyst, an aqueous solution of the salts of both metals is prepared in equimolar proportion. Ce (NO3) 3 · 6H2O and ZrO (NO3) 2 · H2O are used as precursors of both metals. In a beaker, 11.76 g of Ce (NO3) 3 · 6H2O and 6.70 g of ZrO (NO3) 2 · H2O are weighed and dissolved in 120 ml of distilled water. Then, a 28% NH4OH solution is added dropwise until a pH of 10 is reached. Subsequently, the solution is transferred to a closed 250 ml balloon and under stirring, where the mixture is allowed to age at room temperature for 65 hours. Subsequently, the catalyst is washed with distilled water by vacuum filtration until it reaches a pH of 7. The catalyst is allowed to dry overnight at 100 ° C and finally, it is subjected to an activation process by calcination in air at 450 ° C, for 4 , 5 h. The amounts of Ce and Zr measured by ICP coincide with the formula Ce0.5Zr0.5O2, and the X-ray diffractogram obtained for this sample indicates the presence of mixed oxides of Ce and Zr (Fig. 12)
Example 13. Preparation of a catalyst based on mixed oxides of W and Nb

[W-Nb-O impregnation] using a wet impregnation method
This catalyst was synthesized to illustrate catalysts of the type W-Nb mixed oxides commonly used in literature [C. Yue et al., Appl. Catal. B: Environ., 163 (2015) 370-381]. A mixed oxide type catalyst with a W-Nb ratio similar to that used for the catalyst of Example 6 was synthesized, in order to be compared in terms of catalytic activity with the catalysts of the present invention.
The catalyst was prepared by the wet impregnation synthesis method of the mixed W-Nb oxide adapting the procedure published by C. Yue et al. [Appl. Catal.
B: Environ., 163 (2015) 370-381].
To synthesize the W12Nb6.5Ox catalyst, an aqueous solution of the salts of the two metals is prepared in the desired proportion. (NH4) 6H2W12O40.H2O and C4H4NNbO9.H2O are used as precursors of both metals. In a beaker, 3.84 g of (NH4) 6H2W12O40.H2O and 2.36 g of C4H4NNbO9.H2O are weighed and dissolved in 15 ml of distilled water. The mixture is placed under stirring at a temperature of 70 ° C and the solvent is allowed to evaporate slowly. After 10 hours of drying at a temperature of 100 ° C, the catalyst is subjected to an activation process by calcination in air at 450 ° C for 3.5 h. The X-ray diffractogram obtained for this sample indicates the presence of mixed oxides of W and Nb (Fig. 13)
Example 14. Preparation of a catalyst based on mixed oxides of W and Nb [W-Nb-O co-precip.] By the co-precipitation method
This catalyst was synthesized to illustrate catalysts of the type W-Nb mixed oxides commonly used in literature [D. Stosic et al., Catal. Today, 192 (2012) 160168]. A mixed oxide type catalyst with a W-Nb ratio similar to that used for the catalyst of Example 6 was synthesized, in order to be compared in terms of catalytic activity with the catalysts of the present invention.
In this case, a method similar to that used in the preparation of the Ce-Zr mixed oxide type catalyst (Example 11) is used to prepare a W-Nb mixed oxide by a co-precipitation method. To do this, the procedure of


synthesis published by D. Stosic et al. [Catal. Today, 192 (2012) 160-168].
To synthesize the W12Nb18Ox catalyst, an aqueous solution of the salts of the two metals is prepared in the desired proportion. (NH4) 6H2W12O40 · H2O and C4H4NNbO9 · H2O are used as precursors of both metals. In a beaker, 2.96 g of (NH4) 6H2W12O40 · H2O and 5.4536 g of C4H4NNbO9 · H2O are weighed and dissolved in 50 ml of distilled water. Then a solution of 28% NH4OH is added dropwise and with stirring until a pH of 9 is reached. Subsequently, the solution is allowed to age at room temperature for 24 hours. Then, the catalyst is washed with distilled water by vacuum filtration until a pH of 7 is reached.
The catalyst is allowed to dry overnight at 100 ° C, and finally undergoes an activation process by calcination in nitrogen at 550 ° C, for 5h. The X-ray diffractogram obtained for this sample indicates the presence of mixed oxides of W and Nb (Fig. 14) Example 15: Modification of the catalyst of Example 6 by treatment with potassium salt
A solution of 0.13 g of potassium bicarbonate in 100 g of water is prepared to which 8.0 g of the catalyst obtained in Example 6 is added. The mixture is kept under stirring at room temperature for 4 h. The solid is then separated from the solution and treated at 280 ° C for 2h in a stream of air. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 15.
Example 16. Preparation of a catalyst based on W-V-Nb-O mixed oxide with a molar ratio V / W = 0.33 by hydrothermal method and heat treated in nitrogen
31.0 g of ammonium metawolframide and 3.0 g of 37% hydrochloric acid are added to 163.5 g of water, and the mixture is heated at 80 ° C and under stirring for 30 minutes. In parallel, a solution of 13.7 g of vanadyl sulfate in 62.1 g of water at room temperature is prepared, which is added slowly to the first. Then


a solution of 12.0 g of niobium oxalate in 29.1 g of water at 80 ° C is prepared, which is slowly added to the previous mixture. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static for 2 days and the solid obtained is treated at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 16.
Example 17. Preparation of a catalyst similar to that of example 15, with a lower molar ratio V / W (V / W = 0.17) and heat treated in nitrogen
In 68.1 g of water, 12.9 g of ammonium tungsten and 1.29 g of 98% sulfuric acid are added, and the mixture is kept at 80 ° C and stirred for 30 min. In parallel, a solution of 6.7 g of vanadyl sulfate in 30.1 g of water is prepared, which is added to the former. A solution of 37.5 g of niobium oxalate in 90.4 g of water at 80 ° C is then prepared, which is slowly added to the previous mixture. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static for 2 days and the solid obtained is treated at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram as shown in Figure 17.
Example 18. Preparation of a catalyst based on W-Ce-Nb-O mixed oxide by hydrothermal method and heat treated in nitrogen
7.0 g of ammonium metawolframide, 5.4 g of cerium trichloride and 0.52 g of 37% hydrochloric acid are added to 54.1 g of water at 80 ° C, which is kept stirring for 30 minutes. In parallel, a solution of 28.7 g of niobium oxalate in 29.4 g of water at 80 ° C is prepared, which is added slowly to the first, with stirring being maintained for 10 minutes. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static for 2 days and the solid obtained is treated at 100 ° C for 16 h. Finally the material is heated at 550 ° C for 2 h under a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffraction diagram such as the


shown in Figure 18.
Example 19. Preparation of a catalyst based on tungsten and zirconium oxides [W-Zr-O] by hydrothermal method and heat treated in nitrogen
In 105.7 g of water at 80 ° C, 20.4 g of ammonium metawolframate, 1.28 g of oxalic acid, 1.75 g of 37% hydrochloric acid are added and kept under stirring for 30 minutes. In parallel, a solution of 8.9 g of zirconyl chloride in 31.0 g of water is prepared, which is added slowly to the first. The resulting mixture is transferred to a steel autoclave with an internal Teflon sheath. The autoclave is kept at 175 ° C, in static, for 2 days. The solid obtained is treated at 100 ° C for 16 h and finally heated at 450 ° C for 2 h in a stream of nitrogen. This catalyst is characterized by presenting an X-ray diffractogram as shown in Figure 19.
Example 20. Comparative catalytic activity of the W-Nb series catalysts of Examples 1, 3, 6, 7 and 10
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.
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):
Component Content (wt%)
Water 30
Propionaldehyde 25


Hydroxy acetone 5
Acetic acid 30
Ethanol 10
Table 1. Composition of the model aqueous mixture used as initial feed in the autoclave type reactor.
5 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 1-xx were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50 100 μl) were taken at different time intervals up to 7 hours of reaction. The samples
10 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 of 60 m. The identification of the products is carried out by means of an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and
15 equipped with a 30 m long HP-5 MS capillary column.
The quantification of the products is carried out based on the response factors calculated by internal standard (2% by weight solution of chlorobenzene in methanol) and species with more than 5 carbon atoms are classified and quantified in 20 intervals, 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-2pentenal, groups of molecules are distinguished with 5, 6, 7, 8, 9, 10 or more than 10 carbon atoms To simplify the quantification of these reaction products, these
25 molecules are grouped into two large groups of compounds, namely: Products C5-C8 and Products C9-C10 +.
In the examples of catalytic activity illustrated, the following parameters are used to analyze the results obtained:


The conversion (in mole percent) for each of the oxygenated compounds present in the model aqueous mixture, was calculated from the following formula:
Conversion (%) = (initial moles of oxygenated comp - final moles of oxygenated comp. 5 / initial moles of oxygenated comp) * 100
The final yield (in percentage by weight) to each of the products obtained, was calculated from the following formula:
10 Product yield (%) = grams product i in the reactor / total grams in the reactor
The Yield to Total Organic (in percentage by weight), was calculated from the following formula: 15 Total Organic (%) = (Acetone Yield + Yield 3-pentanone + Yield 2-methyl-2-pentenal +
Yield C5-C8 + Yield C9-C10 +)
Thus, the following results were obtained for the catalytic activity experiments with the W and Nb-based catalysts of Examples 1, 3, 6, 7 and 10:
Example one36710
Catalyst W-oW-Nb-O (1.8)W-Nb-O (0.7)W-Nb-O (0.3)Nb-O hydrot.
Conversion (%) Acetic acid0.00%8.04%9.76%10.14%9.99%
Propionaldehyde 86.57%90.13%89.02%91.03%92.34%
Ethanol 49.83%47.11%51.30%52.79%57.57%
Hydroxy acetone 100.00%100.00%100.00%100.00%100.00%
Yield Final (%) Acetone0.22%0.06%0.06%0.15%0.37%
Ethyl acetate 6.69%7.08%5.75%6.15%5.00%
3-pentanone 0.18%0.18%0.18%0.16%0.19%
2-methyl-2-pentenal 8.78%8.81%10.67%10.61%11.57%
C5-C8 3.32%3.92%3.31%2.57%2.76%
C9-C10 + 3.37%4.81%5.12%5.69%5.61%


Total Organic 15.87%17.78%19.34%19.18%20.50%
Table 2. Catalytic activity in the transformation of oxygenated compounds present in aqueous model mix of W and / or Nb based catalysts of Examples 1, 3, 6, 7 and 10.
5 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 acetic acid and propionaldehyde increases with increasing the amount of niobium present in the catalysts used
10 Acetone (acetic acid condensation product) is present in the final mixture in amounts below 0.5%, because it is a very reactive compound that can lead to condensation products of greater molecular weight.
In addition, as the amount of Nb in the catalysts increases, the intermediate condensation products (C5-C8) decrease to produce products of greater molecular weight in subsequent condensation stages.
Also, the increase in the conversion of propionaldehyde causes the amount
20 of 2-methyl-2-pentenal (product of the first self-condensation of propionaldehyde) is growing. Condensation products in the range of C9-C10 + and Total Organic Yield have the same behavior.
These results show that the combination of W and Nb oxides in the structure
25 of these catalysts produce higher yields of condensation products and, in general, greater yield to products in the range of C9-C10 + than their analog W-O catalyst without niobium (example 1). In addition, the Nb-O tungsten catalyst (example 9) also shows improved catalytic activity (both in conversion of oxygenated compounds and in yield to total organics,
30> 20%), even when there are small amounts of W present in the catalyst (See result with low concentrations of W, catalyst of Ex. 7). All this would indicate that there is an optimal range in the W / Nb ratio (between Examples 6 and 10) in the catalyst structure to achieve maximum yields in the


transformation of oxygenated compounds present in aqueous mixtures derived from biomass.
Example 21. Comparative catalytic activity of the 5 W-Nb series catalysts (Examples 3, 6 and 10) against conventional W-Nb oxides (Examples 13 and 14) and commercial Nb2O5 (Sigma-Aldrich, CAS 1313- 96-8)
3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 3, 6, 10, 13, 14 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 220 ° C under continuous stirring. Liquid samples (≈ 50-100 μl) 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 means of
15 gas chromatography on a GC-Bruker 430 equipped with an FID detector and a 60 m TRB-624 capillary column. 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.
20 The following results were obtained:
Example 133146-10
Catalyst W-Nb impreg.W-Nb-O (1.8)W-Nb-O co-precip.W-Nb-O (0.7)Commercial Nb2O5Nb-O hydrot.
Conversion (%) Acetic acid11.13%8.04%13.04%9.76%8.66%9.99%
Propionaldehyde 72.86%90.13%71.69%89.02%76.36%92.34%
Ethanol 51.63%47.11%46.46%51.30%53.47%57.57%
Hydroxy acetone 100.00%100.00%100.00%100.00%100.00%100.00%
Yield Final (%) Acetone0.25%0.06%0.20%0.06%0.40%0.37%
Ethyl acetate 6.51%7.08%7.01%5.75%6.15%5.00%
3-pentanone 0.14%0.18%0.20%0.18%0.13%0.19%
2-methyl-2-pentenal 7.97%8.81%8.14%10.67%8.07%11.57%
C5-C8 3.08%3.92%3.27%3.31%1.73%2.76%
C9-C10 + 2.88%4.81%4.16%5.12%5.40%5.61%
Total Organic 14.33%17.78%15.97%19.34%15.74%20.50%


Table 3. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on W and / or Nb, hydrothermally prepared, Examples 3, 6 and 10, versus the results with other W-Nb catalysts prepared by methods more conventional (Examples 13 and 14) or with commercial Nb2O5.
In Table 3, the catalytic results of the catalysts based on structures containing W-Nb-O and Nb-O prepared hydrothermally and described above (Examples 3, 6 and 10) are compared with other catalysts based on mixed oxides of both metals and prepared by more conventional methods, and whose preparation is described in Examples 13 and 14. In addition, in order to compare the Nb-O catalyst, without W (Example 10), a commercial Nb2O5 catalyst purchased from Sigma- is also used Aldrich, which is activated analogously before use.
From the results in Table 3, 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 10-11%).
The conversion of propionaldehyde is the biggest difference between one type of catalyst and others. While catalysts based on combined W-Nb structures show conversions> 90%, the commercial niobium catalyst and mixed oxides prepared in Examples 13 and 14 have much lower conversions (72-75%). 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 higher molecular weight products originated by second condensation reactions. In these cases, the Total Organic Yield decreases to 1416%, which means that the use of catalysts based on specific W-Nb structures such as Examples 3, 6 and 10 increases the products obtained by 25%. 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.


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
5 commercial materials of similar composition.
Example 22. Comparative catalytic activity of the W-Nb-O series catalysts, prepared by hydrothermal method and treated in nitrogen at different temperatures (Examples 5, 8 and 9)
10 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 5, 8 and 9 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples were taken (≈ 50
15 100 μl) 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 The identification of the products is carried out by means of a gas chromatograph
20 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.
The following results were obtained:
Example 958
Catalyst [Treatment Temperature] W-Nb-O (1.0) [800 ° C]W-Nb-O (1.0) [550 ° C]W-Nb-O (1.0) [300 ° C]
Conversion (%) Acetic acid8.73%9.19%5.84%
Propionaldehyde 83.66%90.34%94.49%
Ethanol 43.55%55.56%52.32%
Hydroxy acetone 100.00%100.00%100.00%
Yield Final (%) Acetone0.19%0.36%0.32%
Ethyl acetate 7.36%4.50%5.73%


3-pentanone 0.14%0.22%0.19%
2-methyl-2pentenal 8.90%8.96%9.90%
C5-C8 4.31%3.08%2.53%
C9-C10 + 3.55%5.00%6.36%
Total Organic 17.09%17.62%19.30%
Table 4. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of catalysts based on W and / or Nb, hydrothermally prepared and treated in nitrogen at different temperatures,
5 Examples 5, 8 and 9.
In Table 4, the catalytic results of the catalysts based on structures containing W-Nb-O (with a molar ratio W / Nb = 1.0) are compared hydrothermally prepared and then heat treated under N2 at different atmospheres.
10 temperatures described above (Examples 5, 8 and 9).
From the results in Table 4, the total conversion of hydroxy-acetone is observed in all cases, while the conversion of acetic acid is quite similar in catalysts treated at high temperatures, that is at 550 and 800 ° C (Examples 9 and 5,
15 respectively); being somewhat lower in the material treated at a lower temperature (300 ° C, Example 8).
However, the distribution of products observed is the biggest difference between these catalysts. Thus, as the temperature at which the catalysts have been treated decreases (from 800 ° C to 550 ° C, and then 300 ° C) a drop in the production of C5-C8 compounds is observed, ranging from 4.31% to 3.08%, finally reaching 2.57%, respectively. At the same time, there is an increase in the generation of C9-> C10 products, from 3.55% to 5.00% (with high temperature treatments), reaching 6.36% (with treatment at 300 ° C) . This same trend of increasing the observed values is evidenced in the yields to Total Organic, which go from 17.09% and 17.62% for the catalysts of Examples 9 and 5, to 19.30% of the catalyst of the Example 8. This means that the


Total Organic yield, and particularly the production of compound C9> C10, can be controlled and even increased by suitable heat treatment of catalysts based on specific W-Nb structures such as that of Examples 5, 8 and 9.
Example 23. Comparative catalytic activity of the W-Nb-O and Nb-O series catalysts, prepared by hydrothermal method (Examples 6 and 10) against a conventional Ce-Zr catalyst (Example 12)
10 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 6, 10 and 12 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50 100 μl) were taken at different time intervals up to 7 hours of reaction. The samples
15 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 of 60 m. The identification of the products is carried out by means of an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and
20 equipped with a 30 m long HP-5 MS capillary column.
The following results were obtained:
Example 61012
Catalyst W-Nb-O (0.7)Nb-O hydrotCe-Zr-O
Conversion (%) Acetic acid9.76%9.99%17.36%
Propionaldehyde 89.02%92.34%93.82%
Ethanol 51.30%57.57%47.81%
Hydroxyacetone 100.00%100.00%100.00%
Yield Final (%) Acetone0.06%0.37%0.21%
Ethyl acetate 5.75%5.00%5.81%
3-pentanone 0.18%0.19%0.15%


2-methyl-2-pentenal 10.67%11.57%11.03%
C5-C8 3.31%2.76%1.61%
C9-C10 + 5.12%5.61%7.57%
Total Organic 19.34%20.50%20.56%
Table 5. Comparative catalytic activity of W and Nb based catalysts of Examples 6 and 10 in the transformation of oxygenated compounds present in model aqueous mixture versus a conventional Ce-Zr catalyst (Example 12).
The conversions of propionaldehyde and hydroxyacetone are very similar in the catalysts of Examples 6, 10 and 12, while the catalyst of Example 12 exhibits a greater conversion of acetic acid and a lower conversion of ethanol (results in Table 5). However, both the overall conversion of reagents and
10 The Total Organic Yield observed are very similar in the three examples studied. The only observable difference between the catalysts based on oxides of W-Nb (Ex. 6 and 10) and the mixed oxide of Ce-Zr (Ex. 12) is that the first two have greater production of organic compounds in the range of C5-C8, while the mixed oxide prepared in Example 12 is capable of catalyzing more
15 easily second condensation reactions, increasing the amount of compounds in the range C9-C10 +.
In general, catalysts based on structures that combine W and Nb have similar results to those demonstrated by a catalyst such as Ce0.5Zr0.5O2
20 traditionally used in bibliography for reactions of this type. The catalysts of Examples 6 and 12 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).
The AE study shows that the Ce-Zr type catalyst of Example 12 has 3.46% by weight of carbon (organic products deposited in the catalyst) after washing. The W-Nb-based catalyst of Example 6 only has 1.42% by weight of carbon, demonstrating that lower substance deposition occurs


carbonates during the reactive process, and therefore it is less sensitive to deactivation caused by coke deposition.
These characterization data are confirmed by TG analyzes. The Ce-Zr catalyst of Example 12 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 6 only shows a mass loss of 3.5% at said temperature. This catalyst also has a mass loss of 3.4% at a temperature close to 100 ° C corresponding to the water absorbed in the channels of the crystalline structure. 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.
Example 24. Comparative catalytic activity during reuse of W-Nb-O (0.7) catalysts (Example 6) and Ce-Zr-O (Example 12)
A series of consecutive reactions with the catalysts prepared in Examples 6 and 12 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).
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 6 and 12 (fresh or already used) were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50-100 μl) 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 The identification of the products is


carried out by means of 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.
The results obtained are shown in Tables 6 and 7, and in Figure 20.
RO R1R2R3
Conversion (%) Acetic acid9.76%7.56%4.92%0.00%
Propionaldehyde 89.02%86.12%86.44%80.37%
Ethanol 51.30%51.10%51.26%49.12%
Hydroxyacetone 100.00%100.00%100.00%100.00%
Yield Final (%) Acetone0.06%0.17%0.33%0.27%
Ethyl acetate 5.75%6.14%6.04%6.49%
3-pentanone 0.18%0.14%0.14%0.18%
2-methyl-2-pentenal 10.67%10.00%9.83%9.25%
C5-C8 3.31%2.76%2.44%2.44%
C9-C10 + 5.12%5.45%5.37%5.70%
Total Organic 19.34%18.52%18.10%17.84%
Table 6. Catalytic activity during reuse of the W-Nb-O catalyst (0.7) of Example 6.
RO R1R2R3
Conversion (%) Acetic acid17.36%13.37%3.84%0.00%
Propionaldehyde 93.82%87.81%84.82%81.21%
Ethanol 47.81%49.73%50.13%55.28%
Hydroxyacetone 100.00%100.00%100.00%100.00%
Yield Final (%) Acetone0.21%0.20%0.09%0.11%
Ethyl acetate 5.81%6.05%5.99%6.27%
3-pentanone 0.15%0.14%0.13%0.15%
2-methyl-2-pentenal 11.03%10.23%9.50%8.37%


C5-C8 1.61%1.89%2.11%2.12%
C9-C10 + 7.57%7.51%7.55%6.52%
Total Organic 20.56%19.98%19.38%17.28%
Table 7. Catalytic activity during reuse of the Ce-Zr-O catalyst of Example 12.
In both catalysts, the same behavior is observed in the conversion of the reagents present in the initial aqueous mixture. Conversions of acetic acid and propionaldehyde decrease with the number of reactions performed. In contrast, the conversion of ethanol increases in the case of the catalyst based on Ce-Zr-O (Ex. 12) and remains constant in the case of the catalyst of W-Nb-O (0.7) (Ex. 6).
10 Consequently, the Total Organic Yield is decreasing slightly with the number of re-uses in both catalysts, but the drop is more pronounced in the case of the Ce-Zr-O catalyst of Example 12 with a percentage loss of catalytic activity with respect to the initial 16%, while the W-Nb-O catalyst prepared in Example 6 shows greater stability with a percentage drop
15 of the catalytic activity of only 7.7% (see Figure 20).
It should be noted that in the case of the Ce-Zr-O catalyst of Example 12, at the end of reuse only 80 mg of the 150 mg initially added is recovered, while 135 mg is recovered in the case of the W catalyst -Nb-O (0.7) of Example 6. The
A smaller 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.
At the same time, the analyzes performed using AE and TG confirm the highest
The stability of the W-Nb-based catalyst of Example 6 compared to the mixed Ce-Zr oxide prepared in Example 12. Thus, in the W-Nb material (Ex. 6) only 1.5 is determined by AE % by weight of coal after the third reuse (R3); while the amount of carbon detected in the Ce-Zr catalyst (Ex. 12) after the same number of re-uses reached 4.8% by weight. Likewise, it is observed by
30 TG analysis that the W-Nb catalyst (Ex. 6) suffers a mass loss of 4.0% at temperatures close to 300-350 ° C corresponding to organic products


absorbed, while the mixed oxide of Ce-Zr (Ex. 12) 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 products heavier reaction absorbed in the catalyst.
Example 25. Comparative catalytic activity of catalysts based on W-Nb-O (Examples 3 and 6) and W-Nb-O with the addition of an alkali metal, W-Nb-K-O (Example 15)
10 3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 3, 6 and 15 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50 100 μl) were taken at different time intervals up to 7 hours of reaction. The samples
15 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 of 60 m. The identification of the products is carried out by means of an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and
20 equipped with a 30 m long HP-5 MS capillary column.
The following results were obtained:
Example 36fifteen
Catalyst W-Nb-O (1.8)W-Nb-O (0.7)W-Nb-K-O
Conversion (%) Acetic acid8.04%9.76%11.45%
Propionaldehyde 90.13%89.02%94.22%
Ethanol 47.11%51.30%47.18%
Hydroxyacetone 100.00%100.00%100.00%
Yield Final (%) Acetone0.06%0.06%0.18%
Ethyl acetate 7.08%5.75%7.10%
3-pentanone 0.18%0.18%0.16%


2-methyl-2-pentenal 8.81%10.67%11.97%
C5-C8 3.92%3.31%3.20%
C9-C10 + 4.81%5.12%4.81%
Total Organic 17.78%19.34%20.32%
Table 8. Comparative catalytic activity for the transformation of oxygenated compounds present in aqueous mixture of catalysts based on W and Nb, of Examples 3, 6 and 15, thermally activated under nitrogen atmosphere.
5 It follows from the results of Table 8 that the incorporation in low concentrations of potassium in the W-Nb-O materials (maintaining a constant W / Nb molar ratio in the composition of the material), generally favors obtaining catalytic activities slightly higher than those observed with
10 W-Nb-O materials of Examples 3 and 6. It should be noted that the presence of K, under these conditions, increases the conversion of acetic acid and the formation of intermediates such as 2-methyl-2-pentenal, practically maintaining constant the formation of products in the range C5-C8 and C9-C10 +, so the Total Organic Performance is slightly increased (> 20%) when using this material W
15 Nb-K-O (Example 15).
Example 26. Comparative catalytic activity of catalysts based on W-Nb-O (Examples 3 and 6) and W-Nb-V-O, with the addition of V as the third metallic element (Examples 16 and 17)
20,000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 3, 6, 16 and 17 were introduced into the autoclave reactor described above. The reactor was tightly sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Samples were taken from
Liquid (≈ 50-100 μl) 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. The identification of the products is carried out by means of a chromatograph of


Agilent 6890 N gases coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with a 30 m long HP-5 MS capillary column.
The results obtained with W-Nb-based catalysts to which a certain amount of vanadium (Examples 16 and 17) have been added are shown below, and the results are compared with W-Nb catalysts of a similar composition:
Example fifteen3166
Catalyst W-Nb-V-O (V / W = 0.33)W-Nb-O (1.8)W-Nb-V-O (V / W = 0.17)W-Nb-O (0.7)
Conv. (%) Acetic acid12.18%8.04%7.88%9.76%
Propionaldehyde 81.60%86.31%90.38%89.02%
Ethanol 48.57%47.11%45.31%51.30%
Hydroxyacetone 100.00%100.00%100.00%100.00%
Yield Final (%) Acetone0.14%0.06%0.42%0.42%
Ethyl acetate 6.46%7.08%6.63%5.75%
3-pentanone 0.17%0.18%0.20%0.18%
2-methyl-2pentenal 9.77%8.81%10.69%10.67%
C5-C8 2.80%3.92%2.77%3.31%
C9-C10 + 4.30%4.81%4.89%5.12%
Total Organic 17.28%17.77%18.97%19.34%
10 Table 9. Catalytic activity in the transformation of oxygenated compounds present in aqueous mixture of W and Nb based catalysts of Examples 3 and 6 against the results of W-Nb-V-O catalysts (Examples 16 and 17).
From the results of Table 9 it is concluded that the catalytic activity of the samples
15 containing V (Ex. 16 and 17) is quite similar to its analog without V and with the same composition (Ex. 3 and 6); although in both cases, when adding vanadium in the structure, a slight decrease in the Performance to Total Organic is observed due to


mainly to the decrease in the production of compounds in the range C9-C10 +.
Example 27. Comparative catalytic activity of catalysts based on W-Nb (Examples 3 and 6) and W-Nb-Ce-O with the addition of Ce as the third metallic element (Example 18)
3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 3, 6 and 18 were introduced into the autoclave reactor described above. The reactor was hermetically sealed, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50 100 μl) 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 The
The identification of the products is carried out by means of an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with a 30 m long HP-5 MS capillary column.
The following results were obtained: 20
Example 3186
Catalyst W-Nb-O (1.8)W-Nb-Ce-OW-Nb-O (0.7)
Conversion (%) Acetic acid8.04%13.77%9.76%
Propionaldehyde 86.31%85.05%89.02%
Ethanol 47.11%47.85%51.30%
Hydroxyacetone 100.00%100.00%100.00%
Yield Final (%) Acetone0.06%0.03%0.42%
Ethyl acetate 7.08%6.32%5.75%
3-pentanone 0.18%0.15%0.18%
2-methyl-2pentenal 8.81%10.59%10.67%
C5-C8 3.92%1.85%3.31%


C9-C10 + 4.81%7.22%5.12%
Total Organic 17.77%19.83%19.34%
Table 10. Comparative catalytic activity of W and Nb-based catalysts of Examples 3 and 6 in the transformation of oxygenated compounds present in model aqueous mixture against a W-Nb-Ce-O catalyst (Example 18).
5 It follows from the results of Table 10 that the partial substitution of W by Ce atoms in W-Nb-O materials (maintaining a constant composition ratio), favors obtaining similar catalytic activities. It should be noted that the presence of Ce, under these conditions, favors condensation reactions
10 consecutive and decreases the number of intermediates located in the range of products C5-C8, while increasing the amount of products generated in the range C9-C10 +.
Example 28. Comparative catalytic activity of catalysts based on W-Nb 15 (Examples 3 and 6) and W-Zr-O (Example 19)
3000 mg of the model aqueous mixture and 150 mg of one of the catalytic materials of Examples 3, 6 and 19 were introduced into the autoclave reactor described above. The reactor was sealed tightly, initially pressurized with 13 bars of N2, and heated to 220 ° C under continuous stirring. Liquid samples (≈ 50 100 μl) 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 The
The identification of the products is carried out by means of an Agilent 6890 N gas chromatograph coupled with an Agilent 5973 N mass detector (GC-MS) and equipped with a 30 m long HP-5 MS capillary column.
The following results were obtained: 30


Example 3196
Catalyst W-Nb-O (1.8)W-Zr-OW-Nb-O (0.7)
Conversion (%) Acetic acid8.04%1.06%9.76%
Propionaldehyde 86.31%89.82%89.02%
Ethanol 47.11%44.98%51.30%
Hydroxyacetone 100.00%100.00%100.00%
Yield Final (%) Acetone0.06%0.05%0.42%
Ethyl acetate 7.08%7.43%5.75%
3-pentanone 0.18%0.22%0.18%
2-methyl-2pentenal 8.81%10.65%10.67%
C5-C8 3.92%3.30%3.31%
C9-C10 + 4.81%4.88%5.12%
Total Organic 17.77%19.09%19.34%
Table 11. Comparative catalytic activity of W and Nb based catalysts of Examples 3 and 6 in the transformation of oxygenated compounds present in model aqueous mixture against a W-Zr-O catalyst (Example 19).
5 It follows from the results of Table 11 that the substitution of Nb by Zr in W-Metal-O materials, leads to results in terms of the formation of products and catalytic activities in general very similar to those observed with W catalysts -Nb-O (Example 3 and 6). It should be noted that the W-Zr combination of the catalyst
10 Example 19, under these conditions, the conversion of acetic acid significantly decreases, while the quantity of products generated in the range C5-C8 and C9-C10 + are similar to those obtained with W-Nb-O materials (Examples 3 and 6).

权利要求:
Claims (27)
[1]
1. A process for the production of mixtures of hydrocarbons and aromatic compounds, characterized in that it comprises at least the following steps:
(to) contacting an aqueous mixture containing oxygenated compounds derived from primary treatments of the biomass with a catalyst, comprising at least W and / or Nb and which, in its calcined form, has at least one material arranged along one of the crystallographic axes and an X-ray diffractogram in which at least diffraction lines corresponding to angles 2 to 22.70.4 and 46.60.4 are observed;
(b) react the mixture with the catalyst in a catalytic reactor at temperatures between 50 and 450 ° C and pressures of 1 to 120 bar;
(C) recover the products obtained in step (b) by means of a liquid / liquid separation process from the aqueous and organic phases.
[2]
2. A process according to claim 1, characterized in that the catalyst has the empirical formula:
WaNbbAcBdOe
in which:-A is a metal of the group of alkali and alkaline earth metals,-B is a chemical element of the group of transition metals, rare earths orelements of groups III, IV and V,-a and b are between 0 and 12.0, with a + b other than zero (a + b ≠ 0),-c is between 0 and 2.0,-d is between 0 and 4.0 and-e has a value that depends on the oxidation state of the elements W, Nb and theitem B.
[3]
3. A process according to claim 2, characterized in that d is zero and the catalyst has the empirical formula:
WaNbbAcOe
in which:-A is a metal of the group of alkali or alkaline earth metals-a and b are between 0 and 12.0, with a + b other than zero (a + b ≠ 0),

-c is between 0.0001 and 1.0 and-e has a value that depends on the oxidation state of the elements W, Nb and A.
[4]
4. A process according to claim 2, characterized in that c is zero and the catalyst has the empirical formula:
WaNbbBdOe
in which: -B is a chemical element of the group of transition metals, rare earths or elements of groups III, IV and V-a and b are between 0 and 12.0, with a + b other than zero ( a + b ≠ 0), -d is between 0.0001 and 4.0 and -e has a value that depends on the oxidation state of elements W, Nb and element B.
[5]
5. A process according to claim 2, characterized in that c and d are zero and the catalyst has the empirical formula:
WaNbbOe
in which:-a and b are between 0 and 12, with a + b other than zero (a + b ≠ 0) and-e has a value that depends on the oxidation state of the elements W and Nb.
[6]
6. A process according to any one of claims 1 to 3, characterized in that A is at least one alkali metal or alkaline earth metal selected from Li, Na, K, Cs, Be, Mg, Ca, Sr, Ba, and combinations thereof .
[7]
7. A process according to claim 6, characterized in that the metal is selected from among Na, K, Cs, Mg, Ca and combinations thereof.
[8]
8. A method according to any of claims 1, 2 and 4, characterized in that element B is selected from the group of transition metals, rare earths, or elements of group III, IV and V.
[9]
9.  A method according to claim 8, characterized in that the element B is a transition metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo,

Ta, Tl, Re and combinations thereof.
[10]
10. A method according to claim 8, characterized in that element B is a rare earth selected from La, Ce and combinations thereof.
[11]
eleven. A method according to claim 8, characterized in that the element B is an element of group III, IV and V selected from B, Al, Ga, Si, Sn, Sb, and combinations thereof.
[12]
12. A method according to claim 8, characterized in that the element B is selected from among Ti, V, Mn, Cu, Zn, Zr, La, Ce, Al, Si, and combinations thereof.
[13]
13. A process according to any of the preceding claims, characterized in that mixtures of hydrocarbons and aromatic compounds of between 5 and 16 carbon atoms are obtained.
[14]
14. A process according to claim 13, characterized in that the products obtained are selected from linear, branched, cyclic aliphatic hydrocarbons of between 5 and 16 carbon atoms, containing between 0 and 4 oxygen atoms.
[15]
fifteen. A process according to claim 13, characterized in that the products obtained are aromatic compounds of between 5 and 16 carbon atoms, containing between 0 and 4 oxygen atoms.
[16]
16. A process according to any one of the preceding claims, characterized in that the aqueous mixture derived from the biomass contains oxygenated compounds that have between 1 and 12 carbon atoms, and also have between 1 and 9 oxygen atoms.
[17]
17. A process according to any of the preceding claims, characterized in that the total concentration of the oxygenated compounds present in the aqueous mixture derived from the biomass are in a range comprised

between 0.5 and 99.5% by weight.
[18]
18. A process according to claim 17, characterized in that the total concentration of the oxygenated compounds present in the aqueous mixture derived from the biomass is in a range of between 1.0 and 70.0% by weight.
[19]
19. A process 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 reactor continuous fluidized bed.
[20]
twenty. A process according to claim 19, characterized in that the reactor is a discontinuous reactor and the reaction is carried out in the liquid phase.
[21]
twenty-one. A method according to claim 20, characterized in that the process is carried out at a pressure of between 1 to 120 bar.
[22]
22 A process according to any of claims 20 or 21, characterized in that the process is carried out at a temperature between 50 ° C and 350 ° C.
[23]
2. 3. A process according to any of claims 20 to 22, characterized in that the contact between the aqueous mixture containing the oxygenated compounds derived from the biomass and the catalyst is carried out in a time ranging from 2 minutes to 200 hours.
[24]
24. A process according to any of claims 20 to 23, characterized in that the weight ratio between the aqueous mixture containing the oxygenated compounds derived from the biomass and the catalyst is between 1 and 200.
[25]
25. A process according to claim 19, characterized in that the reactor is a fixed bed reactor or a fluidized bed reactor.
[26]
26. A method according to claim 25, characterized in that the temperature

The reaction is between 50 ° C and 450 ° C; the contact time - is between 0.001 and 200 s; and the working pressure of between 1 and 100 bars.
[27]
27. A method according to any of the preceding claims,
5 characterized in that the contact between the aqueous fraction containing the oxygenated compounds and the catalyst is carried out under an atmosphere of nitrogen, argon, hydrogen, air atmosphere, nitrogen enriched air, argon enriched air, or combinations thereof.
A method according to claim 27, characterized in that it is carried out in a nitrogen atmosphere.

DRAWINGS
 FIG. one 
 FIG. 2 
10 20 30 40 50 602θ (degrees)

 FIG. 3 
10 20 30 40 50 602

FIG. 4
10 20 30 40 50 602

 FIG. 5 
10 20 30 40 50 602θ (degrees)

FIG. 6
10 20 30 40 50 602θ (degrees)

FIG. 7

FIG. 8
2θ (degrees)
FIG. 9

FIG. 10
10 20 30 40 50 602

FIG. eleven
10 20 3040 50 60 2

 FIG. 12 
2030 405060 70

 FIG. 13 
10 20 30 40 50 602

 FIG. 14 
10 20 30 40 50 602

FIG. fifteen
10 20 30 40 50 602

FIG. 16
10 20 30 40 50 60 2θ

FIG. 17
10 20 3040 50 60 2

FIG. 18

FIG. 19

FIG. twenty

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同族专利:

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公开号 | 公开日

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EP3434364A1|2019-01-30|

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EP3434364A4|2020-05-27|

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US20190367816A1|2019-12-05|

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ES2638719B1|2018-08-01|

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JP2019512530A|2019-05-16|

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US10876049B2|2020-12-29|

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WO2017162900A1|2017-09-28|

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JP6944947B2|2021-10-06|

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BR112018069301A2|2019-01-22|

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ES201630339A|ES2638719B1|2016-03-22|2016-03-22|PROCEDURE FOR THE VALUATION OF OXYGEN COMPOUNDS PRESENT IN WATER FRACTIONS DERIVED FROM BIOMASS|ES201630339A| ES2638719B1|2016-03-22|2016-03-22|PROCEDURE FOR THE VALUATION OF OXYGEN COMPOUNDS PRESENT IN WATER FRACTIONS DERIVED FROM BIOMASS|

---

US16/087,803| US10876049B2|2016-03-22|2017-03-22|Method for recovering the oxygenated compounds contained in aqueous fractions derived from biomass|

---

JP2018550388A| JP6944947B2|2016-03-22|2017-03-22|Method for recovering oxygen-containing compounds contained in water-soluble fraction derived from biomass|

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PCT/ES2017/070167| WO2017162900A1|2016-03-22|2017-03-22|Method for recovering the oxygenated compounds contained in aqueous fractions derived from biomass|

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BR112018069301A| BR112018069301A2|2016-03-22|2017-03-22|procedure for the recovery of oxygenated compounds present in biomass-derived aqueous fractions|

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EP17769506.1A| EP3434364A4|2016-03-22|2017-03-22|Method for recovering the oxygenated compounds contained in aqueous fractions derived from biomass|