WO2016075353A1 - Procedimiento de obtención de 1-octanol - Google Patents
Procedimiento de obtención de 1-octanol Download PDFInfo
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- WO2016075353A1 WO2016075353A1 PCT/ES2015/070812 ES2015070812W WO2016075353A1 WO 2016075353 A1 WO2016075353 A1 WO 2016075353A1 ES 2015070812 W ES2015070812 W ES 2015070812W WO 2016075353 A1 WO2016075353 A1 WO 2016075353A1
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- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
- C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
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- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
Definitions
- the present invention relates to the preparation of 1-octanol using a metal oxide catalyst comprising a noble metal and vanadium and / or gallium. Therefore, the present invention belongs to the field of catalytic processes for obtaining higher alcohols. STATE OF THE PREVIOUS TECHNIQUE
- WO2009026510 describes a method of synthesis of n-butanol by means of a material derived from the thermal decomposition of a hydrotalcite which preferably comprises magnesium and aluminum.
- documents WO2009097312, US20100160693 and WO2009097310 describe materials obtained by the thermal decomposition of hydrotalcites modified by the inclusion of metal carbonates and ethylenediamine tetraacetates, which have been developed by DU PONT as catalysts in the condensation reactions of alcohols operating in a fixed bed at 300 ° C and atmospheric pressure.
- n-hexanol n-HexOH
- 1-octanol 1-OctOH
- 1-Decanol n-DeOH
- n-HexOH produced as an unwanted byproduct, is normally used to reduce the fuel load in furnaces or similar procedures.
- increasing the value of n-HexOH by conversion to higher alcohols such as 1-OctOH and DeOH would help improve the economy of the processes in question.
- the 1-octanol can be produced naturally, from fat, oils and waxes of animal or vegetable origin, as well as synthetically, by petrochemical products such as olefins and paraffins.
- Patent applications EP2679304A1 and EP2679303A1 describe a process for obtaining a metal oxide catalyst comprising gallium and a noble metal for the process of converting lower alcohols to higher alcohols (specifically methanol, ethanol, propanol or isopropanol in n-butanol) which increases the selectivity of the reaction to n-butanol and the productivity of n-butanol. It has been found that precisely this type of catalyst, when contacted with ethanol and n-hexanol, leads to the production of higher alcohols, mainly 1-octanol.
- the present invention relates to a process for obtaining 1-octanol from ethanol and n-hexanol in the presence of a metal oxide catalyst derived from a hydrotalcite, in which the catalyst comprises Ga and / or V together with a noble metal. , preferably the noble metal is Pd.
- the present invention also relates to the process of obtaining a catalyst derived from a hydrotalcite in which the catalyst comprises V or V / Ga and a noble metal, preferably the noble metal is Pd.
- the catalysts derived from hydrotalcite comprising gallium and / or vanadium in their structure provide higher yields of 1-octanol than their analogs without gallium and / or vanadium;
- a first aspect of the present invention relates to a process for obtaining 1-octanol comprising a step of contact between ethanol, n-hexanol and a catalyst, wherein said catalyst comprises: i) a metal oxide which It comprises the following metals:
- M1 is at least one divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe, Ni and Ca;
- M2 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and Ga; ii) a noble metal selected from Pd, Pt, Ru, Rh and Re; Y
- iii) optionally, comprises V; with the proviso that the catalyst comprises at least V, Ga or any of its combinations.
- Divalent metal or “trivalent metal” is understood to mean a metal cation with a +2 or +3 charge, respectively.
- the catalyst is obtained by a process comprising the following steps: a) total or partial thermal decomposition of a hydrotalcite with the formula
- M1 (1. X) M2 x (OH) 2 [A m " ( x / m ) -nH 2 0], in which M1 and M2 have been previously defined;
- A is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II),
- x is a value greater than 0 and less than 1; preferably x is a value between 0.1 and 0.8, m is an integer between 1 and 4; and n is greater than 0, preferably n is a value between 0 and 100, and, more preferably, between 0
- Hydrotalcite is understood to mean the structural family of laminar mixed hydroxides with the formula described above.
- the general structure of hydrotalcites is well known to those skilled in the art.
- thermal decomposition is understood to mean a chemical decomposition or structural change produced by the action of heat. This decomposition may be total or partial, depending on whether said decomposition is carried out completely or, on the contrary, is partially performed. This thermal decomposition can be carried out at temperatures above 150 ° C and in the presence of an oxidizing or non-oxidizing gas.
- hydrotalcite as described above is obtained by co-precipitation of compounds of M1 and M2.
- the co-precipitation is carried out in the aqueous phase.
- Co-precipitation of the compounds may preferably be carried out after the addition of a solution of at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate , phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one M1 compound and at least one M2 compound.
- anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate,
- This anion can be introduced between the sheets of the resulting hydrotalcite.
- sodium and / or potassium salts thereof can be used.
- the at least one anion is selected from carbonate, bicarbonate and hydroxide. The best results are obtained when the co-precipitation is performed at a pH greater than 7, preferably between 10 and 14.
- preferably sodium and / or potassium hydroxide are used.
- Soluble M1 and M2 compounds are understood to mean any salt that, when contacted with a solvent, dissociates, preferably in a polar solvent, more preferably water.
- Examples of soluble M1 and M2 compounds may be nitrates, halides, sulfates, carboxylates and, in general, oxoacids comprising M1 or M2; preferably, the soluble M1 and M2 compounds are nitrates.
- M1 comprises Mg, preferably, M 1 is Mg.
- M2 comprises Al, Ga or any combination thereof. In another embodiment of the first aspect of the present invention, M2 comprises Al. In another embodiment of the first aspect of the present invention, M2 comprises Al and Ga.
- M1 comprises Mg
- M2 comprises Al
- the molar ratio of Mg / AI is between 3 and 4.
- M 1 is Mg, M2 is Al and Ga and the catalyst comprises V. In another embodiment of the first aspect of the present invention, M 1 is Mg, M2 is Al and the catalyst comprises V.
- M1 is Mg
- M2 comprises Ga and the catalyst does not comprise V.
- A is preferably at least one anion selected from the list comprising C0 3 2 “ , HC0 3 “ , 0 2 “ , OH “ , CI “ , N0 3 2” , CI “ , F, Br “ , I “ , CI0 4 “ , CH 3 COO “ , C 6 H 5 COO “ and S0 4 2 “ ; even more preferably, C0 3 2” , HC0 3 “ , 0 2 “ and OH “ .
- the gels resulting from the co -precipitation as described above will filter, wash with water and dry properly.
- hydrotalcite-like structure can be corroborated by means of X-ray diffraction analysis (XRD), while the composition (quantity and type of constituent) of the hydrotalcite or the corresponding mixed oxide obtained by thermal decomposition of the hydrotalcite previously This can be determined by means of mass spectrometry with inductive coupling plasma (ICP-MS) and chemical analysis, among others.
- XRD X-ray diffraction analysis
- ICP-MS inductive coupling plasma
- the thermal decomposition of the hydrotalcite is carried out by calcination under an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging from 250 ° C to 650 ° C, preferably between 350 ° C and 550 ° C.
- the thermal decomposition of the hydrotalcite is preferably performed over a range of 0.5 to 48 hours, preferably between 1 and 24 hours.
- This procedure can be performed by heating the hydrotalcite in a gaseous atmosphere and can be performed in a static oven or a calcination reactor with a controlled gas flow, the latter being the preferred system.
- the gas can be an oxidizing gas or a non-oxidizing gas. Examples of oxidizing gases may include air and oxygen.
- non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia.
- the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof, and, even more preferably, in the presence of oxygen and nitrogen.
- the V and / or the noble metal is added to the metal oxide by wet impregnation, impregnation at incipient volume or deposition-precipitation, preferably the V and the noble metal are added to the metal oxide by wet impregnation, impregnation at incipient volume or deposition-precipitation, more preferably by impregnation at incipient volume.
- the impregnation procedure at incipient volume also called the impregnation procedure at incipient humidity, is based on the use of a minimum amount of liquid for impregnation, only that which is necessary to achieve maximum saturation of the corresponding solid.
- the noble metal comprises Pd, preferably the noble metal is Pd.
- Pd preferably the noble metal is Pd.
- the best yields for 1-octanol have been obtained when calcined hydrotalcites containing Ga and / or V are impregnated with Pd.
- hydrotalcite-derived catalysts comprising gallium and / or vanadium in their structure provide higher yields of 1-octanol in a nitrogen atmosphere than their analogs without gallium / vanadium.
- Another embodiment of the first aspect of the present invention is the process as described above, in which the concentration of the noble metal in the catalyst ranges between 0.001% and 10% by weight with respect to the total catalyst, preferably between 0 , 01% and 5%.
- the concentration of vanadium ranges from 0.001% to 10% by weight with respect to the total catalyst, preferably between 0.01% and 5%.
- Another embodiment of the first aspect of the present invention relates to a process for obtaining 1-octanol comprising a step of contact between ethanol, n-hexanol and a catalyst, wherein said catalyst comprises: i) a metal oxide comprising The following metals:
- M1 is at least one divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe, Ni and Ca;
- M2 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and Ga; ii) a noble metal selected from Pd, Pt, Ru, Rh and Re; Y
- iii) optionally, comprises V; with the proviso that the catalyst comprises at least V, Ga or any of its combinations;
- concentration of vanadium ranges between 0.001% and 10% by weight with respect to the total catalyst, preferably between 0.01% and 5%.
- a calcination step is preferably calcination in an atmosphere of oxygen, nitrogen or any mixture thereof. This calcination is preferably performed at a temperature ranging from 250 ° C to 650 ° C, and, even more preferably, between 350 ° C and 550 ° C. This calcination is preferably carried out during an interval ranging from 0.5 to 48 hours, preferably between 1 and 24 hours, and, even more preferably, between 1 and 6 hours.
- This procedure can be performed by heating the hydrotalcite-derived material in a gaseous atmosphere and can be performed in a static oven or a calcination reactor with a controlled gas flow, the latter being the preferred system.
- the gas can be an oxidizing gas or a non-oxidizing gas.
- oxidizing gases may include air and oxygen.
- non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia.
- the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof, and, even more preferably, in the presence of oxygen and nitrogen.
- the process of the invention as described above further comprises a step of reduction after calcination after the addition of the noble metal.
- the noble metal which acts as one of the main active sites in the process, is reduced.
- This reduction step is preferably carried out in an atmosphere of H 2 and, preferably, at a temperature ranging from 200 ° C to 500 ° C, more preferably between 250 ° C and 450 ° C.
- This reduction is preferably performed over a range of between 0.5 and 48 hours, preferably between 1 and 24 hours, and, even more preferably, between 1 and 6 hours.
- the reduction takes place immediately before the step of contact with the reagent.
- the contact between the Ethanol, n-hexanol and the catalyst are carried out in a reactor selected from the list comprising discontinuous reactor, continuous stirred tank reactor, fixed bed continuous reactor and fluidized bed continuous reactor, preferably a discontinuous reactor.
- the reactor is a discontinuous reactor
- the contact between the reagent and the catalyst is carried out at a temperature ranging from 50 ° C to 450 ° C, preferably between 130 ° C and 330 ° C.
- the weight ratio between the reagent and the catalyst is preferably between 2 and 200, preferably between 5 and 100.
- it is carried out during a time interval ranging from 2 minutes to 200 hours, preferably between 1 hour and 100 hours
- the contact between ethanol, n-hexanol and the catalyst is carried out at a pressure of up to 120 bar, preferably between 20 and 80 bar.
- the contact between ethanol, n-hexanol and the catalyst is carried out under an atmosphere of nitrogen, argon, hydrogen or any mixture thereof, preferably in an atmosphere of nitrogen and hydrogen. .
- nitrogen, argon, hydrogen or any mixture thereof preferably in an atmosphere of nitrogen and hydrogen.
- a second aspect of the present invention relates to a process for obtaining a catalyst, comprising the following steps: a) total or partial thermal decomposition of a hydrotalcite with the formula
- M1 is at least one divalent metal selected from Mg, Zn , Cu, Co, Mn, Fe, Ni and Ca
- M2 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and Ga
- A is at least one anion selected from hydroxide, chloride , fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II),
- x is a value greater than 0 and less than 1, preferably x is a value between 0, 1 and 0.8; m is an integer between 1 and 4; and n is greater than 0, preferably n is a value between 0 and 100, and, even more preferably, between 0 and 20; b) addition of V and at least one noble metal selected from Pd, Pt, Ru, Rh and Re to the solid obtained in the previous stage.
- n indicates the number of crystallization water molecules and depends on the composition of the hydrotalcite cations.
- the process for obtaining a catalyst as described above further comprises a step (a ') before step (a), in which the hydrotalcite is synthesized by the co- precipitation of compounds of M1 and M2.
- the co-precipitation is carried out in the aqueous phase.
- Co-precipitation of the compounds may preferably be carried out after the addition of a solution of at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate , phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one M1 compound and at least one M2 compound.
- This anion can be introduced between the sheets of the resulting hydrotalcite.
- sodium and / or potassium salts thereof can be used.
- at least one anion is selected from carbonate, bicarbonate and hydroxide. The best results are obtained when the co-precipitation is performed at a pH greater than 7, preferably between 10 and 14.
- sodium and / or potassium hydroxide are preferably used.
- Soluble M1 and M2 compounds are understood to mean any salt which, when contacted with a solvent, preferably dissociates a polar solvent, more preferably water.
- soluble M1 and M2 compounds may be nitrates, halides, sulfates, carboxylates and, in general, oxoacids comprising M1 or M2; preferably, the soluble M1 and M2 compounds are nitrates.
- M1 comprises Mg, preferably, M1 is Mg.
- M2 comprises Al, Ga or any combination thereof. In another embodiment of the second aspect of the present invention, M2 comprises Al. In another embodiment of the second aspect of the present invention, M2 comprises Al and Ga. In another embodiment of the second aspect of the present invention, M1 comprises Mg, M2 comprises Al and the molar ratio of Mg / AI is between 3 and 4.
- A is preferably at least one anion selected from the list comprising C0 3 2 “ , HC0 3 “ , 0 2 “ , OH “ , CI “ , N0 3 2” , CI “ , F, Br “ , I “ , CI0 4 “ , CH 3 COO “ , C 6 H 5 COO “ and S0 4 2 “ ; even more preferably, C0 3 2” , HC0 3 “ , 0 2 “ and OH “ .
- the thermal decomposition of step (a) is the calcination in an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging from 250 ° C to 650 ° C, preferably between 350 ° C and 550 ° C.
- the thermal decomposition of hydrotalcite is preferably performed over a range of 0.5 to 48 hours, preferably between 1 and 24 hours. This procedure can be performed by heating the hydrotalcite in a gaseous atmosphere and can be performed in a static oven or a calcination reactor with a controlled gas flow, the latter being the preferred system.
- the gas can be an oxidizing gas or a non-oxidizing gas. Examples of oxidizing gases may include air and oxygen.
- non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia.
- the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof, and, even more preferably, in the presence of oxygen and nitrogen.
- the addition of V and / or the addition of the noble metal of step (b) is carried out by wet impregnation, impregnation at incipient volume or deposition-precipitation, preferably V and metal noble are added to the metal oxide by wet impregnation, impregnation to incipient volume or deposition-precipitation, more preferably by impregnation to incipient volume.
- the noble metal that is added in step (b) comprises Pd, preferably the noble metal is Pd. The best yields for 1-octanol have been obtained when calcined hydrotalcites containing V are impregnated with Pd.
- catalysts derived from hydrotalcite comprising vanadium or vanadium and gallium in their structure provide higher yields of 1-octanol in a nitrogen atmosphere than their analogs without vanadium.
- the concentration of the noble metal in the catalyst ranges from 0.001% to 10% by weight with respect to the total catalyst, preferably between 0.01% and 5%.
- the concentration of vanadium ranges between 0.001% and 10% by weight with respect to the total catalyst, preferably between 0.01% and 5%.
- Another embodiment of the second aspect of the present invention relates to a process for obtaining a catalyst, comprising the following steps: a) total or partial thermal decomposition of a hydrotalcite with the formula
- M1 is at least one divalent metal selected from Mg, Zn , Cu, Co, Mn, Fe, Ni and Ca
- M2 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and Ga
- A is at least one anion selected from hydroxide, chloride , fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II),
- x is a value greater than 0 and less than 1, preferably x is a value between 0, 1 and 0.8; m is an integer between 1 and 4; and n is greater than 0, preferably n is a value between 0 and 100, and, even more preferably, between 0 and 20; b) addition of V and at least one noble metal selected from Pd, Pt, Ru, Rh and Re al solid obtained in the previous stage; wherein the concentration of vanadium ranges between 0.001% and 10% by weight with respect to the total catalyst, preferably between 0.01% and 5%.
- the process for obtaining the catalyst as described above further comprises a step (c), subsequent to (b), in which the product obtained in step (b) is calcine, preferably also comprises a reduction stage (d), after (c).
- This calcination is preferably calcination in an atmosphere of oxygen, nitrogen or any mixture thereof.
- This calcination is preferably performed at a temperature ranging from 250 ° C to 650 ° C, and, even more preferably, between 350 ° C and 550 ° C.
- This calcination is preferably carried out during an interval ranging from 0.5 to 48 hours, preferably between 1 and 24 hours, and, even more preferably, between 1 and 6 hours.
- This procedure can be performed by heating the hydrotalcite-derived material in a gaseous atmosphere and can be performed in a static oven or a calcination reactor with a controlled gas flow, the latter being the preferred system.
- the gas can be an oxidizing gas or a non-oxidizing gas.
- oxidizing gases may include air and oxygen.
- non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia.
- the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof, and, even more preferably, in the presence of oxygen and nitrogen.
- the noble metal which acts as one of the main active sites in the process, is reduced.
- This reduction step is preferably carried out in an atmosphere of H 2 and, preferably, at a temperature ranging from 200 ° C to 500 ° C, more preferably between 250 ° C and 450 ° C.
- This reduction is preferably performed over a range of between 0.5 and 48 hours, preferably between 1 and 24 hours, and, even more preferably, between 1 and 6 hours.
- the reduction takes place immediately before the step of contact with the reagent.
- a third aspect of the present invention relates to a catalyst obtained by means of the process for obtaining a catalyst as described above.
- a fourth aspect of the present invention relates to the use of the catalyst as described above to obtain 1-octanol.
- Fig. 1 Shows a comparative graph of the catalytic activities (conversions of EtOH and HexOH and yields in n-ButOH, 1-OctOH and C 4+ OH) of catalysts based on an HT-1 material (Examples 1, 4 and 7) in an atmosphere of N 2 .
- Fig. 2. Shows a comparative graph of the catalytic activities (conversions of EtOH and n-HexOH and yields to n-ButOH, 1-OctOH and C 4+ OH) of catalysts based on an HT-3 material (Examples 2, 5 and 8) in an atmosphere of N 2 . Key to the graph: lines: Example 2 (HT-3); points: Example 5 (0.78% Pd / HT-3); black: Example 8 (0.75% Pd / 0.24% V / HT-3). Fig. 3.
- Fig. 4. Shows a comparative graph of the catalytic activities (conversions of EtOH and n-HexOH and yields to n-ButOH, 1-OctOH and C 4+ OH) of catalysts based on an HT-4 material with Ga (Examples 10, 11 and 12) in an atmosphere of N 2 .
- the first solution contained 17.79 g of Mg (N0 3 ) 2 -6H 2 0 and 26.05 g of AI (N0 3 ) 3 -9H 2 0, dissolved in 48.72 g of Milli-Q water, with a molar concentration of Al + Mg of 1.5.
- the second solution contained 13.95 g of NaOH and 9.86 g of Na 2 C0 3 in 68.85 g of Milli-Q water, and was used to produce adequate precipitation of Al and Mg species, and to fix the pH of the total mixture at ⁇ 13. Both solutions were added, at a total flow rate of 20 ml / h for approx.
- the first solution contained 27.99 g of Mg (N0 3 ) 2 -6H 2 0 and 13.65 g of AI (N0 3 ) 3 -9H 2 0, dissolved in 55.31 g of Milli-Q water, with a molar concentration of Al + Mg of 1.5.
- the second solution contained 13, 13 g of NaOH and 10.23 g of Na 2 C0 3 in 73.61 g of Milli-Q water, and was used to produce adequate precipitation of Al and Mg species, and to fix the pH of the total mixture at ⁇ 13. Both solutions were added, at a total flow rate of 20 ml / h for approx.
- Example 3 Synthesis of the HT-4 catalyst (Mg / AI «4 molar ratio) It was prepared by means of a standard co-precipitation procedure using two solutions.
- the first solution contained 36.45 g of Mg (N0 3 ) 2 -6H 2 0 and 13.60 g of AI (N0 3 ) 3 -9H 2 0, dissolved in 67.79 g of Milli-Q water, with a molar concentration of Al + Mg of 1.5.
- the second solution contained 12.53 g of NaOH and 16.16 g of Na 2 C0 3 in 89.63 g of Milli-Q water, and was used to produce adequate precipitation of the Al and Mg species, and to fix the pH of the total mixture at ⁇ 13.
- Both solutions were added, at a total flow rate of 20 ml / h for approx. 4 h, to a vessel under vigorous stirring at room temperature.
- the gel formed was aged at room temperature for 1-2 h; It was then filtered and washed with distilled water until the carbonate was not detected in the filtered liquid (at pH ⁇ 7). Subsequently, the solid was dried in an oven at 60 ° C for 18 h.
- the hydrotalcite obtained was calcined in air at 450 ° C and a mixed oxide called HT-4 was obtained, with a Mg / AI ⁇ 3.80 molar ratio and a surface area (BET method) of 257 m 2 / g.
- Example 4 Synthesis of catalyst 0.70% Pd / HT-1 It was prepared from the material prepared as described in Example 1, in which the incorporation of Pd (1.0% by weight, theoretical) in the HT-1 material (Mg / AI ⁇ 1) was carried out by means of the incipient moisture impregnation process, using, in this case, 0.0360 g of Pd (NH 3 ) 4 CI 2 -6H 2 0 dissolved in 2 ml of Milli-Q water, to impregnate 1, 4086 g of HT- one.
- the solid obtained was dried in an oven at 100 ° C for 12 h; It was then calcined in air at 450 ° C for 6 h, and then reduced to 450 ° C in an H 2 atmosphere for 3 h before catalytic application.
- the resulting Pd / HT-1 material characterized by chemical analysis and ICP-MS, contained ⁇ 0.70% by weight of Pd.
- Example 6 Synthesis of catalyst 0.77% Pd / HT-4 It was prepared from the material prepared as described in Example 3, in which the incorporation of Pd (1.0% by weight, theoretical) in the HT-4 material (Mg / AI ⁇ 1) was carried out by means of the impregnation process to incipient humidity, using, in this case, 0.030 g of Pd (NH 3 ) 4 CI 2 -6H 2 0 dissolved in 2,000 g of water Milli-Q, to impregnate 1.014 g of HT-4.
- the solid obtained was dried in an oven at 100 ° C for 14-16 h; It was then calcined in air at 450 ° C for 3-4 h and subsequently reduced to 350 ° C in an H 2 atmosphere for 3 h before the catalytic application thereof.
- the resulting Pd / HT-1 material characterized by chemical analysis and ICP-MS, contained ⁇ 0.77% by weight of Pd.
- Example 7
- the incorporation of V (0.2%, theoretical) to the solid obtained was also carried out by means of the impregnation process at incipient humidity, using 0.0098 g of NH 4 V0 3 dissolved in 1 ml of Milli-Q water and 1 ml 0.2 M oxalic acid to impregnate the solid obtained in the first stage. Once impregnated, the solid obtained was dried in an oven at 100 ° C for 12 h; It was then calcined in air at 450 ° C for 6 h and subsequently reduced to 350 ° C in an H 2 atmosphere for 3 h before catalytic application.
- the resulting Pd / V / HT-1 material characterized by chemical analysis and ICP-MS, contained ⁇ 0.77% by weight of Pd and 0.2% by weight of V.
- Example 8 Synthesis of catalyst 0.75% Pd / 0.24% V / HT-3 It was prepared from the material prepared as described in Example 2, in which the incorporation of Pd (1.0% in weight, theoretical) and V (0.2% by weight, theoretical) in the HT-3 material (Mg / AI ⁇ 3) was carried out by means of the impregnation process to incipient moisture in two successive stages. In the first stage, 0.0300 g of Pd (NH 3 ) 4 CI 2 -6H 2 0 dissolved in 2 ml of Milli-Q water were used to impregnate 1, 2094 g of HT-3. Once impregnated, the solid obtained was dried in an oven at 100 ° C for 12 h.
- the resulting Pd / V / HT-3 material characterized by chemical analysis and ICP-MS, contained ⁇ 0.75% by weight of Pd and 0.24% by weight of V.
- Example 9 Synthesis of catalyst 0.97% Pd / 1.00% V / HT-4
- the incorporation of V (2.0%, theoretical) to the solid obtained was also carried out by means of the impregnation process at incipient humidity, using 0.0460 g of NH 4 V0 3 dissolved in 2,000 g of Milli-Q water to impregnate the solid obtained in the first stage. Once impregnated, the solid obtained was dried in an oven at 100 ° C for 14-16 h; It was then calcined in air at 450 ° C for 6 h and subsequently reduced to 350 ° C in an H 2 atmosphere for 3 h before catalytic application.
- the resulting Pd / V / HT-4 material characterized by chemical analysis and ICP-MS, contained ⁇ 0.97% by weight of Pd and 1.0% by weight of V.
- Example 10 Synthesis of catalyst 0.29% Ga-HT-4 It was prepared by means of a standard co-precipitation procedure using two solutions.
- the first solution contained 29.89 g of Mg (N0 3 ) 2 -6H 2 0, 10.90 g of AI (N0 3 ) 3 -9H 2 0 and 0.06 g of Ga (N0 3 ) 3 -9H 2 0, dissolved in 55, 18 g of Milli-Q water, with a molar concentration of (Al + Mg + Ga) of 1.5.
- the second solution contained 12.52 g of NaOH and 10.52 g of Na 2 C0 3 in 72.60 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Ga species, and to set the pH of the total mixture to ⁇ 13. Both solutions were added, at a total flow rate of 30 ml / h for approximately 4 h, to a vessel under vigorous stirring at room temperature. The gel formed was aged at room temperature for 1-2 h; It was then filtered and washed with distilled water until the carbonate was not detected in the filtered liquid (at pH ⁇ 7). Subsequently, the solid was dried in an oven at 60 ° C for 14-16 h.
- the hydrotalcite (Ga-HT-4) obtained was calcined in air at 450 ° C for 3-4 h, to obtain a mixed oxide with a molar ratio of Mg / AI ⁇ 3.8, a Ga content of 0.29 % by weight (measured by chemical analysis and ICP-MS) and a surface area (BET method) of 262 m 2 / g.
- Example 11 Synthesis of catalyst 0.87% Pd / 0.29% Ga-HT-4
- Example 12 Synthesis of catalyst 0.97% Pd / 0.29% V / 0.29% Ga-HT-4 It was prepared from the material prepared as described in Example 10, in which the incorporation of Pd (1.0% by weight, theoretical) and V (0.2% by weight, theoretical) in the Ga-HT-4 material was carried out by means of the impregnating moisture process in two successive stages. In the first stage, 0.0355 g of Pd (NH 3 ) 4 CI 2 -6H 2 0 dissolved in 2 ml of Milli-Q water were used to impregnate 1.4072 g of 0.29% Ga-HT-4 . Once impregnated, the solid obtained was dried in an oven at 100 ° C for 14-16 h.
- the incorporation of V (0.2%, theoretical) to the solid obtained was also carried out by means of the impregnation process at incipient humidity, using 0.0096 g of NH 4 V0 3 dissolved in 1 ml of Milli-Q water and 1 ml 0.2 M oxalic acid to impregnate the solid obtained in the first stage. Once impregnated, the solid obtained was dried in an oven at 100 ° C for 1-2 h; It was then calcined in air at 450 ° C for 6 h and subsequently reduced to 350 ° C in an H 2 atmosphere for 3 h before catalytic application. The resulting Pd / V / 0.29% Ga-HT-4 material, characterized by chemical analysis and ICP-MS, contained ⁇ 0.97% by weight of Pd and 0.29% of V.
- This catalyst was synthesized to illustrate Cu-containing hydrotalcite type catalysts, such as those cited in WO2009026523.
- Various catalysts were synthesized with different concentrations of Cu, and the catalyst that provided the best results, in terms of selectivity and conversion was selected in order to be compared with the catalysts of the invention.
- the first solution contained 30.0795 g of Mg (N0 3 ) 2 -6H 2 0, 10.4441 g of AI (N0 3 ) 3 -9H 2 0 and 1, 1720 g of Cu (N0 3 ) 2 -3H 2 0, dissolved in 57.6217 g of Milli- Q water, with a molar concentration of (Al + Mg + Cu) of 1.5.
- the second solution contained 13.0492 g of NaOH and 10.5207 g of Na 2 C0 3 in 74.7069 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to set the pH of the total mixture to ⁇ 13.
- the hydrotalcite (Cu-HT-4) obtained was calcined in air at 450 ° C for 3-4 h, to obtain a mixed oxide with a molar ratio of Mg / AI ⁇ 3.8, a Cu content of 4.9 % by weight, characterized by chemical analysis and ICP-MS and a surface area (BET method) of 190.08 m 2 / g.
- Example 14 Catalyst synthesis 0.98% Pd / 0.20% V / 4.9% Cu-HT-4
- the incorporation of V (0.2%, theoretical) to the solid obtained was also carried out by means of the impregnation process at incipient humidity, using 0.0090 g of NH 4 V0 3 dissolved in 1 ml of Milli-Q water and 1 ml 0.2 M oxalic acid to impregnate the solid obtained in the first stage. Once impregnated, the solid obtained was dried in an oven at 100 ° C for 12 h; It was then calcined in air at 450 ° C for 6 h and subsequently reduced to 350 ° C in an H 2 atmosphere for 3 h before catalytic application. The resulting Pd / V / 0.29% Ga-HT-4 material, characterized by chemical analysis and ICP-MS, it contained ⁇ 0.98% by weight of Pd and 0.20% of V.
- Example 15 Comparative catalytic activity of the catalysts of Examples 1 to 13 under N 2 atmosphere
- Liquid samples ( ⁇ 50-100 ⁇ ) were taken at different time intervals until 17 hours of reaction.
- the samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in acetonitrile, and analyzed by means of gas chromatography on a GC-3900. They are equipped with an FID detector and a TRB-624 capillary column. 60 m
- Example 16 Comparative catalytic activity of the catalysts of Examples 6, 9 and 11 under an atmosphere of N 2 with ethanol alone (without n-hexanol)
- the samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in acetonitrile, and analyzed by means of gas chromatography on a GC-3900. They are equipped with an FID detector and a TRB-624 capillary column. 60 m
- Example 17 Comparative catalytic activity of the catalysts of Examples 6, 9, 11 and 12 under an atmosphere of N 2 with n-butanol as raw material (neither ethanol nor n-hexanol)
- Liquid samples ( ⁇ 50-100 ⁇ ) were taken at different time intervals until 17 hours of reaction.
- the samples were filtered and diluted in a standard solution of 2% by weight of chlorobenzene in acetonitrile, and analyzed by means of gas chromatography on a GC-3900. They are equipped with an FID detector and a TRB-624 capillary column. 60 m
- the rest of the products up to 100% mainly comprise 3-methyl-2-butanone, butyl butanoate, n-butyl ether, 4-methyl-2-hexanone, 1,1-dibutoxybutane.
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US11713289B2 (en) | 2018-04-16 | 2023-08-01 | Viridis Chemical, Llc | Composition of catalysts for conversion of ethanol to N-Butanol and higher alcohols |
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