西班牙专利ES2647963A1 Procedure for obtaining 1-octanol (Machine-translation by Google Translate, not legally binding)

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专利摘要:
Procedure for obtaining 1-octanol. The present invention relates to a process for obtaining 1-octanol comprising a contact step between ethanol, N-hexanol and two catalysts a and b, wherein the catalyst a comprises a metal oxide comprising ga and a noble metal and the catalyst b comprises a metal oxide comprising cu, ni or any of its mixtures. (Machine-translation by Google Translate, not legally binding)
公开号:ES2647963A1
申请号:ES201630680
申请日:2016-05-26
公开日:2017-12-27
发明作者:Avelino Corma Canós；Marcelo Eduardo Domine；Juan Luis SANZ YAGÜE；Francisco Antonio Ladrón De Guevara Vidal
申请人:Abengoa Bioenergia Nuevas Technologias SA；
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专利说明:

The present invention relates to a process for obtaining 1-octanol using two catalysts A and B, the catalyst A metal oxide type comprising a noble metal and gallium, and a catalyst B, metal oxide type comprising Cu, Ni or any of their mixtures. Therefore, the present invention belongs to the field of catalytic processes for obtaining higher alcohols. STATE OF THE TECHNIQUE
In recent years, numerous scientific and patent publications have been published on the use of hydrotalcite-like materials as catalysts in alcohol condensation reactions, such as the Guerbet reaction, both in discontinuous systems and in continuous fixed-bed reactors. Most of the reactions described with said catalyst relate to obtaining n-butanol from ethanol. Studies conducted with these mixed Mg-Al oxides revealed that the catalytic activity of these materials depends on the nature, density and resistance of the basic surface sites, which, in turn, depend on the molar composition of Mg / Al in the solid. (JI Di Cosimo, VK Ten, M. Xu, E. Church,
C. R. Apesteguia, J. Catal. 178, 499-510, 1998).
More recently, it has also been established that mixed oxides derived from hydrotalcite based on Cu / Mg / Al show better catalytic activities in the condensation of alcohols than other analogous hydrotalcites, such as those that include supported Ni species (C. Carlini, A Macinai, M. Marchionna, M. Noviello, AMR Galletti, G. Sbrana, J. Mol. Catal. A: Chem. 206, 409, 2003; X. Jiang,
Z. Du, document CN101530802, 2009), among others.
Furthermore, the international application 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. Also, documents WO2009097312, US20100160693 and WO2009097310 describe materials obtained by 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 that operate in a fixed bed at 300 ºC and atmospheric pressure. The best results under these conditions have been achieved with a hydrotalcite derived material based on Cu-Mg-Al (containing OH-as anion), which has high ethanol conversion (≈ 44%) with moderate selectivities (≈ 44%) to n-butanol. When these same materials were tested in the catalytic conversion of ethanol to n-butanol in the presence of hydrogen in the reaction system, the yields of n-butanol obtained were significantly lower in all cases.
The synthesis of high molecular weight alcohols (containing between 8-16 carbon atoms) has been of interest in recent years due to the potential of these oxygenated compounds for use as surfactants and for the addition to polymers, lubricants, cosmetics and Many other specific uses. In particular, n-hexanol (n-HexOH), with an annual production of 450,000 kilograms, with a low market value based on small-scale laboratory supply, could be transformed into 1-octanol (1-OctOH) or 1-Decanol (n-DeOH) more valuable.
1-OctOH and n-DeOH, with a worldwide production exceeding 400,000 tons per year, are mainly used as surfactants and for the addition to polymers, lubricants, cosmetics and many other specific uses.
Currently, n-HexOH, produced as an unwanted byproduct, is normally used to reduce the fuel load in furnaces or similar procedures. However, 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.
The development of catalysts has been of great importance for the improvement of the synthesis procedures of 1-octanol, allowing an increase in yields and a reduction in reaction times and, consequently, reducing the costs of these industrial processes. 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 C1-C3 alcohols into higher alcohols (specifically methanol, ethanol, propanol or isopropanol in n- butanol) which increases the selectivity of the reaction to nbutanol and the productivity of n-butanol. Application WO2016075353 refers to a metal oxide catalyst comprising gallium or gallium and vanadium for obtaining 1-octanol.
It has been found that precisely this type of catalyst used in conjunction with a metal oxide catalyst comprising Ni, Cu or any of its mixtures, leads to the production of higher alcohols, mainly 1-octanol, when contacted with ethanol and n -hexanol. DESCRIPTION OF THE INVENTION
The present invention relates to a process for obtaining 1-octanol from ethanol and n-hexanol in the presence of two catalysts A and B, two catalysts based on metal oxide where A comprises Ga and a noble metal and where B comprises Ni , Cu or any of its mixtures. Likewise, the present invention also relates to the use of said catalysts for obtaining octanol.
The invention has the following advantages over the state of the art:
- the yield of higher alcohols is higher when both catalysts A and B are used, compared to the use of said catalysts separately,
- they are more selective towards the production of linear alcohols and reduce the amount of branched alcohols;
- only catalyst A requires noble metal, which saves the necessary amount of these metals;
- to produce the same amount of linear alcohols will require less mass of
catalyst in an industrial application;
- high yields are obtained at higher alcohols working at temperatures ≤250 ° C and pressures lower than 40 bar, even in the absence of H2.
Therefore, 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 two catalysts A and B, where catalyst A comprises:
i) a metal oxide comprising the following metals:M1 is a divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe,Ni, Ca and any of its mixtures, preferably M1 is a metaldivalent selected from Mg, Ca and any of its mixtures, morepreferably M1 is Mg.M2 is trivalent Ga; Y
ii) a noble metal selected from Pd, Pt, Ru, Rh, Re and any oftheir mixtures;
and catalyst B comprises a metal oxide comprising the following
Metals: M3 is a divalent metal selected from Mg, Zn, Cu Co, Mn, Fe, Ni, Ca and any of its mixtures, M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any of its mixtures,
with the proviso that catalyst B comprises at least Cu, Ni or any combination thereof, wherein Ni comprises divalent, trivalent Ni or any of its mixtures.
"Divalent metal" or "trivalent metal" is understood to mean a metal cation with a +2 or +3 charge, respectively.
Catalysts A and B can be physically mixed prior to contact with ethanol and n-hexanol.
In an embodiment of the first aspect of the present invention, the metal oxide of catalyst A further comprises an M5 metal, where M5 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co and Ni, preferably M5 comprises Al, more preferably M5 is Al.
In another embodiment of the first aspect of the present invention, catalyst A is obtained by a process comprising the following steps:
a) total or partial thermal decomposition of an HTA hydrotalcite with the formula
[M11- (x + y) M2y M5x (OH) 2] [QAm- (x + y) /m.nH2O], where:
M1, M2 and M5 have been defined above,QA 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 between 0 and 0.5; and is a value between 0.00001 and 0.49; m is an integerbetween 1 and 4; and n is greater than 0, preferably n is a value between 1 and 100, and morepreferably between 1 and 20;b) addition to the metal oxide obtained in step a) of:a noble metal selected from Pd, Pt, Ru, Rh, Re and any of its mixtures.
n indicates the number of crystallization water molecules and depends on thecomposition of hydrotalcite cations.
"Hydrotalcite" is understood to mean the structural family of mixed hydroxides.laminar with the formula described above. The general structure of theHydrotalcites is well known to those skilled in the art.
The term "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.
The combination of a catalyst A and a catalyst B, provide higher yields of 1-octanol in a nitrogen atmosphere than if only a catalyst A or a catalyst B is used. That is, there is a synergy in the combined use of the two catalysts. .
With respect to the anion, QA is preferably at least one anion selected from the list comprising CO32-, HCO3-, O2-, OH-, Cl-, NO32-, Cl-, F-, Br-, I-, ClO4- , CH3COO-,
-
C6H5COO-y SO42-; even more preferably, CO32-, HCO3-, O2 and OH-.
In another embodiment of the first aspect of the present invention, the HTA hydrotalcite is obtained by co-precipitation of compounds of M1, M2 and M5.
In another embodiment of the first aspect of the present invention, M1 is a divalent metal selected from Mg, Ca and any of its mixtures, preferably M1 is Mg.
Preferably, 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, ptoluenesulfonate, phenoxide , alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one compound of M1, at least one compound of M2 and at least one compound of M5. This anion can be introduced between the sheets of the resulting hydrotalcite. In order to obtain anion solutions, sodium and / or potassium salts thereof can be used. Preferably, the at least one anion is selected from carbonate, bicarbonate and hydroxide. The best results are obtained when co-precipitation
it is performed at a pH greater than 7, preferably between 10 and 14. In addition, in order toregulate the pH, preferably sodium and / or potassium hydroxide are used.
Preferably, before the precipitation of said compounds, there is dissolution of alat least one compound of M1, at least one compound of M2 and at least oneM5 compound. By compounds of soluble M1, M2 and M5 it is understood thatthey mean any salt that, when contacted with a solvent, dissociates,preferably in a polar solvent, more preferably water. Examples ofSoluble M1, M2 and M5 compounds can be nitrates, halides, sulfates,carboxylates and, in general, oxoacids comprising M1, M2 or M5;preferably, the soluble M1, M2 and M5 compounds are nitrates.
In another embodiment of the first aspect of the present invention, catalyst B isobtained by a procedure comprising a decomposition stageTotal or partial thermal of an HTB hydrotalcite with the formula:[M3 (1-z) M4z (OH) 2] [QBp- (z / n) .rH2O], in which:M3 and M4 have been defined above,QB is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide,
nitrate, perchlorate, chlorate,baking soda,acetate, benzoate,methanesulfonate,p
toluenesulfonate, phenoxide,alkoxide,carbonate,sulfate,terephthalate,phosphate,
hexacyanoferrate (III) and hexacyanoferrate (II),
z is a value greater than 0 and less than 1, preferably z is a value between 0.1 and 0.8; p is an integer between 1 and 4; and r is greater than 0, preferably r is a value between 1 and 100, and more preferably between 1 and 20.
With respect to the anion, QB is preferably at least one anion selected from the list comprising CO32-, HCO3-, O2-, OH-, Cl-, NO32-, Cl-, F-, Br-, I-, ClO4- , CH3COO-,
-
C6H5COO-y SO42-; even more preferably, CO32-, HCO3-, O2 and OH-.
In another embodiment of the first aspect of the present invention, HTB hydrotalcite is obtained by co-precipitation of compounds of M3 and M4.
In another embodiment of the first aspect of the present invention, M3 is a divalent metal selected from Mg, Ca, Cu, Ni and any of its mixtures, preferably M3 is a divalent metal selected from Mg, Cu, Ni and any of its mixtures
In another embodiment of the first aspect of the present invention, M4 is a trivalent metal selected from Al, Ni and any of its mixtures. More preferably M4 is Al.
In another embodiment of the first aspect of the present invention, catalyst B comprises Cu and Ni. The Ni can be both divalent and trivalent, preferably Ni is divalent. Preferably catalyst B comprises Mg, Al, Cu and Ni.
In another embodiment of the first aspect of the present invention, if catalyst B only has Ni, the concentration of Ni is between 0.1% to 10% by weight with respect to the total of catalyst B. In another embodiment of the first aspect of the In the present invention, if the catalyst has only Cu, the concentration of Cu is between 0.1% to 10% by weight with respect to the total weight of catalyst B. In another embodiment of the first aspect of the present invention, the sum of the Cu and Ni concentrations are between 0.2% to 10% by weight with respect to the total of catalyst B. These percentages are based on the weight of Cu and / or Ni, not on the weight of equivalent oxides.
In an embodiment of the first aspect of the present invention, the molar ratio (Mg + Cu + Ni / Al) is between 1 and 6, preferably between 2 and 5.
Preferably, 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, ptoluenesulfonate, phenoxide , alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one compound of M3 and at least one compound of M4. This anion can be introduced between the sheets of the resulting hydrotalcite. In order to obtain anion solutions, sodium and / or potassium salts thereof can be used. Preferably, 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. In addition, in order to regulate the pH, sodium and / or potassium hydroxide are preferably used.
Preferably, before the precipitation of said compounds, there is dissolution of at least one compound of M3 and at least one compound of M4. Soluble M3 and M4 compounds are understood to mean any salt which, when contacted with a solvent, dissociates, preferably in a polar solvent, more preferably water. Examples of soluble M3 and M4 compounds may be nitrates, halides, sulfates, carboxylates and, in general, oxoacids comprising M3 or M4; preferably, the soluble M3 and M4 compounds are nitrates.
The gels resulting from the co-precipitation as described above are filtered, washed with water and dried properly. The presence of a hydrotalcite-like structure can be corroborated by means of X-ray diffraction analysis (XRD), while the composition (quantity and type of constituent) of the hydrotalcites or the corresponding mixed oxides obtained by thermal decomposition of the hydrotalcites above These can be determined by means of mass spectrometry with inductive coupling plasma (ICP-MS) and chemical analysis, among others.
In another embodiment of the first aspect of the present invention, the weight ratio of catalysts A and B is between 1:10 to 10: 1, preferably it is 1: 5 to 5: 1, and more preferably it is 1: 1 .
In another embodiment of the first aspect of the present invention, the thermal decomposition of the HTA and HTB hydrotalcites is carried out by calcination under an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging between 250 ° C and 650 ° C, preferably between 350 ° C and 550 ° C. The thermal decomposition of hydrotalcites is preferably performed over a range of 0.5 to 48 hours, preferably between 1 and 24 hours. This procedure can be carried out by heating the hydrotalcites 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.
Examples of non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia. Preferably, 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.
In another embodiment of the first aspect of the present invention, the noble metal of catalyst A is added to the metal oxide by wet impregnation, impregnation at incipient volume or deposition-precipitation, preferably the noble metal is added to the metal oxide by wet impregnation, impregnation to incipient volume or deposition-precipitation, more preferably by impregnation to 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.
In another embodiment of the first aspect of the present invention, the noble metal of catalyst A comprises Pd, preferably the noble metal is Pd. The best yields for 1-octanol have been obtained when calcined hydrotalcites containing Ga are impregnated with Pd.
In another embodiment of the first aspect of the present invention, the concentration of the noble metal in catalyst A ranges from 0.001% to 10% by weight with respect to total catalyst A, preferably between 0.01% and 5%.
In another embodiment of the first aspect of the present invention, catalyst A is obtained by a process comprising the following steps:
a) total or partial thermal decomposition of an HTA hydrotalcite with the formula
[M11- (x + y) M2y M5x (OH) 2] [QAm- (x + y) /m.nH2O], where:
M1, M2 and M5 have been defined above, preferably M1 is Mg, M5 is Al; QA 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), preferably CO32-, HCO3-, O2 and OH-;x is a value between 0 and 0.5; and is a value between 0.00001 and 0.49; m is an integerbetween 1 and 4; and n is greater than 0, preferably n is a value between 1 and 100, and morepreferably between 1 and 20;b) addition to the metal oxide obtained in step a) of:a noble metal selected from Pd, Pt, Ru, Rh, Re and any of its mixtures,preferably Pd;Y
Catalyst B is obtained by a process comprising a step ofTotal or partial thermal decomposition of an HTB hydrotalcite with the formula:[M3 (1-z) M4z (OH) 2] [QBp- (z / n) .rH2O], in which:M3 and M4 have been defined above, preferably M3 is a divalent metalselected from Mg, Cu, Ni and any of its mixtures, M4 is a metaltrivalent selected from among Al, Ni and any of their mixtures;
QB is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide,nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, ptoluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate,
-
hexacyanoferrate (III) and hexacyanoferrate (II), preferably CO32-, HCO3-, O2 and OH-; z is a value greater than 0 and less than 1, preferably z is a value between 0.1 and 0.8; p is an integer between 1 and 4; and r is greater than 0, preferably r is a value between 1 and 100, and more preferably between 1 and 20.
With respect to the anion, QB is preferably at least one anion selected from the list comprising CO32-, HCO3-, O2-, OH-, Cl-, NO32-, Cl-, F-, Br-, I-, ClO4- , CH3COO-,
-
C6H5COO-y SO42-; even more preferably, CO32-, HCO3-, O2 and OH-.
In another embodiment of the first aspect of the present invention, after the addition of the noble metal of catalyst A, there is a calcination step. 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 HTA 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. Examples of oxidizing gases may include air and oxygen. Examples of non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia. Preferably, 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.
In another embodiment of the first aspect of the present invention, after the addition of the noble metal of catalyst A, there is a calcination stage and a reduction stage subsequent to said calcination.
In a preferred embodiment of the first aspect of the present invention, the process of the invention as described above further comprises a step of reduction after calcination after the addition of the noble metal of catalyst A.
In another preferred embodiment of the first aspect of the present invention, after the addition of noble metal of catalyst A, there is a calcination stage of catalysts A and B, and a reduction stage after calcination of catalysts A and B.
During the reduction, 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 H2 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. Preferably, the reduction can be carried out at a stage prior to the introduction of the catalyst into the catalytic reactor or it can take place immediately before the stage of contact with the reagent, that is to say with ethanol and hexanol, within the same reactor.
In another preferred embodiment of the first aspect of the invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out in a reactor selected from the list comprising discontinuous reactor, continuous stirred tank reactor, continuous reactor of fixed bed and continuous fluidized bed reactor, preferably a discontinuous reactor.
In the particular embodiment of the first aspect of the invention, the reactor is a discontinuous reactor, the contact between the reagent and the catalysts A and B is carried out at a temperature ranging between 50 ° C and 450 ° C, preferably between 130 ° C and 350 ° C . In this process, the weight ratio between the reagent and the catalysts is preferably between 2 and 200, preferably between 5 and 100. In addition, it is carried out during a time interval ranging from 2 minutes to 200 hours, preferably between 1 hour and 100 hours
In another embodiment of the first aspect of the present invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out at a pressure of up to 120 bar, preferably between 20 and 80 bar.
In another embodiment of the first aspect of the present invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out under an atmosphere of nitrogen, argon, hydrogen or any mixture thereof, preferably in a nitrogen atmosphere. and of hydrogen. Normally, higher selectivities are obtained at 1-octanol in the presence of hydrogen.
A second aspect of the present invention relates to the use of catalysts A and B, where catalyst A comprises:
i) a metal oxide comprising the following metals:M1 is a divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe,Ni, Ca and any of its mixtures,
M2 is trivalent Ga; Y
ii) a noble metal selected from Pd, Pt, Ru, Rh, Re and any of its mixtures;
and catalyst B comprises a metal oxide comprising the following
Metals: M3 is a divalent metal selected from Mg, Zn, Cu Co, Mn, Fe, Ni, Ca and any of its mixtures, M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any of its mixtures,
with the proviso that catalyst B comprises at least Cu, Ni or any combination thereof;
to get 1-octanol.
In an embodiment of the second aspect of the present invention, the metal oxide of catalyst A further comprises an M5 metal, where M5 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co and Ni, preferably M5 comprises Al, more preferably M5 is Al.
In another embodiment of the second aspect of the present invention, catalyst A is obtained by a process comprising the following steps:
a) total or partial thermal decomposition of an HTA hydrotalcite with the formula
[M11- (x + y) M2y M5x (OH) 2] [QAm- (x + y) /m.nH2O], where:
M1, M2 and M5 have been defined above,QA 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 between 0 and 0.5; and is a value between 0.00001 and 0.49; m is an integerbetween 1 and 4; and n is greater than 0, preferably n is a value between 1 and 100, and morepreferably between 1 and 20.b) addition to the metal oxide obtained in step a) of:a noble metal selected from Pd, Pt, Ru, Rh, Re and any of its mixtures.
With respect to the anion, QA is preferably at least one anion selected from the list comprising CO32-, HCO3-, O2-, OH-, Cl-, NO32-, Cl-, F-, Br-, I-, ClO4- , CH3COO-,
-
C6H5COO-y SO42-; even more preferably, CO32-, HCO3-, O2 and OH-.
In another embodiment of the second aspect of the present invention, the HTA hydrotalcite is obtained by co-precipitation of compounds of M1, M2 and M5.
In another embodiment of the second aspect of the present invention, M1 is a divalent metal selected from Mg, Ca and any of its mixtures, preferably M1 is Mg.
Preferably, 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, ptoluenesulfonate, phenoxide , alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one compound of M1, at least one compound of M2 and at least one compound of M5. This anion can be introduced between the sheets of the resulting hydrotalcite. In order to obtain anion solutions, sodium and / or potassium salts thereof can be used. Preferably, 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. In addition, in order to regulate the pH, sodium and / or potassium hydroxide are preferably used.
Preferably, before the precipitation of said compounds, there is dissolution of at least one compound of M1, at least one compound of M2 and at least one compound of M5. By compounds of soluble M1, M2 and M5 it is understood that
they mean any salt that, when contacted with a solvent, dissociates,preferably in a polar solvent, more preferably water. Examples ofSoluble M1, M2 and M5 compounds can be nitrates, halides, sulfates,carboxylates and, in general, oxoacids comprising M1, M2 or M5;preferably, the soluble M1, M2 and M5 compounds are nitrates.
In another embodiment of the second aspect of the present invention, catalyst B isobtained by a procedure comprising a decomposition stageTotal or partial thermal of an HTB hydrotalcite with the formula:[M3 (1-z) M4z (OH) 2] [QBp- (z / n) .rH2O], in which:M3 and M4 have been defined above,QB is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide,
nitrate, perchlorate, chlorate,baking soda,acetate, benzoate,methanesulfonate,p
toluenesulfonate, phenoxide,alkoxide,carbonate,sulfate,terephthalate,phosphate,
hexacyanoferrate (III) and hexacyanoferrate (II),
z is a value greater than 0 and less than 1, preferably z is a value between 0.1 and 0.8; p is an integer between 1 and 4; and r is greater than 0, preferably r is a value between 1 and 100, and more preferably between 1 and 20.
With respect to the anion, QB is preferably at least one anion selected from the list comprising CO32-, HCO3-, O2-, OH-, Cl-, NO32-, Cl-, F-, Br-, I-, ClO4- , CH3COO-,
-
C6H5COO-y SO42-; even more preferably, CO32-, HCO3-, O2 and OH-.
In another embodiment of the second aspect of the present invention, HTB hydrotalcite is obtained by co-precipitation of compounds of M3 and M4.
In another embodiment of the second aspect of the present invention, M3 is a divalent metal selected from Mg, Ca, Cu, Ni and any of its mixtures, preferably M3 is a divalent metal selected from Mg, Cu, Ni and any of its mixtures
In another embodiment of the second aspect of the present invention, M4 is a trivalent metal selected from Al, Ni and any of its mixtures. More preferably M4 is Al.
In another embodiment of the second aspect of the present invention, catalyst B comprises Cu and Ni. The Ni can be both divalent and trivalent, preferably Ni is divalent. Preferably catalyst B comprises Mg, Al, Cu and Ni.
In another embodiment of the second aspect of the present invention, if catalyst B only has Ni, the concentration of Ni is between 0.1% to 10% by weight with respect to the total of catalyst B. In another embodiment of the second aspect of the In the present invention, if the catalyst has only Cu, the concentration of Cu is between 0.1% to 10% by weight with respect to the total weight of catalyst B. In another embodiment of the second aspect of the present invention, the sum of the Cu and Ni concentrations are between 0.2% to 10% by weight with respect to the total of catalyst B. These percentages are based on the weight of Cu and / or Ni, not on the weight of equivalent oxides.
In an embodiment of the second aspect of the present invention, the molar ratio (Mg + Cu + Ni / Al) is between 1 and 6, preferably between 2 and 5.
Preferably, 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, ptoluenesulfonate, phenoxide , alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate (III) and hexacyanoferrate (II) at a solution of at least one compound of M3 and at least one compound of M4. This anion can be introduced between the sheets of the resulting hydrotalcite. In order to obtain anion solutions, sodium and / or potassium salts thereof can be used. Preferably, 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. In addition, in order to regulate the pH, sodium and / or potassium hydroxide are preferably used.
Preferably, before the precipitation of said compounds, there is dissolution of at least one compound of M3 and at least one compound of M4. Soluble M3 and M4 compounds are understood to mean any salt which, when contacted with a solvent, dissociates, preferably in a polar solvent, more preferably water. Examples of soluble M3 and M4 compounds may be nitrates, halides, sulfates, carboxylates and, in general, oxoacids comprising M3 or M4; preferably, the soluble M3 and M4 compounds are nitrates.
In another embodiment of the second aspect of the present invention, the weight ratio of catalysts A and B is between 1:10 to 10: 1, preferably 1: 5 to 5: 1, and more preferably 1: 1 .
In another embodiment of the second aspect of the present invention, the thermal decomposition of the HTA and HTB hydrotalcites is carried out by calcination under an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging between 250 ° C and 650 ° C, preferably between 350 ° C and 550 ° C. The thermal decomposition of hydrotalcites is preferably performed over a range of 0.5 to 48 hours, preferably between 1 and 24 hours. This procedure can be carried out by heating the hydrotalcites 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. Examples of non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia. Preferably, 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.
In another embodiment of the second aspect of the present invention, the noble metal of catalyst A is added to the metal oxide by wet impregnation, impregnation at incipient volume or deposition-precipitation, preferably the noble metal is added to the metal oxide by wet impregnation, impregnation to incipient volume or deposition-precipitation, more preferably by impregnation to 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.
In another embodiment of the second aspect of the present invention, the noble metal of catalyst A comprises Pd, preferably the noble metal is Pd. The best yields for 1-octanol have been obtained when calcined hydrotalcites containing Ga are impregnated with Pd.
In another embodiment of the second aspect of the present invention, the concentration of the noble metal in catalyst A ranges from 0.001% to 10% by weight with respect to total catalyst A, preferably between 0.01% and 5%.
In another embodiment of the second aspect of the present invention, after the addition of the noble metal of catalyst A, there is a calcination step. 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 HTA 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. Examples of oxidizing gases may include air and oxygen. Examples of non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia. Preferably, 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.
In a preferred embodiment of the second aspect of the present invention, the process of the invention as described above further comprises a step of reduction after calcination after the addition of the noble metal of catalyst A. During the reduction, the noble metal, which acts as one of the main active sites in the procedure, is reduced. This reduction step is preferably carried out in an atmosphere of H2 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. Preferably, the reduction takes place immediately before the step of contact with the reagent, that is to say with ethanol and hexanol.
In another embodiment of the second aspect of the present invention, after the addition of the noble metal of catalyst A, there is a calcination stage and a reduction stage subsequent to said calcination.
In another preferred embodiment of the second aspect of the invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out in a reactor selected from the list comprising discontinuous reactor, continuous stirred tank reactor, continuous reactor of fixed bed and continuous fluidized bed reactor, preferably a discontinuous reactor.
In the particular embodiment of the second aspect of the invention, the reactor is a discontinuous reactor, the contact between the reagent and the catalysts A and B is carried out at a temperature ranging between 50 ° C and 450 ° C, preferably between 130 ° C and 350 ° C . In this process, the weight ratio between the reagent and the catalysts is preferably between 2 and 200, preferably between 5 and 100. In addition, it is carried out during a time interval ranging from 2 minutes to 200 hours, preferably between 1 hour and 100 hours
In another embodiment of the second aspect of the present invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out at a pressure of up to 120 bar, preferably between 20 and 80 bar.
In another embodiment of the second aspect of the present invention, the contact between ethanol, n-hexanol and catalysts A and B is carried out under an atmosphere of nitrogen, argon, hydrogen or any mixture thereof, preferably in a nitrogen atmosphere. and of hydrogen. Normally, higher selectivities are obtained at 1-octanol in the presence of hydrogen.
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 "comprise" 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 examples, drawings, are provided by way of illustration and are not intended to be limiting of the present invention. DESCRIPTION OF THE DRAWINGS
Fig. 1. Shows a comparative graph of the catalytic activities (conversions of EtOH and HexOH and yields to n-ButOH, 1-OctOH and the sum of C4 + OH) of catalysts based on different mixed oxides derived from hydrotalcites (Examples 3 a 7) in an atmosphere of N2. %: conversion or yield percentage, as indicated on the x axis; CEtOH: conversion of ethanol, CHexOH: conversion of n-hexanol, rButOH: yield to n-ButOH; rOctOH: yield at 1-octanol; rC4 + OH: yield to C4 + alcohols; E3, example 3 (0.63% Pd / 0.16% Ga-HT-1); E4, example 4 (0.24% Pd / 0.29% Ga-HT-4); E5, example 5 (2.5% Cu / HT-4); E6, example 6 (2.5% Ni-HT4 ); E7, example 7 (0.77% Cu-0.92% Ni-HT-4).
Fig. 2. Shows a comparative graph of the catalytic activities (conversions of EtOH and HexOH and yields to n-ButOH, 1-OctOH and the sum of C4 + OH) of physical mixtures of catalysts based on different mixed oxides derived from hydrotalcites ( Examples 3 + 7, 4 + 7, 4 + 5 and 4 + 6) in an atmosphere of N2. %: conversion or yield percentage, as indicated on the x axis; CEtOH: conversion of ethanol, CHexOH: conversion of n-hexanol, rButOH: yield to n-ButOH; rOctOH: yield at 1-octanol; rC4 + OH: yield to C4 + alcohols; E3, example 3 (0.63% Pd / 0.16% Ga-HT-1); E4, example 4 (0.24% Pd / 0.29% Ga-HT-4); E5, example 5 (2.5% Cu / HT-4); E6, example 6 (2.5% Ni-HT -4); E7, example 7 (0.77% Cu-0.92% Ni-HT4).
Fig. 3. Shows a comparative graph of the catalytic activities (yields at 1-OctOH and the sum of C4 + OH) of physical mixtures in different proportions or ratios of the catalysts of Examples 3 and 7 in an N2 atmosphere. %: percentage yield; r (OctOH): yield in 1-octanol; r (∑C4 + OH): yield at the sum of C4 + OH (in points); g cat; amount in grams of catalyst from Example 3 (0.63% Pd / 0.16% Ga-HT-1) + amount in grams of catalyst from Example 7 (0.77% Cu-0.92% Ni-HT-4 ). Examples
Next, the present inventors will illustrate the invention by means of tests carried out by the inventors, which demonstrate the efficacy of hydrotalcite derived catalysts comprising gallium in their structure used in conjunction with hydrotalcite derived catalysts comprising Cu, Ni or any of their mixtures in obtaining 1-octanol.
Example 1. Synthesis of catalyst 0.16% Ga-HT-1
It was prepared by means of a standard co-precipitation procedure using two solutions. The first solution contained 18.50 g of Mg (NO3) 2 · 6H2O, 26.75 g of Al (NO3) 3 · 9H2O and 0.06 g of Ga (NO3) 3 · 9H2O, dissolved in 50.61 g of Milli-Q water, with a molar concentration of (Al + Mg + Ga) of 1.5. The second solution contained 14.40 g of NaOH and 10.40 g of Na2CO3 in 70.83 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Ga species, and to fix the pH of the total mixture at ≈ 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-1) obtained was calcined in air at 450 ° C for 3-4 h, to obtain a mixed oxide with a molar ratio of Mg / Al ≈ 1.48, a Ga content of 0.16% in weight (measured by chemical analysis and ICP-MS) and a surface area (BET method) of 319 m2 / g.
Example 2. 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 (NO3) 2 · 6H2O, 10.90 g of Al (NO3) 3 · 9H2O and 0.06 g of Ga (NO3) 3 · 9H2O, 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 Na2CO3 in 72.60 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Ga species, and to fix the pH of the total mixture at ≈ 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 / Al ≈ 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 m2 / g.
Example 3. Synthesis of catalyst 0.63% Pd / 0.16% Ga-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 Ga-HT-1 material was carried out by means of the impregnation process incipient humidity, using, in this case, 0.025 g of Pd (NH3) 4Cl2 · 6H2O dissolved in 2,000 g of Milli-Q water, to impregnate 1.003 g of 0.16% of Ga-HT-1. 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 3-4 h, and subsequently reduced to 350 ° C in an H2 atmosphere for 3 h before the catalytic application thereof. The resulting Pd / 0.16% Ga-HT-1 material, characterized by chemical analysis and ICP-MS, contained ≈ 0.63% by weight of Pd.
Example 4. Synthesis of catalyst 0.24% Pd / 0.29% Ga-HT-4
It was prepared from the material prepared as described in Example 2, in which the incorporation of Pd (0.3% by weight, theoretical) in the Ga-HT-4 material was carried out by means of the impregnation process incipient humidity, using, in this case, 0.008 g of Pd (NH3) 4Cl2 · 6H2O dissolved in 1,800 g of Milli-Q water, to impregnate 1,011 g of 0.29% Ga-HT-4. 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 3-4 h, and subsequently reduced to 350 ° C in an H2 atmosphere for 3 h before the catalytic application thereof. The resulting Pd / 0.29% Ga-HT-4 material, characterized by chemical analysis and ICP-MS, contained ≈ 0.24% by weight of Pd.
Example 5. Synthesis of catalyst 2.5% Cu-HT-4
It was prepared by means of a standard co-precipitation procedure using two solutions. The first solution contained 30.01 g of Mg (NO3) 2 · 6H2O, 10.16 g of Al (NO3) 3 · 9H2O and 0.58 g of Cu (NO3) 2 · 2.5H2O, dissolved in 57.01 g of Milli-Q water, with a molar concentration of (Al + Mg + Cu) of 1.5. The second solution contained 12.80 g of NaOH and 10.37 g of Na2CO3 in 74.58 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to fix the pH of the total mixture at ≈ 13. Both solutions (total flow rate = 30 ml / h for approximately 4 h) were added to a vessel under vigorous stirring at room temperature. The gel formed was aged at room temperature for 12 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 (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 / Al ,83.88, a Cu content of 2.5% by weight, characterized by chemical analysis and ICP-MS and a surface area (BET method) of 191 m2 / g.
Example 6. Synthesis of catalyst 2.5% Ni-HT-4
It was prepared by means of a standard co-precipitation procedure using two solutions. The first solution contained 29.29 g of Mg (NO3) 2 · 6H2O, 10.94 g of Al (NO3) 3 · 9H2O and 0.78 g of Ni (NO3) 2 · 6H2O, dissolved in 56.29 g of Milli-Q water, with a molar concentration of (Al + Mg + Cu) of 1.5. The second solution contained 12.88 g of NaOH and 10.38 g of Na2CO3 in 74.12 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to fix the pH of the total mixture at ≈ 13. Both solutions (total flow rate = 30 ml / h for approximately 4 h) were added to a vessel under vigorous stirring at room temperature. The gel formed was aged at room temperature for 12 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 (Ni-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 / Al ≈ 3.58, a Ni content of 2.5% by weight, characterized by chemical analysis and ICP-MS and a surface area (BET method) of 190 m2 / g.
Example 7. Catalyst synthesis 0.77% Cu-0.92% Ni-HT-4
It was prepared by means of a standard co-precipitation procedure using two solutions. The first solution contained 29.25 g of Mg (NO3) 2 · 6H2O, 10.86 g of Al (NO3) 3 · 9H2O, 0.28 g of Cu (NO3) 2 · 2.5H2O and 0.39 g of Ni (NO3) 2 · 6H2O, dissolved in 55.69 g of Milli-Q water, with a molar concentration of (Al + Mg + Cu) of 1.5. The second solution contained 12.82 g of NaOH and 10.31 g of Na2CO3 in 72.70 g of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Cu species, and to fix the pH of the total mixture at ≈ 13. Both solutions (total flow rate = 30 ml / h for approximately 4 h) were added 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 (Cu-Ni-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 / Al≈3.99, Cu and Ni contents of 0 , 77 and 0.92% by weight, respectively, characterized by chemical analysis and ICP-MS and a surface area (BET method) of 208 m2 / g.
Example 8. Comparative catalytic activity of the catalysts of Examples 3 to 7 under N2 atmosphere
1750 mg of ethanol, 1790 mg of n-hexanol and 350 mg of one of the catalytic materials of Examples 3 to 7 (or physical mixtures thereof) were introduced into a 12 ml stainless steel autoclave reactor, with a reinforced interior lined with PEEK (polyether-ethyl ketone) and a magnetic stirrer. The reactor was closed tightly, with the system having a connector to a pressure gauge (pressure gauge), another connector for gas loading and a third outlet that made it possible to take samples at different time intervals. The reactor was initially pressurized with 24 bar of N2, and heated at 250 ° C under continuous stirring, until the total system pressure reached approx. 35-40 bar (reaction time = 0). Liquid samples (≈ 50-100 μl) 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 gas chromatography on a GC-3900 Varian equipped with an FID detector and a TRB-624 capillary column. 60 m
The conversion of ethanol, in mole percent (Conv. Of EtOH), was calculated from the composition of the mixture obtained:
(initial moles of ethanol - final moles of ethanol) / (initial moles of ethanol * 100)
The conversion of n-hexanol, in mole percent (Conv. Of n-HexOH), was calculated from the composition of the mixture obtained:
(initial moles of n-hexanol - final moles of n-hexanol) / (initial moles of nhexanol * 100)
The total yield of n-butanol, in mole percent (yield of n-ButOH), was calculated as:
(moles of n-butanol / moles of total products) * Conv. of EtOH / 100
The total yield of 1-octanol, in mole percent (Yield of 1-OctOH) was calculated as:
(moles of 1-octanol / moles of total products) * Conv. of EtOH / 100
The total yield of linear C4 + alcohols, in mole percent (yield of linear C4 + OH), which include n-butanol and 1-octanol, of course, was calculated as: (moles of linear C4 + / moles of total products) * Conv . of EtOH / 100
5 The total yield of branched C4 + alcohols, in mole percent (Yield of branched C4 + OH), was calculated as: (moles of branched C4 + / moles of total products) * Conv. EtOH / 100 10 Thus, the following results were obtained:
Ex. CatalystT (h)Conv. EtOHConv. n-HexOHRdto. n-ButOHRdto. 1-OctOHRdto. C4 + OH
Lin. RAM.
3 0.63% Pd / 0.16% Ga-HT-1552.315.622.17.6030.32.6
4 0.24% Pd / 0.29% Ga-HT-4541.120.222.06.9030.02.6
5 2.5% Cu / HT-4 549.819.222.56.6429.10.9
6 2.5% Ni-HT-4542.116.39.14.3013.70.4
7 0.77% Cu-0.92% Ni-HT-4551.416.226.88.0036.82.9
3+ 7 0.63% Pd / 0.16% Ga-HT-1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)549.217.326.310.8239.03.6
4+ 5 0.24% Pd / 0.29% Ga-HT-4 (0.20 g) + 2.5% Cu-HT-4 (0.15 g)529.59.415.07.7124.01.9
4+ 6 0.24% Pd / 0.29% Ga-HT-4 (0.20 g) + 2.5% Ni-HT-4 (0.15 g)528.413.418.05.3323.30.7
4+ 7 0.24% Pd / 0.29% Ga-HT-4 (0.20 g) + 0.77% Cu0.92% Ni-HT-4 (0.15 g)539.710.123.08.5631.62.1
Table 1. Catalytic activity of different mixed metal oxides and physical mixtures thereof in the transformation of ethanol + n-hexanol under nitrogen atmosphere.
Comparison of the results of the physical mixtures of the catalysts of Examples 3 + 7, 4 + 5, 4 + 6, and 4 + 7 show that the best results are obtained with the mixtures of Examples 3 + 7 and 4+ 7. Moreover, these catalyst mixtures show superior results than those obtained with the individual catalysts, which implies that there is a synergistic and not only additive effect with the use of the physical mixtures of the catalysts. In particular, the combination of the catalyst comprising Ga (Example 3) with the catalyst of Example 7 (Cu-Ni-HT-4), which results in higher yields in 1-octanol and, in general, higher yield in C4 + alcohols, stands out that the respective catalysts used individually, as seen in Figures 1 and 2.
Example 9. Comparative catalytic activity of the catalysts of Examples 3 and 7 and of physical mixtures thereof under N2 atmosphere
1750 mg of ethanol, 1790 mg of n-hexanol and 350 mg of one of the catalytic materials of Examples 3 and 7 and physical mixtures of different proportions thereof (always adding a total of 350 mg) were introduced into a reactor 12 ml stainless steel autoclave, with a reinforced interior lined with PEEK (polyether-ethyl ketone) and a magnetic stirrer. The reactor was closed tightly, with the system having a connector to a pressure gauge (pressure gauge), another connector for gas loading and a third outlet that made it possible to take samples at different time intervals. The reactor was initially pressurized with 20 bar of N2, and heated at 250 ° C under continuous stirring, until the total system pressure reached approx. 35-40 bar (reaction time = 0). Liquid samples (≈ 50-100 μl) 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 gas chromatography on a GC-3900 Varian equipped with an FID detector and a TRB-624 capillary column. 60 m
The conversion of ethanol, in mole percent (Conv. Of EtOH), was calculated from the composition of the mixture obtained:
(initial moles of ethanol - final moles of ethanol) / (initial moles of ethanol * 100) The conversion of n-hexanol, in mole percent (Conv. of n-HexOH), was calculated from the composition of the mixture obtained : (initial moles of n-hexanol - final moles of n-hexanol) / (initial moles of n
5 hexanol * 100) The total yield of n-butanol, in mole percent (Rd. Of n-ButOH), was calculated as:
10 (moles of n-butanol / moles of total products) * Conv. of EtOH / 100 The total yield of 1-octanol, in mole percent (Rd. of 1-OctOH) was calculated as: 15 (moles of 1-octanol / moles of total products) * Conv. of EtOH / 100 The total yield of linear C4 + alcohols, in mole percent (Rd. of linear C4 + OH), which include n-butanol and 1-octanol, of course, was calculated as: 20 (linear C4 + moles / moles) of total products) * Conv. of EtOH / 100 The total yield of branched C4 + alcohols, in mole percent (Rd. of branched C4 + OH), was calculated as: 25 (moles of branched C4 + / moles of total products) * Conv. of EtOH / 100 Thus, the following results were obtained:
Ex. CatalystTConv.Conv. n-Rdto. n-Rdto.Rdto. C4 + OH
(h) EtOHHexButOH1-OctOHLin.RAM.
3 0.63% Pd / 0.16% Ga-HT-1552.315.622.17.6030.32.6
3 + 7 0.63% Pd / 0.16% Ga-HT-1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)549.217.326.310.8239.03.6
Ex. CatalystTConv.Conv. n-Rdto. n-Rdto.Rdto. C4 + OH
(h) EtOHHexButOH1-OctOHLin.RAM.
3 + 7 0.63% Pd / 0.16% Ga-HT-1 (0.20 g) + 0.77% Cu0.92% Ni-HT-4 (0.15 g)558.019.926.013.542.33.5
3 + 7 0.63% Pd / 0.16% Ga-HT-1 (0.10 g) + 0.77% Cu0.92% Ni-HT-4 (0.25 g)551.714.625.211.1738.53.5
7 0.77% Cu-0.92% Ni-HT-4551.416.226.88.0036.82.9
Table 2. Catalytic activity of the catalysts 0.63% Pd / 0.16% Ga-HT-1 and 0.77% Cu0.92% Ni-HT-4 and of physical mixtures of different proportions thereof in the transformation of ethanol + n-hexanol under nitrogen atmosphere.
5 If the physical mixtures are compared in different proportions of the catalysts of Examples 3 and 7, the results show that a synergistic and not merely additive effect is observed with the use of the catalyst mixture, and that there is also an optimum in the proportions of each of the catalysts. So, the elders
10 yields in 1-octanol and, in general, higher yield in C4 + alcohols are observed with the ratio in the mixture of 200 mg of the catalyst of Example 3 (Pd / Ga-HT-1) and 150 mg of the catalyst of Example 7 ( Cu-Ni-HT-4), as seen in Figure 3. This demonstrates not only the synergistic effect of the catalyst mixture with respect to the respective individual catalysts, but also that
Both the type of catalyst and its proportions are not trivial, nor can they be calculated or pre-established in advance based on the data obtained with each individual catalyst.
Example 10. Comparative catalytic activity of the catalysts of the Examples 3, 5-7 and the physical mixture of the catalysts of Examples 3 and 7 under H2 (or N2) atmosphere with ethanol alone (without n-hexanol)
3500 mg of ethanol and 350 mg of one of the catalytic materials of Examples 3 and 5 to 7 were introduced, as well as the mixture of Examples 3 (200 mg) and 7 (150
25 mg) in a 12 ml stainless steel autoclave reactor, with a reinforced interior
PEEK coated (polyether ethyl ketone) and a magnetic stirrer. The reactor was closed tightly, with the system having a connector to a pressure gauge (pressure gauge), another connector for gas loading and a third outlet that made it possible to take samples at different time intervals. The reactor was initially pressurized 5 with 10 bar of H2 and subsequently carried up to 24 bar with the addition of N2, and heated at 200 ° C under continuous stirring, until the total system pressure reached approx. 30 bar (reaction time = 0). Liquid samples (≈ 50-100 μl) 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
10 chlorobenzene in acetonitrile, and analyzed by gas chromatography on a GC-3900 Varian equipped with an FID detector and a 60 m TRB-624 capillary column.
The following results were obtained: 15
Ex. CatalystT (h)Conv. EtOHRdto. n-ButOHRdto. n-HexOHRdto. 1-OctOHRdto. C4 + OH
Lin. RAM.
3 0.63% Pd / 0.16% Ga-HT-1511.28.80.00.08.80.0
5 2.5% Cu / HT-4 57.75.70.80.06.50.0
5 2.5% Cu / HT-4 (Without H2) 59.44.71.50.06.20.0
6 2.5% Ni-HT-456.94.80.70.05.50.0
6 2.5% Ni-HT-4 (Without H2)57.82.51.00.03.50.0
7 0.77% Cu-0.92% Ni-HT-4510.78.40.20.08.60.0
3 + 7 0.63% Pd / 0.16% Ga-HT-1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)513.24.97.50.3312.70.1
Table 3. Catalytic activity of the catalysts of Examples 3, 5-7 and the mixture of the catalysts of Examples 3 and 7 in the transformation of ethanol under hydrogen (or nitrogen) atmosphere.
The rest of the products up to 100% mainly comprise aldehydes (ethanal, butanal, hexanal, ethylacetate and diethoxyethane).
The results obtained with the physical mixture of the catalysts of Examples 3 and 7 clearly show that it is possible to obtain high yields of 1-hexanol (and the sum of 1-butanol + 1-hexanol) using only ethanol as the starting reagent. However, these results also show that both the individual catalysts and the physical mixture of the same object of the present invention when reacting with ethanol as a reagent do not produce 1-octanol in a high percentage. Therefore, it is shown that n-hexanol and ethanol are required to obtain high yields of 1-octanol.
Example 11. Comparative catalytic activity of the catalysts of Examples 3, 5, 7 and of the physical mixture of the catalysts of Examples 3 and 7 under H2 atmosphere with n-butanol as raw material (neither ethanol nor n-hexanol)
3,500 mg of n-butanol and 350 mg of one of the catalytic materials of Examples 3, 5 and 7 were introduced, as well as the mixture of Examples 3 (200 mg) and 7 (150 mg) in an autoclave reactor 12 ml stainless steel, with a reinforced interior lined with PEEK (polyether-ethyl ketone) and a magnetic stirrer. The reactor was closed tightly, with the system having a connector to a pressure gauge (pressure gauge), another connector for gas loading and a third outlet that made it possible to take samples at different time intervals. The reactor was initially pressurized with 10 bar of H2 and subsequently carried up to 24 bar with the addition of N2, and heated at 250 ° C under continuous stirring, until the total system pressure reached approx. 40 bar (reaction time = 0). Liquid samples (≈ 50-100 μl) 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 gas chromatography on a GC-3900 Varian equipped with an FID detector and a TRB-624 capillary column. 60 m
The following results were obtained: Table 4. Catalytic activity of the catalysts of Examples 3, 7 and of physical mixtures of Examples 3 and 7 in the transformation of n-butanol under hydrogen atmosphere.
Ex. CatalystT (h)Conv. n-ButOHRdto. butanalRdto. aldehydesRdto.1-OctOHRdto. C4 + OH
Lin RAM
3 0.63% Pd / 0.16% Ga-HT-1522.22.51.21.111.93.3
7 0.77% Cu-0.92% Ni-HT-4523.14.12.10.510.23.5
3 + 7 0.63% Pd / 0.16% Ga-HT-1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)527.92.81.81.913.25.4
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.
These results show that both the individual catalysts and the mixture
The physics of catalysts object of the present invention when reacting with nbutanol as a reagent does not produce 1-octanol in a high percentage. Therefore, it is shown that n-hexanol and ethanol are required to obtain high yields of 1octanol.

权利要求:
Claims (30)
[1]
1. Process for obtaining 1-octanol comprising a step of contact between ethanol, n-hexanol and two catalysts A and B, where catalyst A comprises:
i) a metal oxide comprising the following metals:M1 is a divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe,Ni, Ca and any of its mixtures,M2 is trivalent Ga; Y
ii) a noble metal selected from Pd, Pt, Ru, Rh, Re and any oftheir mixtures;
and catalyst B comprises a metal oxide comprising the following
Metals: M3 is a divalent metal selected from Mg, Zn, Cu Co, Mn, Fe, Ni, Ca and any of its mixtures, M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any of its mixtures,
with the proviso that catalyst B comprises at least Cu, Ni or any combination thereof, wherein Ni comprises divalent, trivalent Ni or any of its mixtures.
[2]
2. Method for obtaining according to the preceding claim, wherein the metal oxide of catalyst A further comprises an M5 metal, where M5 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co and Ni.
[3]
3. The process according to any of the preceding claims, wherein catalyst A is obtained by a process comprising the following steps:
a) total or partial thermal decomposition of an HTA hydrotalcite with the formula
[M11- (x + y) M2y M5x (OH) 2] [QAm- (x + y) /m.nH2O], where:
M1 and M2 are defined in claim 1,M5 is defined in claim 2,QA 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 between 0 and 0.5; and is a value between 0.00001 and 0.49; m is an integerbetween 1 and 4; and n is greater than 0.b) addition to the metal oxide obtained in step a) of:a noble metal selected from Pd, Pt, Ru, Rh, Re and any of its mixtures.
[4]
Four. The method according to the preceding claim, wherein the HTA hydrotalcite isobtained by co-precipitation of compounds of M1, M2 and M5.
[5]
5. The method according to any of the preceding claims, wherein M1 isa divalent metal selected from Mg, Ca and any of its mixtures.
[6]
6. The process according to the preceding claim, wherein M1 is Mg.
[7]
7. The method according to any of the preceding claims, wherein M5comprises Al.
[8]
8. The method according to any of the preceding claims, wherein theCatalyst B is obtained by a process comprising a step ofTotal or partial thermal decomposition of an HTB hydrotalcite with the formula:[M3 (1-z) M4z (OH) 2] [QBp- (z / n) .rH2O], in which:M3 and M4 are defined in claim 1,QB is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide,nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, ptoluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate,hexacyanoferrate (III) and hexacyanoferrate (II),z is a value greater than 0 and less than 1; p is an integer between 1 and 4; and r is
greater than 0.
[9]
9. The process according to any of the preceding claims, wherein M3 is a divalent metal selected from Mg, Ca, Cu, Ni and any of its mixtures.
[10]
10. The process according to the preceding claim, wherein M3 is a divalent metal selected from Mg, Cu, Ni and any of its mixtures.
[11]
eleven. The process according to any of the preceding claims, wherein M4 is a trivalent metal selected from Al, Ni and any of its mixtures.
[12]
12. The method according to any of the preceding claims wherein M4 is Al.
[13]
13. The process according to any of the preceding claims, wherein catalyst B comprises Cu and Ni.
[14]
14. The process according to the preceding claim, wherein the sum of the concentrations of Cu and Ni is between 0.2% to 10% by weight with respect to the total of catalyst B.
[15]
fifteen. The method according to any of the preceding claims, wherein the molar ratio (Mg + Cu + Ni / Al) is between 1 and 6.
[16]
16. The process according to any of the preceding claims, wherein the weight ratio of catalysts A and B is between 1:10 to 10: 1.
[17]
17. The process according to any of the preceding claims, wherein the ratio of catalysts A and B is 1: 1.
[18]
18. The process according to any of claims 3 to 17, wherein the thermal decomposition of hydrotalcite HTA is carried out by calcination under an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature range between 250 ° C and 650 ° C, preferably between 350 ºC and 550 ºC.
[19]
19. The process according to any of claims 8 to 18, wherein the thermal decomposition of HTB hydrotalcite is carried out by calcination under an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature range between 250 ° C and 650 ° C, preferably between 350 ºC and 550 ºC.
[20]
twenty. The method according to any of claims 3 to 19, wherein QA is at
-
minus an anion selected from CO32-, HCO3-, O2 and OH-.
[21]
21. The method according to any of claims 8 to 20, wherein QB is at
-
minus an anion selected from CO32-, HCO3-, O2 and OH-.
[22]
22 The process according to any of the preceding claims, the noble metal is added to the metal oxide of catalyst A by wet impregnation, impregnation at incipient volume or deposition-precipitation.
[23]
2. 3. The process according to the preceding claim, wherein after the addition of the noble metal, a calcination stage and a reduction stage subsequent to said calcination are produced.
[24]
24. The process according to any of the preceding claims, wherein the contact between ethanol, n-hexanol and catalysts A and B is carried out at a pressure of up to 120 bar, preferably between 20 and 80 bar.
[25]
25. The process according to any of the preceding claims, wherein the contact between ethanol, n-hexanol and catalysts A and B is carried out at a temperature ranging from 50 ° C to 450 ° C.
[26]
26. The process according to any of the preceding claims, wherein the contact between ethanol, n-hexanol and catalysts A and B is carried out under an atmosphere of nitrogen, argon, hydrogen or any mixture thereof, preferably in an atmosphere of nitrogen and of hydrogen.
[27]
27. Use of catalysts A and B, where catalyst A comprises:
i) a metal oxide comprising the following metals:M1 is a divalent metal selected from Mg, Zn, Cu, Co, Mn, Fe,Ni, Ca and any of its mixtures,M2 is trivalent Ga; Y
ii) a noble metal selected from Pd, Pt, Ru, Rh, Re and any oftheir mixtures;
and catalyst B comprises a metal oxide comprising the following
Metals: M3 is a divalent metal selected from Mg, Zn, Cu Co, Mn, Fe, Ni, Ca and any of its mixtures, M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any of its mixtures,
with the proviso that catalyst B comprises at least Cu, Ni or any combination thereof;
to get 1-octanol.
[28]
28. Use according to the preceding claim wherein the metal oxide of catalyst A further comprises an M5 metal, where M5 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co and Ni.
[29]
29. Use according to any of claims 27 or 28, wherein the ratio of catalysts A and B is between 1:10 to 10: 1.
[30]
30 The process according to the preceding claim, wherein the ratio of catalysts A and B is 1: 1.
DRAWINGS
FIG. one
FIG. 2
FIG. 3

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同族专利:

公开号 | 公开日

EP3466913A4|2020-02-12|

WO2017203089A1|2017-11-30|

BR112018074365A2|2019-03-06|

US10538469B2|2020-01-21|

ES2647963B1|2018-10-03|

US20190300463A1|2019-10-03|

EP3466913A1|2019-04-10|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US7700810B2|2007-08-22|2010-04-20|E.I. Du Pont De Nemours And Company|Catalytic conversion of ethanol to a 1-butanol-containing reaction product using a thermally decomposed hydrotalcite catalyst|

US8071823B2|2008-01-28|2011-12-06|E.I. Du Pont De Nemours And Company|Catalytic conversion of ethanol and hydrogen to a 1-butanol-containing reaction product using a thermally decomposed hydrotalcite/metal carbonate|

US8071822B2|2008-01-28|2011-12-06|E.I. Du Pont De Nemours And Company|Catalytic conversion of ethanol and hydrogen to a 1-butanol-containing reaction product using a thermally decomposed hydrotalcite containing the anion of ethylenediaminetetraacetic acid|

US8318989B2|2008-12-22|2012-11-27|E I Du Pont De Nemours And Company|Process for producing guerbet alcohols using water tolerant basic catalysts|

CN101530802B|2009-04-16|2011-11-30|浙江大学|Bi-component supported catalyst of ethanol condensed n-butanol and a method of preparing thereof|

EP2679304A1|2012-06-29|2014-01-01|Abengoa Bioenergía Nuevas Tecnologías, S. A.|Process for obtaining higher alcohols in the presence of a gallium containing mixed oxide|

ES2570233B1|2014-11-14|2017-02-22|Abengoa Bioenergía Nuevas Tecnologías, S.A.|Procedure for obtaining 1-octanol|

ES2570231B1|2014-11-14|2017-04-19|Abengoa Bioenergia Nuevas Tecnologias, S.A.|PROCESS FOR THE PREPARATION OF HIGHER ALCOHOLS FROM ETHANOL AND N-HEXANOL BY GUERBET CONDENSATION|CN111514899A|2020-05-11|2020-08-11|云南大学|Catalyst for treating organic wastewater and preparation method thereof|

CN113145155A|2021-03-09|2021-07-23|广东工业大学|Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof|

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