METHOD FOR PRODUCING 1-OCTANOL

Abstract

The present invention relates to a method for producing 1-octanol comprising a contact step between ethanol, n-hexanol and two catalysts A and B, wherein catalyst A comprises a metal oxide comprising Ga and a noble metal and catalyst B comprises a metal oxide comprising Cu, Ni or any mixture thereof.

Claims

1. A method for producing 1-octanol comprising a contact step between ethanol, n-hexanol and two catalysts A and B, wherein 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 mixture thereof, M2 is trivalent Ga; and ii) a noble metal selected from Pd, Pt, Ru, Rh, Re and any mixture thereof; 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 mixture thereof, M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any mixture thereof, with the condition that catalyst B comprises at least Cu, Ni or any combination thereof, wherein the Ni comprises divalent or trivalent Ni or any mixture thereof.

2. The method according to claim 1, wherein the metal oxide of catalyst A further comprises an M5 metal, wherein M5 is at least one trivalent metal selected from Al, La, Fe, Cr, Mn, Co and Ni.

3. The method according to claim 2, wherein catalyst A is produced by means of a method comprising the following steps: a) total or partial thermal decomposition of a hydrotalcite HT.sub.A with the formula
[M1.sub.1(x+y)M2.sub.yM5.sub.x(OH).sub.2][Q.sub.A.sup.m.sub.(x+y)/m.nH.sub.2O], wherein: Q.sub.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 between 0 and 0.5; y is a value between 0.00001 and 0.49; m is an integer between 1 and 4; and n is greater than 0. b) addition to the metal oxide produced in step a) of: a noble metal selected from Pd, Pt, Ru, Rh, Re and any mixture thereof.

4. The method according to claim 3, wherein the hydrotalcite HT.sub.A is produced by the co-precipitation of M1, M2 and M5 compounds.

5. The method according to claim 1, wherein M1 is a divalent metal selected from Mg, Ca and any mixture thereof.

6. The method according to claim 5, wherein M1 is Mg.

7. The method according to claim 2, wherein M5 comprises Al.

8. The method according to claim 1, wherein catalyst B is produced by means of a method comprising a step of total or partial thermal decomposition of a hydrotalcite HT.sub.B with the formula:
[M3.sub.(1z)M4.sub.z(OH).sub.2][Q.sub.B.sup.p.sub.(z/n).rH.sub.2O], wherein: M3 is a divalent metal selected from Mg, Zn, Cu Co, Mn, Fe, Ni, Ca and any mixture thereof, and M4 is a trivalent metal selected from Al, La, Fe, Cr, Mn, Co, Ni and any mixture thereof, Q.sub.B 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), z is a value higher than 0 and lower than 1; p is an integer between 1 and 4; and r is higher than 0.

9. The method according to claim 8, wherein M3 is a divalent metal selected from Mg, Ca, Cu, Ni and any mixture thereof.

10. The method according to claim 9, wherein M3 is a divalent metal selected from Mg, Cu, Ni and any mixture thereof.

11. The method according to claim 8, wherein M4 is a trivalent metal selected from Al, Ni and any mixture thereof.

12. The method according to claim 11 wherein M4 is Al.

13. The method according to claim 8, wherein catalyst B comprises Cu and Ni.

14. The method according to claim 13, 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. The method according to claim 8, wherein the molar ratio (Mg+Cu+Ni/Al) is between 1 and 6.

16. The method according to claim 1, wherein the weight ratio of catalysts A and B is between 1:10 to 10:1.

17. The method according to claim 16, wherein the proportion of catalysts A and B is 1:1.

18. The method according to claim 3, wherein the thermal decomposition of hydrotalcite HT.sub.A is performed by means of calcination under atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging between 250 C. and 650 C.

19. The method according to claim 8, wherein the thermal decomposition of hydrotalcite HT.sub.B is performed by means of calcination under atmosphere of oxygen, nitrogen or any mixture thereof at a temperature ranging between 250 C. and 650 C.

20. The method according to claim 3, wherein Q.sub.A is at least one anion selected from CO.sub.3.sup.2, HCO.sub.3.sup., O.sub.2.sup. and OH.sup..

21. The method according to claim 8, wherein Q.sub.B is at least one anion selected from CO.sub.3.sup.2, HCO.sub.3.sup., O.sub.2.sup. and OH.sup..

22. The method according to claim 1, the noble metal is added to the metal oxide of catalyst A by wet impregnation, incipient volume impregnation or deposition-precipitation.

23. The method according to claim 22, wherein, following the addition of the noble metal, there is a calcination step and a reduction step subsequent to the calcination.

24. The method according to claim 1, wherein the contact between ethanol, n-hexanol and catalysts A and B is performed at a pressure of up to 120 bar.

25. The method according to claim 1, wherein the contact between ethanol, n-hexanol and catalysts A and B is performed at a temperature ranging between 50 C. and 450 C.

26. The method according to claim 1, wherein the contact between ethanol, n-hexanol and catalysts A and B is performed under atmosphere of nitrogen, argon, hydrogen or any mixture thereof.

27. (canceled)

28. (canceled)

29. (canceled)

30. (canceled)

Description

DESCRIPTION OF THE DRAWINGS

[0135] FIG. 1. Shows a comparative graph of the catalytic activities (conversions of EtOH and HexOH and yields of n-ButOH, 1-OctOH and of the sum of C.sub.4+OH) of catalysts based on different mixed oxides derived from hydrotalcites (Examples 3 to 7) in a N.sub.2 atmosphere. %: percentage of conversion or yield, as indicated on the x-axis; CEtOH: ethanol conversion, CHexOH: n-hexanol conversion, rButOH: yield of n-ButOH; rOctOH: yield of 1-octanol; rC4+OH: yield of alcohols C.sub.4+; 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-HT-4).

[0136] FIG. 2. Shows a comparative graph of the catalytic activities (conversions of EtOH and HexOH and yields of n-ButOH, 1-OctOH and of 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 a N.sub.2 atmosphere. %: percentage of conversion or yield, as indicated on the x-axis; CEtOH: ethanol conversion, CHexOH: n-hexanol conversion, rButOH: yield of n-ButOH; rOctOH: yield of 1-octanol; rC4+OH: yield of alcohols C4+; 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-HT-4).

[0137] FIG. 3. Shows a comparative graph of the catalytic activities (yields of 1-OctOH and of the sum of C.sub.4+OH) of physical mixtures in different proportions or ratios of the catalysts of Examples 3 and 7 in a N.sub.2 atmosphere %: percentage of yield; r(OctOH): yield of 1-octanol; r(C4+OH): yield of the sum of C.sub.4+OH (in points); g cat; quantity in grams of catalyst of the Example 3 (0.63% Pd/0.16% Ga-HT-1)+quantity in grams of catalyst of the Example 7 (0.77% Cu-0.92% Ni-HT-4).

EXAMPLES

[0138] Below, the present inventors shall illustrate, by means of assays performed by the inventors, that demonstrate the efficacy of the hydrotalcite-derived catalysts comprising gallium in their structure used together with hydrotalcite-derived catalysts comprising Cu, Ni or any mixture thereof in the production of 1-octanol.

Example 1. Synthesis of the 0.16% Ga-HT-1 Catalyst

[0139] It was prepared by means of a standard co-precipitation method using two solutions. The first solution contained 18.50 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 26.75 g of Al(NO.sub.3).sub.3.9H.sub.2O and 0.06 g of Ga(NO.sub.3).sub.3.9H.sub.2O, 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 Na.sub.2CO.sub.3 in 70.83 g of Milli-Q water, and it was used to produce the suitable precipitation of the Mg, Al and Ga species, and to set 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 receptacle under vigorous stirring at ambient temperature. The gel formed was aged at ambient 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 pH7). Next, the solid was dried in an oven at 60 C. for 14-16 h. The hydrotalcite (Ga-HT-1) produced was calcined in air at 450 C. for 3-4 h, to produce a mixed oxide with a molar ratio of Mg/Al1.48, a Ga content of 0.16% by weight (measured by chemical analysis and ICP-MS) and a surface area (BET method) of 319 m.sup.2/g.

Example 2. Synthesis of the 0.29% Ga-HT-4 Catalyst

[0140] It was prepared by means of a standard co-precipitation method using two solutions. The first solution contained 29.89 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 10.90 g of Al(NO.sub.3).sub.3.9H.sub.2O and 0.06 g of Ga(NO.sub.3).sub.3.9H.sub.2O, 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.sub.2CO.sub.3 in 72.60 g of Milli-Q water, and it was used to produce the suitable precipitation of the Mg, Al and Ga species, and to set 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 receptacle under vigorous stirring at ambient temperature. The gel formed was aged at ambient 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 pH7). Next, the solid was dried in an oven at 60 C. for 14-16 h. The hydrotalcite (Ga-HT-4) produced was calcined in air at 450 C. for 3-4 h, to produce a mixed oxide with a molar ratio of Mg/Al3.8, a Ga content of 0.29% by weight (measured by chemical analysis and ICP-MS) and a surface area (BET method) of 262 m.sup.2/g.

Example 3. Synthesis of the 0.63% Pd/0.16% Ga-HT-1 Catalyst

[0141] It was prepared from the material prepared as described in Example 1, wherein the incorporation of Pd (1.0% by weight, theoretical) in the Ga-HT-1 material was performed by means of the incipient wetness impregnation method, using, in this case, 0.025 g of Pd(NH.sub.3).sub.4Cl.sub.2.6H.sub.2O 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 produced 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, was subsequently reduced to 350 C. in an H.sub.2 atmosphere for 3 h prior to the catalytic application thereof. The resulting Pd/0.16% Ga-HT-1 material, characterised by chemical analysis and ICP-MS, contained 0.63% by weight of Pd.

Example 4. Synthesis of the 0.24% Pd/0.29% Ga-HT-4 Catalyst

[0142] It was prepared from the material prepared as described in Example 2, wherein the incorporation of Pd (0.3% by weight, theoretical) into the Ga-HT-4 material was performed by means of the incipient wetness impregnation method, using, in this case, 0.008 g of Pd(NH.sub.3).sub.4Cl.sub.2.6H.sub.2O dissolved in 1.800 g of Milli-Q water, to impregnate 1.011 g of 0.29% of Ga-HT-4. Once impregnated, the solid produced 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, was subsequently reduced to 350 C. in an H.sub.2 atmosphere for 3 h prior to the catalytic application thereof. The resulting Pd/0.29% Ga-HT-4 material, characterised by chemical analysis and ICP-MS, contained 0.24% by weight of Pd.

Example 5. Synthesis of the 2.5% Cu-HT-4 Catalyst

[0143] It was prepared by means of a standard co-precipitation method using two solutions. The first solution contained 30.01 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 10.16 g of Al(NO.sub.3).sub.3.9H.sub.2O and 0.58 g of Cu(NO.sub.3).sub.2.2.5H.sub.2O, 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 Na.sub.2CO.sub.3 in 74.58 g of Milli-Q water, and it was used to produce the suitable precipitation of the Mg, Al and Cu species, and to set the pH of the total mixture at 13. Both solutions were added (total flow rate=30 ml/h for approximately 4 h) to a receptacle under vigorous stirring at ambient temperature. The gel formed was aged at ambient 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 pH7). Next, the solid was dried in an oven at 60 C. for 18 h. The hydrotalcite (Cu-HT-4) produced was calcined in air at 450 C. for 3-4 h, to produce a mixed oxide with a molar ratio of Mg/Al3.88, a Cu content of 2.5% by weight, characterised by chemical analysis and ICP-M5 and a surface area (BET method) of 191 m.sup.2/g.

Example 6. Synthesis of the 2.5% Ni-HT-4 Catalyst

[0144] It was prepared by means of a standard co-precipitation method using two solutions. The first solution contained 29.29 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 10.94 g of Al(NO.sub.3).sub.3.9H.sub.2O and 0.78 g of Ni(NO.sub.3).sub.2.6H.sub.2O, 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 Na.sub.2CO.sub.3 in 74.12 g of Milli-Q water, and it was used to produce the suitable precipitation of the Mg, Al and Cu species, and to set the pH of the total mixture at 13. Both solutions were added (total flow rate=30 ml/h for approximately 4 h) to a receptacle under vigorous stirring at ambient temperature. The gel formed was aged at ambient 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 pH7). Next, the solid was dried in an oven at 60 C. for 18 h. The hydrotalcite (Ni-HT-4) produced was calcined in air at 450 C. for 3-4 h, to produce a mixed oxide with a molar ratio of Mg/Al3.58, a Ni content of 2.5% by weight, characterised by chemical analysis and ICP-M5 and a surface area (BET method) of 190 m.sup.2/g.

Example 7. Synthesis of the 0.77% Cu-0.92% Ni-HT-4 Catalyst

[0145] It was prepared by means of a standard co-precipitation method using two solutions. The first solution contained 29.25 g of Mg(NO.sub.3).sub.2.6H.sub.2O, 10.86 g of Al(NO.sub.3).sub.3.9H.sub.2O, 0.28 g of Cu(NO.sub.3).sub.2.2.5H.sub.2O and 0.39 g of Ni(NO.sub.3).sub.2.6H.sub.2O, 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 Na.sub.2CO.sub.3 in 72.70 g of Milli-Q water, and it was used to produce the suitable precipitation of the Mg, Al and Cu species, and to set the pH of the total mixture at 13. Both solutions were added (total flow rate=30 ml/h for approximately 4 h) to a receptacle under vigorous stirring at ambient temperature.

[0146] The gel formed was aged at ambient 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 pH7). Next, the solid was dried in an oven at 60 C. for 18 h. The hydrotalcite (CuNi-HT-4) produced was calcined in air at 450 C. for 3-4 h, to produce 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, characterised by chemical analysis and ICP-M5 and a surface area (BET method) of 208 m.sup.2/g.

Example 8. Comparative Catalytic Activity of the Catalysts of Examples 3 to 7 Under N.SUB.2 .Atmosphere

[0147] 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 in a 12 ml stainless steel autoclave reactor, with a reinforced PEEK (polyether ethyl ketone)-coated inside and a magnetic stirrer. The reactor was hermetically closed, with the system having a connector to a pressure meter (manometer), another connector for the loading of gases and a third outlet which made it possible to take samples at different time intervals. The reactor was initially pressurised with 24 bar of N.sub.2 and was heated to 250 C. under continuous stirring, until the total system pressure reached approx. 35-40 bar (reaction time=0). Liquid samples were taken (50-100 l) in different time intervals until 17 hours of reaction. The samples were filtered and diluted in a 2% by weight of chlorobenzene in acetonitrile standard solution, and they were analysed by means of gas chromatography in a GC-3900 Varian equipped with an FID detector and a 60 m TRB-624 capillary column.

[0148] The ethanol conversion, in molar percentage (EtOH conv.), was calculated from the composition of the mixture obtained:

(initial moles of ethanolfinal moles of ethanol)/(initial moles of ethanol*100)

[0149] The n-hexanol conversion, in molar percentage (Cony. of n-HexOH), was calculated from the composition of the mixture obtained:

(initial moles of n-hexanolfinal moles of n-hexanol)/(initial moles of n-hexanol*100)

[0150] The total yield of n-butanol, in molar percentage (Yield of n-ButOH), was calculated as:

(moles of n-butanol/moles of total products)*EtOH conv./100

[0151] The total yield of 1-octanol, in molar percentage (Yield of 1-OctOH) was calculated as:

(moles of 1-octanol/moles of total products)*EtOH conv./100

[0152] The total yield of linear C.sub.4+ alcohols, in molar percentage (Yield of linear C.sub.4+OH), including n-butanol and 1-octanol, of course, was calculated as:

(moles of linear C.sub.4+/moles of total products)*EtOH conv./100

[0153] The total yield of branched C.sub.4+ alcohols, in molar percentage (Yield of branched C.sub.4+OH), was calculated as:

(moles of branched C.sub.4+/moles of total products)*EtOH conv./100

[0154] In this way, the following results were obtained:

TABLE-US-00001 TABLE 1 Catalytic activity of the different mixed metal oxides and of physical mixtures thereof in the transformation of ethanol + n-hexanol under nitrogen atmosphere. n- T EtOH HexOH n-ButOH 1-OctOH C.sub.4+OH yield Ex. Catalyst (h) conv. conv. yield yield Lin. Bra. 3 0.63% Pd/0.16% Ga-HT-1 5 52.3 15.6 22.1 7.60 30.3 2.6 4 0.24% Pd/0.29% Ga-HT-4 5 41.1 20.2 22.0 6.90 30.0 2.6 5 2.5% Cu/HT-4 5 49.8 19.2 22.5 6.64 29.1 0.9 6 2.5% Ni-HT-4 5 42.1 16.3 9.1 4.30 13.7 0.4 7 0.77% Cu0.92% Ni-HT-4 5 51.4 16.2 26.8 8.00 36.8 2.9 3 + 7 0.63% Pd/0.16% Ga-HT- 5 49.2 17.3 26.3 10.82 39.0 3.6 1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g) 4 + 5 0.24% Pd/0.29% Ga-HT- 5 29.5 9.4 15.0 7.71 24.0 1.9 4 (0.20 g) + 2.5% Cu- HT-4 (0.15 g) 4 + 6 0.24% Pd/0.29% Ga-HT- 5 28.4 13.4 18.0 5.33 23.3 0.7 4 (0.20 g) + 2.5% Ni-HT- 4 (0.15 g) 4 + 7 0.24% Pd/0.29% Ga-HT- 5 39.7 10.1 23.0 8.56 31.6 2.1 4 (0.20 g) + 0.77% Cu0.92% Ni-HT-4 (0.15 g)

[0155] The 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 produced with the mixtures of Examples 3+7 and 4+7. Even more so, these mixtures of catalysts show better results to those produced with the individual catalysts, which implies there is a synergic factor and not only additive 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 (CuNi-HT-4) is particularly noteworthy, which gives higher yields of 1-octanol and, in general, higher yield of C.sub.4+ alcohols than the respective catalysts used individually, as observed in FIGS. 1 and 2.

Example 9. Comparative Catalytic Activity of the Catalysts of Examples 3 and 7 and of Physical Mixtures Thereof Under N.SUB.2 .Atmosphere

[0156] 1750 mg of ethanol, 1790 mg of n-hexanol and 350 mg of one of the catalytic materials of Examples 3 and 7 and of physical mixtures of different proportions thereof (always giving a total of 350 mg) were introduced in a 12 ml stainless steel autoclave reactor, with a reinforced PEEK (polyether ethyl ketone)-coated inside and a magnetic stirrer. The reactor was hermetically closed, with the system having a connector to a pressure meter (manometer), another connector for the loading of gases and a third outlet which made it possible to take samples at different time intervals. The reactor was initially pressurised with 20 bar of N.sub.2 and was heated to 250 C. under continuous stirring, until the total system pressure reached approx. 35-40 bar (reaction time=0). Liquid samples were taken (50-100 l) in different time intervals until 17 hours of reaction. The samples were filtered and diluted in a 2% by weight of chlorobenzene in acetonitrile standard solution, and they were analysed by means of gas chromatography in a GC-3900 Varian equipped with an FID detector and a 60 m TRB-624 capillary column.

[0157] The ethanol conversion, in molar percentage (EtOH conv.), was calculated from the composition of the mixture obtained:

(initial moles of ethanolfinal moles of ethanol)/(initial moles of ethanol*100)

[0158] The n-hexanol conversion, in molar percentage (Cony of n-HexOH), was calculated from the composition of the mixture obtained:

(initial moles of n-hexanolfinal moles of n-hexanol)/(initial moles of n-hexanol*100)

[0159] The total yield of n-butanol, in molar percentage (Yield of n-ButOH), was calculated as:

(moles of n-butanol/moles of total products)*EtOH conv./100

[0160] The total yield of 1-octanol, in molar percentage (Yield of 1-OctOH) was calculated as:

(moles of 1-octanol/moles of total products)*EtOH conv./100

[0161] The total yield of linear C.sub.4+ alcohols, in molar percentage (Yield of linear C.sub.4+OH), including n-butanol and 1-octanol, of course, was calculated as:

(moles of linear C.sub.4+/moles of total products)*EtOH conv./100

[0162] The total yield of branched C.sub.4+ alcohols, in molar percentage (Yield of branched C.sub.4+OH), was calculated as:

(moles of branched C.sub.4+/moles of total products)*EtOH conv./100

[0163] In this way, the following results were obtained:

TABLE-US-00002 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. n- n- T EtOH HexOH ButOH 1-OctOH C.sub.4+OH yield Ex. Catalyst (h) conv. conv. yield yield Lin. Bra. 3 0.63% Pd/0.16% Ga-HT-1 5 52.3 15.6 22.1 7.60 30.3 2.6 3 + 7 0.63% Pd/0.16% Ga-HT-1 5 49.2 17.3 26.3 10.82 39.0 3.6 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g) 3 + 7 0.63% Pd/0.16% Ga-HT-1 5 58.0 19.9 26.0 13.5 42.3 3.5 (0.20 g) + 0.77% Cu0.92% Ni-HT-4 (0.15 g) 3 + 7 0.63% Pd/0.16% Ga-HT-1 5 51.7 14.6 25.2 11.17 38.5 3.5 (0.10 g) + 0.77% Cu0.92% Ni-HT-4 (0.25 g) 7 0.77% Cu0.92% Ni-HT-4 5 51.4 16.2 26.8 8.00 36.8 2.9

[0164] If the physical mixtures were compared in different proportions of the catalysts of Examples 3 and 7, the results show that a synergic effect is observed and not merely additive with the use of the catalyst mixture, and that furthermore, there is an optimum in the proportions of each one of the catalysts. Thus, the greatest yields of 1-octanol and, in general, greater yield of C.sub.4+ alcohols were 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 (CuNi-HT-4), as observed in FIG. 3. This demonstrates that not only the synergic effect of the catalyst mixture with respect to the individual catalysts, but also both the type of catalyst and its proportions are not trivial, nor can they be calculated or pre-established beforehand taking the data obtained with each individual catalyst as the base.

Example 10. Comparative Catalytic Activity of the Catalysts of Examples 3, 5-7 and the Physical Mixture of the Catalysts of Examples 3 and 7 Under H.SUB.2 .(or N.SUB.2.) Atmosphere with Ethanol Alone (without n-Hexanol)

[0165] 3500 mg of ethanol and 350 mg of one of the catalytic materials of Examples 3 and 5 to 7, as well as the mixture of Examples 3 (200 mg) and 7 (150 mg) were introduced in a 12 ml stainless steel autoclave reactor, with a reinforced PEEK (polyether ethyl ketone)-coated inside and a magnetic stirrer. The reactor was hermetically closed, with the system having a connector to a pressure meter (manometer), another connector for the loading of gases and a third outlet which made it possible to take samples at different time intervals The reactor was initially pressurised with 10 bar of H.sub.2 and next it was taken to 24 bar with addition of N.sub.2 and was heated to 200 C. under continuous stirring, until the total system pressure reached approx. 30 bar (reaction time=0). Liquid samples were taken (50-100 l) in different time intervals until 17 hours of reaction. The samples were filtered and diluted in a 2% by weight of chlorobenzene in acetonitrile standard solution, and they were analysed by means of gas chromatography in a GC-3900 Varian equipped with an FID detector and a 60 m TRB-624 capillary column.

[0166] The following results were obtained:

TABLE-US-00003 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. n- n- T EtOH HexOH HexOH 1-OctOH C.sub.4+OH yield Ex. Catalyst (h) conv. conv. yield yield Lin. Bra. 3 0.63% Pd/0.16% Ga-HT-1 5 11.2 8.8 0.0 0.0 8.8 0.0 5 2.5% Cu/HT-4 5 7.7 5.7 0.8 0.0 6.5 0.0 5 2.5% Cu/HT-4 (Sin H.sub.2) 5 9.4 4.7 1.5 0.0 6.2 0.0 6 2.5% Ni-HT-4 5 6.9 4.8 0.7 0.0 5.5 0.0 6 2.5% Ni-HT-4 (Sin H.sub.2) 5 7.8 2.5 1.0 0.0 3.5 0.0 7 0.77% Cu0.92% Ni-HT-4 5 10.7 8.4 0.2 0.0 8.6 0.0 3 + 7 0.63% Pd/0.16% Ga-HT-1 5 13.2 4.9 7.5 0.33 12.7 0.1 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)

[0167] The rest of the products up 100% mainly comprise aldehydes (ethanal, butanal, hexanal, ethylacetate and dietoxyethane).

[0168] The results obtained with the physical mixture of the catalysts of Examples 3 and 7 clearly show that it is possible to produce high yields of 1-hexanol (and the sum of 1-butanol+1-hexanol) using only ethanol as starting reagent. However, these results also show that both the individual catalysts and the physical mixture thereof object of the present invention do not produce 1-octanol in a high percentage when they react with ethanol as reagent. Therefore, it shows that n-hexanol and ethanol are required to produce 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 H.SUB.2 .Atmosphere with n-Butanol as Raw Material (Neither Ethanol Nor n-Hexanol)

[0169] 3500 mg of n-butanol and 350 mg of one of the catalytic materials of Examples 3, 5 and 7, and the mixture of Examples 3 (200 mg) and 7 (150 mg), were introduced in a 12 ml stainless steel autoclave reactor, with a reinforced PEEK (polyether ethyl ketone)-coated inside and a magnetic stirrer. The reactor was hermetically closed, with the system having a connector to a pressure meter (manometer), another connector for the loading of gases and a third outlet which made it possible to take samples at different time intervals The reactor was initially pressurised with 10 bar of H.sub.2 and next it was taken to 24 bar with addition of N.sub.2 and was heated to 250 C. under continuous stirring, until the total system pressure reached approx. 40 bar (reaction time=0). Liquid samples were taken (50-100 l) in different time intervals until 17 hours of reaction. The samples were filtered and diluted in a 2% by weight of chlorobenzene in acetonitrile standard solution, and they were analysed by means of gas chromatography in a GC-3900 Varian equipped with an FID detector and a 60 m TRB-624 capillary column.

[0170] The following results were obtained:

TABLE-US-00004 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. n- 1- T ButOH Butanal Aldehydes OctOH C.sub.4+OH yield Ex. Catalyst (h) conv. yield yield yield Lin. Bra. 3 0.63% Pd/0.16% Ga-HT-1 5 22.2 2.5 1.2 1.1 11.9 3.3 7 0.77% Cu0.92% Ni-HT-4 5 23.1 4.1 2.1 0.5 10.2 3.5 3 + 7 0.63% Pd/0.16% Ga-HT-1 5 27.9 2.8 1.8 1.9 13.2 5.4 (0.25 g) + 0.77% Cu0.92% Ni-HT-4 (0.10 g)

[0171] 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.

[0172] These results show that both the individual catalysts and the physical mixture of catalysts object of the present invention do not produce 1-octanol in a high percentage. Therefore, it shows that n-hexanol and ethanol are required to produce high yields of 1-octanol.