PROCESS FOR THE PRODUCTION OF N-BUTANOL AND 1,4-BUTANEDIOL FROM FURAN

Abstract

The present invention provides a process for the production of n-butanoland 1,4-butanediol, said process comprising contacting furan with hydrogen and water in the presence of a catalytic composition, comprising at least one element selected from those in groups 8, 9, 10 and 11 of the periodic table on a solid support comprising an amorphous or crystalline aluminosilicate in an acidic form, wherein the catalyst does not contain metals selected from those in groups 6 and 7 of the periodic table.

Claims

1. A process for the production of n-butanol and 1,4-butanediol, said process comprising contacting furan with hydrogen and water in the presence of a catalytic composition, comprising at least one element selected from those in groups 8, 9, 10 and 11 of the periodic table on a solid support comprising an amorphous or crystalline aluminosilicate in an acidic form, wherein the catalyst does not contain metals selected from those in groups 6 and 7 of the periodic table.

2. A process according to claim 1, wherein the solid support comprises an amorphous aluminosilicate in an acidic form.

3. A process according to claim 1, wherein the solid support comprises a zeolite in an acidic form.

4. A process according to claim 1, wherein at least one element selected from those in groups 8, 9, 10 and 11 of the periodic table is selected from the group of at least one of cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium or platinum in their elemental form or as compounds.

5. A process according to claim 1, wherein the total amount of the at least one element selected from those in groups 8, 9, 10 and 11 of the periodic table considered as its element on the catalyst is in the range of from 0.01 to 20wt %.

6. A process according to claim 1, wherein the furan is contacted with hydrogen in the liquid phase at a temperature in the range of from 25 to 250° C., a pressure of from 0.1 to 10 MPa and a H2:furan molar ratio in the range of from 0.2:1 to 100:1.

7. A process according to claim 1, wherein the furan is contacted with hydrogen and water is co-fed at a water:furan molar ratio in the range of from 0.2:1 to 100:1, at a temperature in the range of from 100 to 350° C., a pressure of from 0.1 to 15 MPa and a H2:furan molar ratio in the range of from 0.2:1 to 100:1.

Description

EXAMPLES

[0028] A number of catalysts were evaluated in a 16-reactor testing unit that can operate at up to 80 bar and 500° C. The testing unit can be fed with up to 5 gases (hydrogen, CO, N.sub.2, argon and air) and two liquids. The unit allowed for on-line GC analysis of gases and semi-automated off-line GC analysis of the liquid product. Gas and liquid product yields were determined in reference to a gas standard (He) and a liquid standard (diethylene-glycol diethyl ether) that were fed together with the gas and liquid feed and were selectively collected in the gas and liquid samples, respectively.

[0029] The reactor consisted of SS316 tubes of 4.6 mm ID and 35.5 cm long, of which the central 10 cm length is isothermal. The reactor tubes were loaded with about 1 mL of catalyst, centered in the middle of the reactor while the remaining upper and lower void was filled with inert material such as SiC particles and/or porous SS316 cylinders.

[0030] The supports used in Examples 1 to 9 of the invention were either based on amorphous silica-alumina or a mixture of amorphous silica-alumina with H-Beta zeolite. The support indicated as “ASA” contained amorphous silica-alumina, which contained silica and alumina in a weight ratio of 75:25, bound in a weight ratio of 70:30 with alumina (weight ratio of silica-alumina:alumina). The support indicated as “H-Beta/ASA” comprised 4 wt % H-Beta zeolite, 66 wt % amorphous silica-alumina bound with 30 wt % alumina. The support used in examples 5-6 and indicated as “H-Beta” comprised 35 w % of zeolite Beta that has a silica/alumina weight ratio of 730, is in acidic form and bound with alumina. The supports used in Examples 10 to 13 indicated as “H-ZSM5” comprised a silica bound ZSM-5 zeolite in its acidic form with a zeolite content of 30-60 w % and with an silica:alumina weight ratio 30-50 in the zeolite.

[0031] These catalysts were prepared by incipient wetness impregnation of the support with solution of the following salts: Pt(NH.sub.3).sub.4(NO.sub.3).sub.2, Ru(NO.sub.3).sub.3NO. The solutions were prepared with the concentration required to achieve the targeted metal loading. The catalysts were dried at 120° C. for 2 h in air and for half an hour at 225° C. temperature.

[0032] The catalysts were dried and reduced for 1 h at 75° C., 4 h at 120° C. and 4 h at 275° C. under a 30% H.sub.2/70% N.sub.2 flow of 0.625 NL/h (per reactor) at nearly atmospheric pressure. Subsequently, the temperature is lowered to 120° C., the pressure is raised to 50 atmosphere and the gas flow set to 0.25 NL/h (per reactor) and 100% H.sub.2 and subsequently 0.25 NL/h and 85% H.sub.2/15% H.sub.2 to be ready for start-up.

[0033] The gas feed consisted of a mixture of 10% He and 90% H.sub.2 and was fed at a rate of about 280 NL per liter catalyst bed per hour. The liquid feed consisted of a mixture of 24 w % furan, 21 w % water, 50 w % ethanol and 4 w % standard. The liquid feed was introduced at a rate of about 0.8 litre per litre catalyst bed per hour. The run was carried out at a pressure of 50 bars. The temperature was ramped from 140 to 200° C. by steps of 20° C. and back to 160° C. The run lasted for 200-250 hours in total.

[0034] The average yields measured are reported in Table 1. The yields are expressed as fraction of the carbon of furan that is converted into the desired product. The yield may occasionally add up to slightly more than 100C % as results of experimental inaccuracies.

[0035] As shown in Table 1, good overall yields were obtained for the process of the invention, with the combined yields of butanol and 1,4-BDO being higher than that of THF.

[0036] Advantageously, it was also found that using different metals in the process of the invention allows said process to be tailored to provide higher relative yields of either 1,4-BDO or n-butanol.

TABLE-US-00001 TABLE 1 Catalysts of the Invention BDO THF NBA Metal Temp yield yield yield Support Metal w % ° C. C % C % C % 1 H-Beta/ASA Pt 0.8 160 6.5 18.5 31.4 2 H-Beta/ASA Pt 0.8 185 4.2 16.3 23.6 3 ASA Pt 0.5 160 8.7 19.1 49.1 4 ASA Pt 0.5 185 6.8 19.0 48.7 5 H-Beta Ru 0.5 160 26.2 35.5 14.7 6 H-Beta Ru 0.5 185 17.3 36.2 16.2 7 ASA Ru 0.1 120 7.3 31.5 5.2 8 ASA Ru 0.1 140 0.6 3.3 0.9 9 ASA Cu 15%  140 0.7 3.9 1.3 10 H-ZSM5 Pt 1.0 140 1.5 4.2 6.3 11 H-ZSM5 Pt 1.0 160 1.3 6.3 10.2 12 H-ZSM5 Pt 1.0 180 2.0 5.7 14.3 13 H-ZSM5 Pt 1.0 200 2.1 6.4 20.9

[0037] Comparative catalysts were produced and tested according to similar processes. The results of these tests are shown in Table 2. It can be seen that catalysts containing rhenium provide much higher levels of THF rather than 1,4-BDO and/or n-butanol. Catalyst 26, which does not contain rhenium, and also does not use an acidic aluminosilicate support provides very low levels of 1,4-BDO, with the vast majority of the product being THF.

TABLE-US-00002 TABLE 2 Comparative Examples THF BDO NBA Metal Metal Metal 1 Metal 2 Yield Yield Yield Support 1 2 w % w % C % C % C % 14 Carbon Pt Re 0.50 5.0 63.9 12.2 12.7 15 TiO.sub.2 Pt Re 0.10 5.0 48.9 4.2 20.5 16 ZrO.sub.2 Pt Re 0.10 5.0 48.0 1.7 18.8 17 ZrO.sub.2 Pt Re 0.50 3.0 49.8 0.8 17.3 18 Carbon Ru Re 1.00 5.0 66.0 12.1 15.6 19 Carbon Ru Re 0.20 2.0 3.3 3.7 3.3 20 TiO.sub.2 Ru Re 0.10 10 24.4 3.0 10.3 21 TiO.sub.2 Ru Re 1.00 10 59.1 1.7 26.9 22 TiO.sub.2 Ru Re 0.50 5.0 58.1 1.3 22.8 23 TiO.sub.2 Ru Re 1.67 5.0 48.3 0.1 10.5 24 Carbon Ru Ni 0.52 4.0 87.9 5.1 2.2 25 Carbon Ru Cu 3.00 3.0 35.3 1.8 16.1 26 Ce/Zr* Ru — 1.5 — 57.7 0.1 13.0 *Ce.sub.0.75Zr.sub.0.25O.sub.2