Patent Application
20180186760
The present invention relates to a process for the production of 1,4-butanediol and THF from furan.
Furan and its derivatives are useful precursors for industrial chemicals. In particular, furan may be converted into 1,4-butanediol (1,4-BDO) and tetrahydrofuran (THF), both of which are valuable industrially-used chemicals.
1,4-BDO is used as an industrial solvent and in the manufacture of polyurethanes and polymers such as polyesters.
THF, on the other hand, is used in the production of elastic fibres such as elastane/spandex (marketed as e.g. Lycre®), as well as being used as an industrial solvent for PVC and in varnishes.
THF and 1,4-BDO are usually produced industrially from petrochemical (fossil fuel) derived feedstocks such as acetylene and propylene, via a number of routes.
An industrial route for the production of 1,4-BDO requires the reaction of acetylene with two equivalents of formaldehyde followed by hydrogenation of the resultant 1,4-butynediol to form 1,4-butanediol. In an alternative process, propylene oxide is converted to allyl alcohol. The allyl alcohol is then hydroformylated to form 4-hydroxybutyraldehyde, which may be hydrogenated to form 1,4-butanediol.
A route that is becoming more popular for the production of 1,4-BDO is the oxidation of butane to maleic anhydride followed by its selective hydrogenation to 1,4-BDO and THF. Other traditional routes for the production of 1,4-BDO use butadiene, allyl acetate or succinic acid as starting materials.
One industrial route for the production of THF proceeds via the hydrogenation of furan over a nickel catalyst (McKillip, W. J., ACS Symposium Series, Issue 385, 1989, Pages 408-423). In turn, Furan may be produced by Paal-Knorr synthesis which reacts 1,4-diketones with phosphorus pentoxide (P2O5), or by Feist-Benary synthesis which uses α-halogen ketones and β-dicarbonyl compounds as feedstock. In any event, such feedstocks are fossil fuel derived.
In recent years, to reduce the demand for fossil fuels, increased efforts have focused on producing chemicals, including 1,4-BDO and THF, from non-fossil fuel/renewable feedstocks such as hemicellulose. This route initially involves the production of furfural, followed by its conversion to its derivatives, such as furan.
A method for obtaining furan from renewable resources involves the decarbonylation of furfural. Examples of reaction processes for achieving this, and the subsequent conversion of the furan into its derivatives, can be found in: (i) Hoydonck, H. E., Van Rhijn, W. M., Van Rhijn, W., De Vos, D. E. & Jacobs, P. A. (2012) “Furfural and Derivatives”, in Ulmann's Encyclopedia of Industrial Chemistry (volume 16, pp 285-313), Wiley-VCH Verlag GmbH & Co. KGaA; (ii) Dunlop, A. P. and Peters, F. N., in “The Furans” Reinhold Publ. Co, 1953; (iii) K.J. Zeitsch, in “The Chemistry and Technology of Furfural and its Many By-products” Sugar Series 13, Elsevier, 2000; (iv) Lange, J-P, van der Heide, E, van Buijtenen, J., and Price, R. “Furfural—A Promising Platform for Lignocellulosic Biofuels”, ChemSusChem 2012, 5, 150-166; and (v) Watson, J. M., Ind. Eng. Chem. Prod. Res. Develop., 1973, 12(4), 310.
Furfural may be obtained from hemicellulose via acid hydrolysis in the liquid phase as well as in the gas phase as described in WO 2002/22593 and WO 2012/041990.
The conversion of furan to THF and 1,4-BDO by hydrogenation in the presence of water, acetic acid and Raney nickel or oxide supported nickel catalyst is described in Watson, J. M., Ind. Eng. Chem. Prod. Res. Develop., 1973, 12(4), 310.
A process for the conversion of furan into THF, 1,4-BDO and n-butanol is taught in U.S. Pat. No. 5,905,159. This document teaches a process in which furan is converted as a reaction mixture with water and in the presence of hydrogen, but in the absence of a water-soluble acid, in a single stage over a hydrogenation catalyst. The hydrogenation catalyst of U.S. Pat. No. 5,905,159 contains at least one element of subgroup I, V, VI, VII or VIII in the form of a compound or in elemental form, with the restriction that the catalyst does not contain nickel alone. The catalysts taught in U.S. Pat. No. 5,905,159 generally contain two metals with most containing rhenium as a promoter. The most preferred catalyst taught in U.S. Pat. No. 5,905,159 for the process contains rhenium and ruthenium supported on active carbon.
Challenges remain concerning the method of production of 1,4-BDO and THF from furan. It is desirable that non-fossil fuel renewable feedstock(s) is/are used for the production of 1,4-BDO and THF, as a contribution to minimising fossil fuel use.
The non-fossil fuel based production processes of 1,4-BDO and THF from furan requires the use of catalyst compositions that contain expensive and rare metals, so the activity, the product selectivity and the life-span of such catalysts, as well as their cost, are of particular concern to the operators of such processes. Therefore, it is in the interest of such operators to prolong the life-span of these catalysts, to maintain their maximum activity for as long as possible, and to keep their product selectivity within the required commercial and operational margins. However, commercial and operational needs may, for example, require reaction conditions to be altered for periods of time in ways that may be unfavourable to the integrity and activity of such catalysts, thus shortening the catalyst's life-span and/or or adversely affecting its product selectivity. It would therefore be advantageous to have available catalysts that can withstand broader operational conditions.
It would also be advantageous to the producers of 1,4-BDO and THF from non-fossil fuel-derived furan to tailor the respective amounts of 1,4-BDO and THF produced so that they can respond quickly to changes in the demand for these products at any given time. A way to respond quickly to such changes in demand is to have multiple reactor vessels, each charged with a different catalyst of a particular product selectivity, so that production can be switched between the reactor vessels depending on the desired product at that particular time. However, this would be an impractical and expensive option as some reactor vessels would have to remain idle during times when the product ratio they can produce is not needed. A simpler, cheaper and a more practical way of altering product ratio remains to be made available.
Accordingly, the present invention provides a method for increasing the molar ratio of tetrahydrofuran to 1,4-butanediol in a process for the production of 1,4-butanediol and tetrahydrofuran, said process comprising contacting furan with hydrogen and water in a reactor vessel, at an initial partial pressure of hydrogen and in the presence of a catalytic composition comprising at least one metal on a solid support, wherein the at least one metal is selected from cobalt, nickel, ruthenium, palladium and platinum and wherein the molar ratio of tetrahydrofuran to 1,4-butanediol is increased by increasing the partial pressure of hydrogen in the reactor vessel above the initial partial pressure of hydrogen.
The present invention also provides a method for increasing the molar ratio of 1,4-butanediol to tetrahydrofuran in a process for the production of 1,4-butanediol and tetrahydrofuran, said process comprising contacting furan with hydrogen and water in a reactor vessel, at an initial partial pressure of hydrogen and in the presence of a catalytic composition comprising at least one metal on a solid support, wherein the at least one metal is selected from cobalt, nickel, ruthenium, palladium and platinum, and wherein the molar ratio of 1,4-butanediol to tetrahydrofuran is increased by decreasing the partial pressure of hydrogen in the reactor vessel below the initial partial pressure of hydrogen.
The present inventors have surprisingly found that in the process of reacting furan with hydrogen and water in the presence of a solid-supported catalytic composition comprising at least one metal selected from cobalt, nickel, ruthenium, palladium and platinum, the molar ratio of THF to 1,4-BDO can be tailored to produce the product that suits market demand for 1,4-BDO and THF at the prevailing time. The present inventors have surprisingly found that in such a process, increasing the partial pressure of hydrogen in the reactor vessel leads to more THF being produced relative to 1,4-BDO, and lowering the partial pressure of hydrogen in the reactor vessel leads to more 1,4-BDO being produced relative to THF.
The present inventors have, therefore, found that the abovementioned surprising effects can be utilised to tailor the molar ratio of the products of the process, i.e. THF and 1,4-BDO, with minimal cost and operational burden.
The catalytic composition used in the process of the present invention contains at least one metal selected from the group consisting of cobalt, nickel, ruthenium, palladium and platinum (Co, Ni, Ru, Pd, Pt respectively) on a solid support, more preferably the at least one metal is selected from the group consisting of Ru, Pd, Pt, and most preferably the at least one metal is Ru. The at least one metal may be present on the catalytic composition in its elemental form or as one or more compounds.
Further to the above-mentioned metal or metals, the catalytic composition used in the present invention may contain an additional metal, for example a promotor metal or metals that will at least in part catalyse different reactions, such as ring-opening. A suitable example of such an additional metal is rhenium (Re). The additional metal of the catalytic composition may be present in its elemental form, or as one or more compounds.
The method of application of the at least one metal and, if present, the additional metal to the support is not critical and may be effected in a wide range of ways. Such metals may be applied to the support using the same or different methods and either sequentially of simultaneously. Suitable methods include, for example, impregnation of the support with solutions or suspensions of the salts, complexes, hydroxides, oxides or other organic or inorganic compounds of the relevant metals, drying and optional calcination. Another possibility for applying such metals to the support is to impregnate the latter with a solution of thermally readily decomposable complexes, for example with carbonyl or hydride complexes of the rhenium and/or palladium, and to heat the carrier thus impregnated to, for example, 150° C. to 600° C. for thermal decomposition of the absorbed metal compounds. Said metals may furthermore be deposited on the catalyst carrier by vapour deposition or by flame spraying. Another suitable preparation method consists of ion-exchange of the support with cationic salts or complexes of the metals followed by drying. Subsequent reduction of the metal compound to the relevant metals or compounds of lower oxidation states by means of a reducing agent may be carried out after any method of deposition.
The total amount of the at least one metal selected from Co, Ni, Ru, Pd and Pt (considered as elements) on the catalytic composition may vary within wide ranges, and may be preferably at least 0.01 wt %, more preferably at least 0.02 wt %, more preferably at least 0.03 wt %, more preferably at least 0.1 wt %, more preferably at least 0.3 wt %, most preferably at least 1.0 wt %. Further, preferably, the total amount of the at least one metal selected from Co, Ni, Ru, Pd and Pt (considered as elements) on the catalytic composition is at most 20 wt %, more preferably at most 10 wt %, most preferably at most 3 wt %.
The total amount of the additional metal (considered as its elemental form), if present, on the catalyst may vary within wide ranges, and may be preferably at least 0.02 wt %, more preferably at least 0.03 wt %, more preferably at least 0.1 wt %, more preferably at least 0.3 wt %, most preferably at least 1.0 wt %. Further, preferably, the total amount of the additional metal (considered as its elemental form), if present, on the catalyst is at most 20 wt %, more preferably at most 10 wt %, most preferably at most 5 wt %.
Preferably, the combined total amount of the abovementioned metals (the at least one metal and the additional metal in the catalytic composition), considered as their elemental form may be at least 0.01 wt %, more preferably at least 0.1 wt %, more preferably at least 0.5 wt %, more preferably at least 1.0 wt %. Further, preferably, the total amount of said metal or metals is at most 20 wt %, more preferably at most 10 wt %, most preferably at most 5 wt %.
The composition of the solid support suitably includes oxides of aluminium, titanium, zirconium, silicon, and combinations thereof. The solid support may be amorphous and/or crystalline. The solid support may also comprise clays such as montmorillonite or zeolites, such as ZSM-5 or ZSM-10 zeolites. In another embodiment, the solid support may be composed of carbon, such as active carbon or carbon fibres. The carbon can be amorphous or graphitic, or a mixture of the two. Mixtures of different supports can, of course, also serve as solid supports for the catalytic compositions to be used in the process of the invention. Preferred solid supports comprise zirconium dioxide, titanium oxides and active carbon. More preferably, the solid support comprises titanium dioxide or active carbon. Most preferably, the solid support comprises active carbon.
In the process of the invention, furan is contacted with hydrogen and water in a reactor vessel in the presence of the catalytic composition. The furan may be contacted with hydrogen and water either in the gas or in the liquid phase. Suitable conditions for the production of a mixture of BDO and THF from furan include co-feeding water as a gas or liquid at a molar ratio of water:furan of at least 0.2:1, preferably at least 1:1, and most preferably at least at 3:1. Suitable conditions for the production of a mixture of BDO and THF from furan include co-feeding water as a gas or liquid at a molar ratio of water:furan of at most 100:1, preferably at most 20:1, and most preferably at most 10:1.
Further suitable conditions for the production of a mixture of BDO and THF from furan include the use of a solvent comprising water and/or oxygenates, preferably the reaction product (THF) or the eventually by-products.
In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a molar ratio of hydrogen:furan of at most at 100:1, preferably at most at 10:1, and most preferably at most at 3:1. In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a molar ratio of hydrogen:furan of at least at 0.2:1, preferably at least at 0.5:1, and most preferably at least at 1:1.
In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a reactor temperature at most at 350° C., preferably at most at 250° C., more preferably at most at 200° C., and most preferably at most at 180° C. In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a reactor temperature of at least 25° C., preferably of at least 75° C., more preferably of at least 125° C., and most preferably of at least 140° C.
In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a total reactor pressure of at most 15 MPa, preferably of at most 10 MPa, more preferably of at most 8 MPa, and most preferably of at most 5 MPa. In general, the process for the production of 1,4-BDO and THF from furan can be carried out at a total reactor pressure of at least 0.1 MPa, preferably of at least 1 MPa, more preferably of at least 2 MPa, and most preferably of at least 3 MPa.
In general, a total reactor pressure above 15 MPa is avoided in the process for the production of 1,4-BDO and THF from furan, as this will require the process to be carried out in specialised equipment designed to withstand high pressures and variations in the reaction pressure.
Typically, the process for the production of 1,4-BDO and THF from furan is carried out at an initial total reactor pressure of at least 0.1 MPa, preferably at least 2 MPa, more preferably at least 4 MPa, even more preferably at least 6 MPa, and most preferably at least 6 MPa. Typically, the initial total reactor pressure is at most 15 MPa, preferably at most 13 MPa, more preferably at most 11 MPa, even more preferably at most 10 MPa, and most preferably at most 8 MPa.
Typically, the process for the production of 1,4-BDO and THF from furan is carried out at an initial reactor temperature of at least 25° C., preferably at least 50° C., more preferably at least 100° C., even more preferably at least 150° C., and most preferably at least 170° C. Typically, the initial reactor temperature is at most 350° C., preferably at most 300° C., more preferably at most 250° C., even more preferably at most 200° C., and most preferably at most 175° C.
Typically, the process for the production of 1,4-BDO and THF from furan is carried out at an initial molar ratio of water:furan of at least 0.2:1, preferably at least 1:1, and most preferably at least at 3:1. Typically, the initial molar ratio of water:furan of at most 100:1, preferably at most 20:1, and most preferably at most 10:1.
Typically, the process for the production of 1,4-BDO and THF from furan is carried out at an initial molar ratio of hydrogen:furan of at most at 100:1, preferably at most at 10:1, and most preferably at most at 3:1. Typically, the initial molar ratio of hydrogen:furan of at least at 0.2:1, preferably at least at 0.5:1, and most preferably at least at 1:1.
In the process of the present invention, the initial partial pressure of hydrogen in the reactor vessel at any given time is dependent on both the reactor temperature and the total reactor pressure, could readily be determined by the skilled person, and in any event is always lower than the total reactor pressure. Typically, the partial pressure of hydrogen is 2 MPa lower that the total reactor pressure at 140° C., and 40 MPa lower than the total reactor pressure at 180° C.
In the process of the present invention, the molar ratio of THF to 1,4-BDO produced may be increased by increasing the partial pressure of hydrogen in the reactor vessel above the initial partial pressure of hydrogen in the reactor vessel. The partial pressure of hydrogen in the reactor vessel may be increased above the initial partial pressure of hydrogen in the reactor vessel by a number of methods including, but not limited to, increasing the total reactor pressure above the initial reactor pressure, decreasing the reactor temperature below the initial reactor temperature, increasing the molar ratio of water:furan in the reactor vessel above the initial molar ratio of water:furan, and/or by increasing the molar ratio of hydrogen:furan in the reactor vessel above the initial molar ratio of hydrogen:furan.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is increased by increasing the total reactor pressure. This may be achieved by, amongst other ways, restricting the exit of gaseous effluent from the reactor vessel, or any other means available in the art to the skilled person. In this embodiment, the total reactor pressure is increased above the initial total reactor pressure preferably by at least 0.5 MPa, more preferably by at least 2 MPa, even more preferably by at least 5 MPa, and most preferably by at least 9 MPa. In this embodiment, the total reactor pressure may be increased above the initial reactor pressure in the reactor vessel preferably by at most 13 MPa, more preferably by at most 10 MPa. The operator of the process of the present invention may select and deploy any such increase in the total reactor pressure above the initial reactor pressure once, or more than once, subject to the total reactor pressure remaining at all times at, or below, 15 MPa.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is increased above the initial partial pressure of hydrogen in the reactor vessel by decreasing the reactor temperature below the initial reactor temperature. In this embodiment, the reactor temperature is decreased below the initial reactor temperature preferably by at least 10° C., more preferably by at least 25° C., even more preferably by at least 50° C., and most preferably by at least 100° C. In this embodiment, the reactor temperature is decreased below the initial the reactor temperature preferably by at most 175° C., more preferably at most by 125° C., even more preferably at most by 50° C., and most preferably at most by 10° C. The operator of the process of the present invention may select and deploy any such decrease in the reactor temperature below the initial reactor temperature once, or more than once, or in any combination, subject to the reactor temperature remaining at all times at, or above, 25° C.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is increased above the initial partial pressure of hydrogen in the reactor vessel by increasing the molar ratio of water:furan in the reactor vessel. In this embodiment, the molar ratio of water:furan in the reactor vessel is preferably increased above the initial molar ratio of water:furan by a factor of 1.5, more preferably by a factor of 2, even more preferably by a factor of 4, and most preferably by a factor of 10.
In one embodiment of the invention, to increase the molar ratio of THF to 1,4-BDO produced by the process of the present invention, the partial pressure of hydrogen in the reactor vessel is increased above the initial partial pressure of hydrogen in the reactor vessel by increasing the molar ratio of hydrogen:furan in the reactor vessel. In this embodiment, the molar ratio of hydrogen:furan in the reactor vessel is preferably increased above the initial molar ratio of hydrogen:furan by a factor of 1.5, more preferably by a factor of 2, even more preferably by a factor of 4, and most preferably by a factor of 10.
Conversely, in the process of the present invention the molar ratio of 1,4-BDO to THF produced may be increased by lowering the partial pressure of hydrogen in the reactor vessel below the initial partial pressure of hydrogen in the reactor vessel. The partial pressure of hydrogen in the reactor vessel may be decreased below the initial partial pressure of hydrogen in the reactor vessel by a number of methods, including, but not limited to decreasing the total reactor pressure below the initial reactor pressure, increasing the reactor temperature above the initial reactor temperature, decreasing the molar ratio of water:furan in the reactor vessel below the initial molar ratio of water:furan, and/or by decreasing the molar ratio of hydrogen:furan in the reactor vessel below the initial molar ratio of hydrogen:furan.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is decreased by decreasing the total reactor pressure. This may be achieved by, amongst other ways, facilitating the exit of gaseous effluent, or any other means available in the art to the skilled person. In this embodiment, the total reactor pressure is preferably decreased below the initial total reactor pressure by at least 0.5 MPa, preferably by at least 2 MPa, more preferably by at least 5 MPa, and even more preferably by at least 9 MPa. In this embodiment, to decrease the partial pressure of hydrogen in the reactor vessel, the total reactor pressure may be preferably decreased below the initial reactor pressure in the reactor vessel by at most 13 MPa, and more preferably by at most 10 MPa.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is decreased below the initial partial pressure of hydrogen by increasing the reactor temperature above the initial reactor temperature. In this embodiment, the reactor temperature is preferably increased above the initial the reactor temperature by at least 10° C., more preferably by at least 25° C., even more preferably by at least 50° C., and most preferably by at least 100° C. In such embodiment, the reactor temperature is increased above the initial the reactor temperature preferably by at most 125° C. The operator of the process of the present invention may select and deploy any such increase in the reactor temperature above the initial reactor temperature once, or more than once, or in any combination, subject to the reactor temperature remaining at all times at, or below, 350° C.
In one embodiment of the invention, the partial pressure of hydrogen in the reactor vessel is decreased below the initial partial pressure of hydrogen by decreasing the molar ratio of water:furan in the reactor vessel. In this embodiment, the molar ratio of water:furan in the reactor vessel is preferably decreased below the initial molar ratio of water:furan by 25%, more preferably by 50%, even more preferably by 75%, most preferably by 90%.
In one embodiment of the invention, to increase the molar ratio of 1,4-BDO to THF produced by the process of the present invention, the partial pressure of hydrogen in the reactor vessel is decreased above the initial partial pressure of hydrogen by decreasing the molar ratio of hydrogen:furan in the reactor vessel. In this embodiment, the molar ratio of hydrogen:furan in the reactor vessel is preferably decreased below the initial molar ratio of hydrogen:furan by 25%, more preferably by 50%, even more preferably by 75%, and most preferably by 90%.
Any suitable reactor vessel may be used for the production of 1,4-BDO and THF from furan. These include, but are not limited to fixed bed and slurry reactors.
The invention will now be illustrated by the following non-limiting examples.
Catalysts were evaluated in a four-barrel microflow unit that consists of 4 parallel Hastelloy HC 276 reactor (1 cm ID). The reactors had an isothermal zone of 25 cm length and an internal volume of 41 mL. The reactors can be operated between 40 and 500° C. under 0.15 to 14 MPa pressure. The liquid feed was fed to the reactor by 1000 mL ISCO 1000D pumps with a maximum flow rate of 100 mL/h. Hydrogen was applied to the reactor through a mass flow controller with a maximum flow rate of 5 NL/h.
The catalysts were loaded as crushed (30-80 mesh) particles, as 3 g load, and diluted in an equal weight of SiC (0.2 mm). The catalysts used in each reactor comprised an active carbon support (RX3, commercially available from Norrit) that was impregnated with 4 wt % of Re and 0.04 wt % of Pd.
The initial catalyst reduction was carried at 275° C. for 16 h under atmospheric pressure and 1 Nl/h flow of 50 vol % H2 in N2 and, subsequently, for 2 h at 4 bara and a 1 NL/h flow of pure 100% H2. After reduction the temperature was lowered to 200° C., the hydrogen flow and pressure were set to target and the furan-containing liquid flow was admitted to the reactor.
The reaction was then carried out over a wide operation window for some 900 h time on stream, which is abbreviated herein as TOS. The window covered temperatures of 130-200° C., pressures of 30-130 bar, WHSV of 0.2-2/h, and feed concentrations of 12-30 w % for furan and 27-34 w % for water with EtOH as balance.
Table 1 reports the ratio of THF to 1,4-BDO produced under the conditions identified therein.
Example 1 was repeated with a catalyst comprising an active carbon support (RX3, commercially available from Norrit) that was impregnated with 5 wt % of Re and 1 wt % of Ru. The results are shown in Table 2.
Example 1 was repeated with a catalyst comprising a TiO2 support that was impregnated with 10 wt % of Re and 1 wt % of Ru. The results are shown in Table 3.
Example 1 was repeated with a catalyst comprising a TiO2 support that was impregnated with 2.6 wt % of Ru. The results are shown in Table 4.
| Number | Date | Country | Kind |
|---|---|---|---|
| 15174599.9 | Jun 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/064956 | 6/28/2016 | WO | 00 |
