Production of alpha, omega-diols
View Patent ↗Disclosed herein are processes for preparing an α,ω-C n -diol, wherein n is 5 or greater, from a feedstock comprising a C n oxygenate. In one embodiment, the process comprises contacting the feedstock with hydrogen gas in the presence of a catalyst comprising Pt, Cu, Ni, Pd, Pt, Rh, Ir, Ru, or Fe on a WO 3 or WO x support. In one embodiment, the process comprises contacting the feedstock with hydrogen in the presence of a catalyst comprising a metal M1 and a metal M2 or an oxide of M2, and optionally a support. In one embodiment, M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Co. The C n oxygenate may be obtained from a biorenewable resource.
1. A process for preparing an α,ω-C n -diol, comprising the steps:
(a) providing a feedstock comprising a C n oxygenate;
(b) contacting the feedstock with hydrogen gas, in the presence of a catalyst at a temperature and for a time sufficient to form a product mixture comprising an α,ω-C n -diol; wherein n is 5 or greater;
and wherein the catalyst comprises a metal M1 and a metal M2 or an oxide of M2, and optionally a support, wherein:
M1 is Pd, Pt, or Ir; and M2 is Mo, W, V, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ge, Sn, Ti, Au, or Co.
2. The process of claim 1 , wherein n=5 or 6.
3. The process of claim 1 wherein the optional support is present in the catalyst and comprises WO 3 , SiO 2 , Al 2 O 3 , carbon, TiO 2 , ZrO 2 , SiO 2 —Al 2 O 3 , montmorillonite, SiO 2 —TiO 2 , tungstated ZrO 2 , zeolites, V 2 O 5 , MoO 3 , or mixtures thereof.
4. The process of claim 1 wherein the C n oxygenate comprises 1,2,6-hexanetriol; 1,2,5-pentanetriol; 2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol; furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol; levoglucosenone; levoglucosan; levoglucosenol; 1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide; hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol; 3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol; 1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol; 5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol; pentoses; dimers containing pentose; oligomers containing pentose; hexoses; dimers containing hexose; oligomers containing hexose; condensation products from the reaction of 5-(hydroxymethyl)-2-furfural with ketones and/or aldehydes, or condensation products from the reaction of furfural with ketones and/or aldehydes.
5. The process of claim 4 , wherein the C n oxygenate comprises 1,2,6-hexanetriol; 2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol; levoglucosenone; 3,4-dihydro-2H-pyran-2-carbaldehyde, or mixtures thereof.
6. The process of claim 5 , wherein the C n oxygenate comprises 1,2,6-hexanetriol.
7. The process of claim 4 , wherein the C n oxygenate comprises 1,2,5-pentanetriol; furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol; xylitol; or mixtures thereof.
8. The process of claim 1 , wherein:
M1 is Pd, Pt, or Ir; and M2 is Mo, W, Mn, Re, Zr, Ni, Cu, Zn, Cr, Ti, Au, or Co.
9. The process of claim 3 , wherein the support comprises TiO 2 , a zeolite, or mixtures thereof, and M1 is Pt, and M2 is W.
10. The process of claim 3 , wherein step (b) further comprises adding an additive comprising WO 3 , SiO 2 , Al 2 O 3 , carbon, TiO 2 , ZrO 2 , SiO 2 —Al 2 O 3 , montmorillonite, SiO 2 —TiO 2 , tungstated ZrO 2 , zeolites, V 2 O 5 , MoO 3 , or mixtures thereof.
11. The process of claim 1 , further comprising the steps:
(c) optionally, isolating the α,ω-C n -diol from the product mixture;
(d) contacting the α,ω-C n -diol with ammonia and hydrogen in the presence of a reductive amination catalyst at a temperature and for a time sufficient to form a second product mixture comprising an α,ω-C n -diaminoalkane; and
(e) optionally, isolating the α,ω-C n -diaminoalkane from the second product mixture.
12. The process of claim 11 , wherein the α,ω-C n -diaminoalkane comprises 1,6-diaminohexane.
13. A process for preparing an α,ω-C n -diol, comprising the steps:
(a) providing a feedstock comprising a C n oxygenate;
(b) contacting the feedstock with hydrogen gas, in the presence of a catalyst at a temperature and for a time sufficient to form a product mixture comprising α,ω-C n -diol; wherein n is 5 or greater; and wherein the catalyst comprises Pt, Cu, Ni, Pd, Rh, Ir, Ru, or Fe on a WO 3 or WO x support.
14. The process of claim 13 , wherein n=5 or 6.
15. The process of claim 13 wherein the C n oxygenate comprises 1,2,6-hexanetriol; 1,2,5-pentanetriol; 2H-tetrahydropyran-2-methanol; tetrahydrofuran-2,5-dimethanol; furan-2,5-dimethanol; 2,5 dihydrofuran-2,5-dimethanol; levoglucosenone; levoglucosan; levoglucosenol; 1,6-anhydro-3,4-dideoxy-p-D-pyranose-2-one; isosorbide; hydroxymethylfurfural; sorbitol; glucose; fructose; xylitol; 3,4-dihydro-2H-pyran-2-carbaldehyde; 1,2,5,6-hexanetetraol; 1,2,3,5,6-hexanepentanol; 1,5-anhydro-3,4-dideoxy-hexitol; 5-hydroxy-2H-tetrahydropyran-2 methanol; furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol; pentoses; dimers containing pentose; oligomers containing pentose; hexoses; dimers containing hexose; oligomers containing hexose; condensation products from the reaction of 5-(hydroxymethyl)-2-furfural with ketones and/or aldehydes, or condensation products from the reaction of furfural with ketones and/or aldehydes.
16. The process of claim 13 , further comprising the steps:
(c) optionally, isolating the α,ω-C n -diol from the product mixture;
(d) contacting the α,ω-C n -diol with ammonia and hydrogen in the presence of a reductive amination catalyst at a temperature and for a time sufficient to form a second product mixture comprising an α,ω-C n -diaminoalkane; and
(e) optionally, isolating the α,ω-C n -diaminoalkane from the second product mixture.
17. The process of claim 16 , wherein the α,ω-C n -diaminoalkane comprises 1,6-diaminohexane.
18. The process of claim 1 , wherein M1 is Pt and M2 is W.