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 a first metal component comprising Ni, Ir, Pt, Rh, Ru, Pd, Fe, Ag, or Au; a heteropoly acid component comprising H 3 [P(W 3 O 10 ) 4 ], H 4 [Si(W 3 O 10 ) 4 ], H 4 [P(Mo 3 O 10 ) 4 ], H 4 [Si(Mo 3 O 10 ) 4 ], Cs 2.5 H 0.5 [P(W 3 O 10 ) 4 ]Cs 2.5 H 0.5 [Si(W 3 O 10 ) 4 ], or mixtures thereof; optionally a second metal component comprising Cr, a Cr oxide, Ni, a Ni oxide, Fe, a Fe oxide, Co, a Co oxide, Mn, a Mn oxide, Mo, a Mo oxide, W, a W oxide, Re, a Re oxide, Zn, a Zn oxide, SiO 2 , or Al 2 O 3 ; optionally at least one promoter comprising Na, K, Mg, Rb, Cs, Ca, Sr, Ba, Ce, or mixtures thereof; and optionally a support. In one embodiment, 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. 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 and 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 first metal component, a heteropoly acid component, optionally a second metal component, optionally at least one promoter, and optionally a support; wherein:
the first metal component comprises Ni, Ir, Pt, Rh, Ru, Pd, Fe, Ag, or Au;
the heteropoly acid component comprises H 3 [P(W 3 O 10 ) 4 ], H 4 [Si(W 3 O 10 ) 4 ], H 4 [P(Mo 3 O 10 ) 4 ], H 4 [Si(Mo 3 O 10 ) 4 ], Cs 2.5 H 0.5 [P(W 3 O 10 ) 4 ], Cs 2.5 H 0.5 [Si(W 3 O 10 ) 4 ], or mixtures thereof;
the second metal component comprises Cr, a Cr oxide, Ni, a Ni oxide, Fe, a Fe oxide, Co, a Co oxide, Mn, a Mn oxide, Mo, a Mo oxide, W, a W oxide, Re, a Re oxide, Zn, a Zn oxide, SiO 2 , or Al 2 O 3 ; and
the promoter comprises Na, K, Mg, Rb, Cs, Ca, Sr, Ba, Ce, or mixtures thereof.
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 3 , wherein the support comprises SiO 2 , TiO 2 , zeolites, or mixtures thereof.
5. 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; 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; and condensation products from the reaction of furfural with ketones and/or aldehydes.
6. The process of claim 5 , 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.
7. The process of claim 6 , wherein the C n oxygenate comprises 1,2,6-hexanetriol.
8. The process of claim 5 , wherein the C n oxygenate comprises 1,2,5-pentanetriol; furfural; furfuryl alcohol; tetrahydrofurfuryl alcohol; xylitol; or mixtures thereof.
9. The process of claim 1 , wherein the first metal component comprises Ni, Pt, Pd, Fe, or Ru.
10. The process of claim 1 , wherein the heteropoly acid component comprises H 3 [P(W 3 O 10 ) 4 ], H 4 [Si(W 3 O 10 ) 4 ], or Cs 2.5 H 0.5 [P(W 3 O 10 ) 4 ].
11. The process of claim 1 , wherein the optional second metal component is present in the catalyst and comprises W or Re.
12. The process of claim 1 , wherein the optional promoter is present in the catalyst and comprises Cs.
13. The process of claim 1 , wherein the first metal component comprises Ni, Pt, Pd, Fe, or Ru; the heteropoly acid component comprises H 3 [P(W 3 O 10 ) 4 ], H 4 [Si(W 3 O 10 ) 4 ], or Cs 2.5 H 0.5 [P(W 3 O 10 ) 4 ]; and the optional second metal component is present in the catalyst and comprises W or Re.
14. 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.
15. The process of claim 14 , wherein the α,ω-C n -diaminoalkane comprises 1,6-diaminohexane.