Production of α,ω-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 Cu, a Cu oxide, or mixtures thereof; 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, Mn, a Mn oxide, Fe, an Fe oxide, Co, a Co oxide, Mo, a Mo oxide, W, a W oxide, Re, a Re oxide, Zn, or a Zn oxide, Ag, a Ag 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.
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 Cu, a Cu oxide, or mixtures thereof;
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, Mn, a Mn oxide, Fe, an Fe oxide, Co, a Co oxide, Mo, a Mo oxide, W, a W oxide, Re, a Re oxide, Zn, or a Zn oxide, Ag, a Ag 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 .
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 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 ].
10. The process of claim 1 , wherein the optional second metal component is present in the catalyst and comprises Cr, a Cr oxide, Mn, a Mn oxide, Zn, a Zn oxide, or mixtures thereof.
11. The process of claim 1 , wherein the optional promoter is present in the catalyst and comprises Ba, Cs, or mixtures thereof.
12. The process of claim 1 , wherein the catalyst comprises from 2 weight percent to 98 weight percent Cu and/or CuO, and further comprises from 98 weight percent to 2 weight percent of at least one oxide selected from the group consisting of zinc oxide, magnesium oxide, barium oxide, chromium oxide, silica, alumina, zirconium dioxide, nickel oxide, manganese oxide, sodium oxide, potassium oxide, cerium oxide, lanthanum oxide, iron oxide, silver oxide, and cobalt oxide, based on the total weight of the first metal component and the second metal component.
13. 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.
14. The process of claim 13 , wherein the α,ω-C n -diaminoalkane comprises 1,6-diaminohexane.