Crystalline microporous material mediated conversion of C1-3 oxygenate compounds to C4 oxygenate compounds

Abstract

A process for the preparation of C.sub.4 oxygenate compounds such as threose, erythrose or erythrulose starting from a composition comprising C.sub.1-3 oxygenate compounds such as formaldehyde, glycolaldehyde, glyoxal, pyruvaldehyde or acetol, wherein the process is carried out in the presence of a crystalline microporous material having a ring pore structure selected from an eight-membered ring pore structure or a ten-membered ring pore structure.

Claims

1. A process for the preparation of one or more C.sub.4 oxygenate compounds of the formula C.sub.4H.sub.8O.sub.4 from a composition comprising C.sub.1-3 oxygenate compounds, the C.sub.4 oxygenate compounds selected from one or more of the group consisting of threose, erythrose and erythrulose, wherein the composition comprising C.sub.1-3 oxygenate compounds comprises glycolaldehyde and wherein the C.sub.4 oxygenates are selectively formed from glycolaldehyde in the presence of a solvent and a crystalline microporous material comprising a zeotype material comprising a metal selected from one or more of the group consisting of zirconium, aluminum, tin or titanium and having a structure selected from the group consisting of CHA, LTA, MFI, MEL, MTT, MWW, TON, HEU, AEL, AFO, and FER, wherein the C.sub.4 oxygenate compounds do not further react to form oxygenate compounds with a greater number of carbon atoms.

2. The process according to claim 1, wherein the composition comprising C.sub.1-3 oxygenate compounds further comprises one or more compounds selected from the group consisting of formaldehyde, glyoxal, pyruvaldehyde and acetol.

3. The process according to claim 2, wherein the composition comprising C.sub.1-3 oxygenate compounds comprises glycolaldehyde at a concentration of at least 5 wt %.

4. The process according to claim 1, wherein the solvent is selected from one or more of the groups consisting of water, alcohol and a water and alcohol mixture.

5. The process according to claim 4, wherein the alcohol is selected from one or more of the group consisting of methanol and ethanol.

6. The process according to claim 1, wherein the crystalline microporous material comprises from 0.1 wt % to 15 wt % of the metal.

7. The process according to claim 1, wherein the process is carried out at a temperature between 25° C. and 150° C.

8. The process according to claim 1, further comprising the step of hydrogenating the C.sub.4 oxygenate compounds.

9. The process according to claim 1, wherein the process is a one-step process.

10. The process according to claim 1, further comprising the steps of isomerizing and esterifying the C.sub.4 oxygenate compounds in the presence of Sn zeolite beta (Sn-BEA).

11. The process according to claim 1, further comprising the step of converting the C.sub.4 oxygenate compounds to one or more compounds selected from the group consisting of erythritol and threitol.

12. The process according to claim 1, wherein a prior step is performed of pyrolyzing biomass or one or more oxygenate compounds selected from the group consisting of fructose, glucose, sucrose, xylose or isomers thereof, to produce a composition comprising the C.sub.1-3 oxygenate compounds.

Description

EXAMPLE 1

(1) Crystalline Microporous Material (Sn-MFI, Ti-MFI, Sn-BEA and Sn-LTA) Preparation:

(2) Sn-MFI:

(3) 200 Sn-MFI (Si/Sn=200) is prepared according to the method described by Mal et al. (Mal, N. K.; Ramaswamy, V.; Ra-jamohanan, P. R.; Ramaswamy, A. V. Sn-MFI molecular sieves: Synthesis methods, 29Si liquid and solid MAS-NMR, 119Sn static and MAS NMR studies. Microporous Mater., 1997, 12, 331-340). According to this procedure NH.sub.4F (5.35 g) is dissolved in demineralized water (25.0 g). A solution of SnCl.sub.4.5H.sub.2O (0.25 g) in H.sub.2O (10.0 g) is added under rapid stirring. After this, of tetrapropylammonium bromide [TPABr (9.8 g)] in H.sub.2O (56.0 g) is added slowly. Fumed silica (8.6 g) is dissolved in the mixture. The mixture is stirred for 3 hours and the gel is then transferred to a Teflon lined autoclave and crystallized at 200° C. for 6 days. The product is then suction filtrated with ample water and dried over-night at 80° C. Recovered powder is calcined at 550° C. (2° C./min) for 6 hours. 400Sn-MFI (Si/Sn=400) is prepared following the same procedure but adjusting the amount of SnCl.sub.4.5H.sub.2O.

(4) Sn-MFI (Alternative Preparation):

(5) 200 Sn-MFI (Si/Sn=200) can be prepared from ZSM-5 (Ze-ochem, ZEOcat® PZ-2 100H). ZSM-5 is treated under steam at 450° C. for 6 h, acid washed with HCl 1 M at 100° C. for 16 h, and washed with ample water. The solid is dried at 120° C. for 16 h, impregnated with an aqueous solution of SnCl.sub.2 and calcined at 550° C. (2° C./min) for 6 h.

(6) Ti-MFI:

(7) 200 Ti-MFI (Si/Ti=200) is prepared according to a modification of the method described by Mal et al. (Mal, N. K.; Ramaswamy, V.; Rajamohanan, P. R.; Ramaswamy, A. V. Sn-MFI molecular sieves: Synthesis methods, 29Si liquid and solid MAS-NMR, 119Sn static and MAS NMR studies. Microporous Mater., 1997, 12, 331-340). According to this procedure NH.sub.4F (5.35 g) is dissolved in demineralized water (25.0 g). A solution of Ti (IV) ethoxide (0.17 g) in H.sub.2O (3.5 g) and H.sub.2O.sub.2 (6.5 g) is added under rapid stirring. After this, a solution of tetrapropylammonium bromide [TPABr (9.8 g)] in H.sub.2O (56.0 g) is added slowly. Fumed silica (8.6 g) is dissolved in the mixture. The mixture is stirred for 20 hours and the gel is then transferred to a Teflon lined autoclave and crystallized at 200° C. for 6 days. The product is then suction filtrated with ample water and dried overnight at 80° C. Recovered powder is calcined at 550° C. (2° C./min) for 6 hours.

(8) Sn-BEA:

(9) Sn-BEA was prepared according to the method described in EP 2184270 B1.

(10) Sn-LTA:

(11) 125 Sn-LTA with (Si/Sn=125) can be prepared from LTA zeolite (Sigma-Aldrich, Molecular sieves, 4Å). LTA is treated under steam at 450° C. for 6 h, acid washed with HCl 1 M at 100° C. for 16 h, and washed with ample water. The solid is dried at 120° C. for 16 h, impregnated with an aqueous solution of SnCl.sub.2 and calcined at 550° C. (2° C./min) for 6 h.

(12) Preparation of C.sub.4 oxygenate compounds from glycolaldehyde:

EXAMPLE 2

(13) Crystalline microporous material (0.15 g) prepared according to Example 1, glycolaldehyde dimer [SAFC, 0.25 g] and deionized water (5 g) are added in a 20 mL vial (Ace pressure tube) and heated at 80° C. under vigorous stirring (600 rpm). Samples of the reaction are taken at selected times (0.5-24 h). Analysis of the liquid samples after filtration is carried out using a HPLC Agilent 1200 equipped with a BIORAD Amminex HPX-87H column at 65° C. and 0.004 M H.sub.2SO.sub.4 solution in water at 0.6 ml min.sup.−1.

(14) TABLE-US-00001 TABLE 1 The percentage yield of C.sub.4 oxygenate compounds produced from an aqueous glycolaldehyde solution over time with various crystalline microporous materials. Percentage yield (%) of C.sub.4-oxygenate compounds Time (h) 400Sn-MFI 200Sn-MFI Ti-MFI Sn-BEA Sn-LTA 1 30.8 66.3 18.5 26.1 37.5 3 59.2 70.8 34.5 23.9 51.17 24 73.4 53.6 57.7 0 55.58

EXAMPLE 3

(15) Compositions comprising C.sub.1-3 oxygenate compounds may be prepared by pyrolysis of biomass or C.sub.5-6 sugars (C.sub.5-6 oxygenate compounds) such as glucose, sucrosqe, fructose or xylose. Exemplary pyrolysis reactions are provided in U.S. Pat. No. 7,094,932 B2 and PCT/EP2014/053587. The C.sub.1-3 oxygenate compositions comprise 5 wt % glycolaldehyde or greater, such as between 5 wt % and 65 wt %.

(16) A composition comprising C.sub.1-3 oxygenate compounds obtained from the pyrolysis of glucose according to U.S. Pat. No. 7,094,932 B2 is diluted in water to obtain 5 g of a solution comprising 8 wt % glycolaldehyde. Crystalline microporous material (0.15 g), prepared according to Example 1 is added to the mixture in a 20 mL vial (Ace pressure tube) and the reaction is heated at 80° C. under vigorous stirring (600 rpm). Samples of reaction are taken at selected times (0.5-24 h). Analysis of the liquid samples after filtration is carried out as previously explained.

(17) TABLE-US-00002 TABLE 2 The percentage yield of C.sub.4 oxygenate compounds produced from an aqueous solution of a C.sub.1-3 oxygenate mixture according to Example 2 versus time. Various crystalline microporous materials are shown. Percentage yield (%) of C.sub.4 oxygenate compounds Time (h) 400Sn-MFI 200Sn-MFI Ti-MFI Sn-BEA 1 7.7 21.7 6.7 7.4 3 13.1 35.5 11.2 22.5 24 39.4 52.9 40.2 21.8

EXAMPLE 4

(18) Hydrogenation of C.sub.4 oxygenate compounds is carried out in an autoclave reactor at pressures 30-90 bar of H.sub.2. The reaction is carried out by addition of a composition comprising C.sub.4 oxygenate compounds (15 g), prepared according to Example 2 or 3, into a Parr autoclave (50 mL) together with of Ru/C catalyst (0.2 g; 5% on activated charcoal from Aldrich). The reactor is heated at 80° C. and stirred at 500 rpm for 3 h.

EXAMPLE 5

(19) Concomitant conversion of glycolaldehyde to C.sub.4 oxygenate compounds and subsequent hydrogenation. (‘one-pot’ or ‘one-step’ conversion and hydrogenation).

(20) Glycolaldehyde dimer (SAFC, 0.25 g), Sn-MFI (0.1 g) prepared according to Example 1, Ru/C catalyst (0.075 g; 5% on activated charcoal from Aldrich) and water (15 g) are added in a 50 mL Parr autoclave. The first condensation reaction is carried out at 80° C. in air atmosphere. After 3 h of reaction, the autoclave is pressurized with hydrogen at 90 bar and the reaction is allowed to proceed for 3 h. Samples of the products are obtained after the condensation step and the hydrogenation and analyzed after filtration in an HPLC as previously explained.

(21) Alternatively, vinyl glycolic acid or methyl vinyl glycolate (MVG) can be obtained by reaction of a composition comprising C.sub.4 oxygenate compounds prepared according to Examples 1 or 2 with Sn-BEA catalyst in water or methanol respectively; Green Chemistry (2012) 14, pp 702-706.

(22) FIG. 1: The percentage yield of C.sub.4 oxygenate compounds prepared according to Example 2 versus time. Various crystalline microporous materials are shown. The crystalline microporous materials are:

(23) Squares: 200Sn-MFI;

(24) Circles: Ti-MFI;

(25) Triangles: Sn-BEA.

(26) FIG. 2: The percentage yield of C.sub.4 oxygenate compounds prepared according to Example 3 versus time. Various crystalline microporous materials are shown.

(27) The crystalline microporous materials are:

(28) Squares: 200Sn-MFI;

(29) Circles: Ti-MFI;

(30) Triangles: Sn-BEA.