Integrated process for direct saccharification and dehydration of intact biomass to furfurals
A method of converting a lignocellulosic biomass to monosaccharides, and optionally further converting the monosaccharides to one or both of furfural and HMF, includes contacting the biomass with a reactive liquid phase comprising LiBr, H 2 SO 4 , and water, wherein H 2 SO 4 preferably constitutes at most 1.0 wt %, more preferably at most 0.5 wt %, and most preferably at most 0.1 wt % of the reactive liquid phase, and water preferably constitutes at most at most 60 wt %, more preferably at most 50 wt %, and most preferably at most 30 wt % of the reactive liquid phase.
1. An integrated one-pot two-step method of converting an intact lignocellulosic biomass to C5 and C6 monosaccharides, and further converting the C5 and C6 monosaccharides to furfural and HMF, said method comprising:
a first step of contacting the intact lignocellulosic biomass with a reactive liquid phase comprising LiBr, H 2 SO 4 , and water to convert the biomass to C5 and C6 monosaccharides, and
a second step of contacting the reactive liquid phase with a Lewis acid and an organic solvent immiscible with the reactive liquid phase to form a biphasic system, wherein a conversion of C5 and C6 monosaccharides to furfural and HMF occurs in the reactive liquid phase with concurrent extraction of furfural and HMF from the reactive liquid phase to the organic solvent phase,
wherein a ratio by volume of the reactive liquid phase to the organic solvent phase is in a range from 1:10 to 10:1,
wherein H 2 SO 4 constitutes at most 1.0 wt % of the reactive liquid phase, and water constitutes at most 60 wt % of the reactive liquid phase, and
wherein the reactive liquid phase is a LiBr-molten salt hydrate phase.
2. The integrated method according to claim 1 , wherein the Lewis acid is selected from the group consisting of AlCl 3 , CrCl 3 , SnCl 4 , ZrO(OCl), Sn-Beta, Zr-Beta, Hf-Beta, Sn-MFI, TiO 2 , and Lewis acidic-carbonaceous materials, and wherein the Lewis acid is present in an amount of at least 10 mol % and at most 200 mol % relative to total C5 and C6 monosaccharides in the reactive liquid phase.
3. The integrated method according to claim 1 , wherein the organic solvent phase comprises ethyl acetate and wherein the ratio by volume of the reactive liquid phase to the solvent phase is in a range from 1:5 to 5:1.
4. The integrated method according to claim 3 , wherein the step of contacting the reactive liquid phase with the organic solvent phase is performed at a temperature of at least 25° C. and no higher than 140° C.
5. The integrated method according to claim 1 , wherein at least 60% of each of the C5 and C6 monosaccharides are converted to furfural and HMF respectively.
6. The integrated method according to claim 1 , wherein the C5 and C6 monosaccharides comprise glucose and xylose and wherein the yields of glucose and xylose in the reactive liquid phase are each individually at least 50%, based on the glucan and xylan content of the biomass, respectively.
7. The integrated method according to claim 1 , wherein the yields of HMF and furfural in the organic solvent phase are each individually at least 50%, based on the amount of C5 and C6 monosaccharides produced in the reactive liquid phase, respectively.
8. The integrated method according to claim 1 , wherein the viscosity of the reactive liquid phase is at least 2 mPa·s.
9. The integrated method according to claim 1 further comprising the steps of separating the organic solvent phase from the biphasic system and reusing the reactive MSH liquid phase containing LiBr, H 2 SO 4 , water, and the Lewis acid by:
contacting the used reactive MSH liquid phase with another batch of intact lignocellulosic biomass, and
adding the organic solvent comprising ethyl acetate to the used reactive MSH liquid phase such that a ratio by volume of the used reactive MSH liquid phase to the organic solvent phase is in a range from a range from 1:10 to 10:1.
10. An integrated one-pot two-step method of converting a lignocellulosic biomass to C5 and C6 monosaccharides, and further converting the C5 and C6 monosaccharides to furfural and HMF, said method comprising:
a first step of contacting the lignocellulosic biomass with a reactive molten salt hydrates (MSH) liquid phase comprising LiBr, H 2 SO 4 , and water to convert the biomass to C5 and C6 monosaccharides, and
a second step of contacting the reactive MSH liquid phase with a Lewis acid and an organic solvent immiscible with the reactive MSH liquid phase to form a biphasic system, wherein a conversion of C5 and C6 monosaccharides to furfural and HMF occurs in the reactive MSH liquid phase with concurrent extraction of furfural and HMF from the reactive MSH liquid phase to the organic solvent phase,
wherein the organic phase comprises ethyl acetate,
wherein a ratio by volume of the reactive MSH liquid phase to the organic solvent phase is in a range from 1:10 to 10:1, and
wherein H 2 SO 4 constitutes at most 1.0 wt % of the reactive MSH liquid phase, and water constitutes at most 60 wt % of the reactive MSH liquid phase.
11. The integrated method according to claim 10 , wherein the Lewis acid is selected from the group consisting of AlCl 3 , CrCl 3 , SnCl 4 , ZrO(OCl), Sn-Beta, Zr-Beta, Hf-Beta, Sn-MFI, TiO 2 , and Lewis acidic-carbonaceous materials and wherein the Lewis acid constitutes at least 10 mol % and at most 200 mol % relative to total monosaccharides in the reactive liquid phase.
12. The integrated method according to claim 10 , wherein the lignocellulosic biomass is not pretreated prior to said contacting.
13. The integrated method according to claim 10 , wherein the lignocellulosic biomass comprises intact or extractive-free and partially lignin-removed biomass; or intact or extractive-free wood, switch grass, corn stover, pine, douglas fir, alder, partially lignin-removed cellulose pulp or cellulose.
14. The integrated method according to claim 10 , wherein the yields of HMF and furfural in the organic solvent phase are each individually at least 60%, based on the amount of C5 and C6 monosaccharides produced in the reactive phase, respectively.
15. The integrated method according to claim 10 further comprising the steps of separating the solvent phase from the biphasic system and reusing the reactive MSH liquid phase containing LiBr, H 2 SO 4 , water, and the Lewis acid by:
contacting the reactive MSH liquid phase with another batch of lignocellulosic biomass, and
adding an organic solvent comprising ethyl acetate to the used reactive MSH liquid phase such that a ratio by volume of the used reactive MSH liquid phase to the organic solvent phase is in a range from a range from 1:10 to 10:1.
16. The integrated method according to claim 10 , wherein the step of contacting the reactive MSH liquid phase with the organic solvent phase is performed at a temperature of at least 25° C. and no higher than 140° C.
17. The integrated method according to claim 10 , wherein side products of the conversion of C5 and C6 monosaccharides to furfural and HMF remain in the reactive MSH liquid phase, the side products comprising levulinic acid, humins and formic acid.