Biphasic solvent catalytic process for the direct production of light naphtha from carbohydrate-containing feedstock
The disclosure describes a one-step liquid biphasic catalytic process for converting a carbohydrate-containing feedstock, preferably lignocellulose, to light naphtha (e.g., hexane, pentane, methyl cyclopentane, cyclohexane, etc.) in the presence of an acidic reactive aqueous phase and a redox catalyst in the organic extracting/reaction phase. The process provides a cost-effective route for producing light-naphtha components, in presence or not of deoxygenates. The light naphtha components are useful as feedstock for steam and catalytic cracking to produce value-added platform molecules like ethylene and propylene, as precursor for the synthesis of bioaromatics like benzene and as gasoline fuel feedstock, and as fuel additives (e.g., the concomitantly formed oxygenates) to improve the biological origin of carbon in the fuel.
1. A biphasic solvent catalytic process of producing light naphtha, the process comprising:
supplying an aqueous reaction solution, a carbohydrate-containing feedstock, an acid catalyst, a substantially water-immiscible organic phase, and a redox catalyst into a reaction vessel under hydrogen pressure to generate a biphasic liquid medium, wherein the biphasic liquid medium comprises the aqueous reaction solution mainly comprising the carbohydrate-containing feedstock and the acid catalyst, and wherein the organic phase mainly comprises the redox catalyst and functions as an organic extraction and reaction solution,
energizing or heating the biphasic liquid medium, thus inducing conversion of carbohydrate in the aqueous phase to a furan derivative, and
extracting the furan derivative into the organic phase so as to hydrogenate the furan derivative into light naphtha,
wherein the redox catalyst is typified by an H factor larger than 2.
2. A process to make light naphtha, the process comprising:
utilizing a reaction vessel under hydrogen pressure containing a biphasic liquid medium comprising an aqueous reaction solution and a substantially water-immiscible organic extraction and reaction solution;
wherein the aqueous reaction solution contains at least a carbohydrate-containing feedstock and an acid catalyst and the substantially water-immiscible organic extraction and reaction solution contains at least a redox catalyst to attain light naphtha;
wherein the carbohydrate is converted in the aqueous reaction solution into a furan derivative,
wherein the furan derivative is extracted from the aqueous reaction solution and converted to light naphtha in the substantially water-immiscible organic extraction and reaction solution in presence of the redox catalyst; and
wherein the redox catalyst favorably hydrogenates furan derivatives in presence of hexoses.
3. The process according to claim 2 , wherein the redox catalyst is characterized by an H-factor larger than 2.
4. The process according to claim 1 , wherein the carbohydrate in the carbohydrate-containing feedstock is selected from the group consisting of starch, cellulose, hemicellulose, lignocellulose, and a mixture thereof.
5. A biphasic solvent catalytic process for producing light naphtha, the process comprising:
supplying into a reaction vessel under hydrogen pressure: an aqueous reaction solution, a carbohydrate-containing feedstock, an acid catalyst, a substantially water-immiscible organic phase, and a redox catalyst so as to generate a biphasic liquid medium comprising an aqueous phase and an organic phase, wherein the organic phase mainly comprises the redox catalyst and functions as an organic extraction and reaction solution,
energizing or heating the biphasic liquid medium to induce conversion of carbohydrate in the aqueous phase to a furan derivative, and
extracting the furan derivative with the organic phase so as to hydrogenate the furan derivative into light naphtha, wherein the relative hydrogenation reactivity factor H of the redox catalyst is greater than or equal to 1.25.
6. The process according to claim 1 , wherein the redox catalyst comprises a metal selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ir, and Pt, and mixtures thereof.
7. The process according to claim 1 , wherein the redox catalyst is modified with heteropolyacid (HPA).
8. The process according to claim 1 , wherein the acid catalyst is an inorganic acid.
9. The process according to claim 1 , wherein the acid catalyst is selected from the group consisting of homopolyacids and heteropolyacids.
10. The process according to claim 1 , wherein the organic extraction and reaction solution comprises a solvent selected from the group consisting of water-immiscible, linear, branched and cyclic alkanes, or mixtures thereof.
11. The process according to claim 1 , wherein the major part of the hydrolysis and dehydration reactions mainly occur at a temperature ranging from 70° C. to 200° C., and a further hydrodeoxygenation is occurring at a temperature ranging from 150° C. to 350° C.
12. The process according to claim 1 , wherein the hydrogen pressure(s) ranges from 1 to 150 bars.
13. The process according to claim 1 , wherein the carbohydrate-containing feedstock comprises 1 to 50 wt % of the total reaction mixture.
14. A method of converting a carbohydrate-containing feedstock directly to light naphtha and a family of organic phase soluble oxygenates, essentially comprising molecules with 5 and 6 carbon atoms in a reaction vessel under hydrogen pressure, the method comprising:
at least the carbohydrate and an acid catalyst in an aqueous reaction phase and at least a redox catalyst in an organic extractive and reaction phase,
wherein the carbohydrate is converted to hydroxymethylfurfural (“HMF”) in the aqueous reaction phase,
wherein the HMF is extracted in the organic extractive and reaction phase and further hydrodeoxygenated to light naphtha.
15. The method according to claim 14 , wherein the carbohydrate in the carbohydrate-containing feedstock is selected from the group consisting of starch, cellulose, hemicellulose, lignocellulose, and a mixture thereof.
16. The method according to claim 14 , wherein relative hydrogenation reactivity factor H of the redox catalyst is equal to or larger than 1.25.
17. The method according to claim 14 , wherein the redox catalyst comprises a metal selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Ir, and Pt, or a mixture thereof.
18. The method according to claim 14 , wherein the redox catalyst is modified with heteropolyacid (HPA).
19. The method according to claim 14 , wherein the acid catalyst is an inorganic acid.
20. The method according to claim 14 , wherein the acid catalyst is selected from the group consisting of homopolyacids and heteropolyacids.
21. The method according to claim 14 , wherein the organic extractive and reaction solution comprises a solvent selected from the group consisting of water-immiscible, linear, branched, cyclic alkanes, and mixtures thereof.
22. The method according to claim 14 , wherein the major part of the hydrolysis and dehydration reactions mainly occur at a temperature ranging from 70° C. to 200° C., and the further hydrodeoxygenation is occurring at a temperature ranging from 150° C. to 350° C.
23. The method according to claim 14 , wherein the hydrogen pressure(s) ranges from 1 to 150 bars.
24. The method according to claim 14 , wherein the carbohydrate-containing feedstock comprises 1 to 50 wt % of the total reaction mixture.