Condensation of glycols to produce biofuels
View Patent ↗The present disclosure relates to methods for converting light glycol streams of biological origin into products suitable for use as oxygenated fuel additives. These methods involve the acidic condensation of light glycols to form larger products, termed low molecular weight poly-glycols. The remaining hydroxyl functional groups of the poly-glycol products are then modified to decrease the overall polarity of the products, and improve their suitability for use as an oxygenated fuel additive.
1. A process comprising the steps of:
(a) providing a biomass-derived feedstream comprising light glycols, wherein said glycols comprise molecules containing two, three or four carbon atoms;
(b) contacting the feedstream of step (a) with a first catalyst in a reactor, wherein the contacting results in an acidic condensation reaction that converts a least a portion of the feedstream to condensation products, wherein said condensation products comprise at least 4 carbon atoms at least one ether functional group, and one or more remaining hydroxyl functional groups;
(c) converting at least a portion of the remaining hydroxyl functional groups on the condensation products from step (b) to ether functional groups by combining the condensation products with a second catalyst to produce a liquid hydrocarbon mixture suitable for use as an additive to liquid hydrocarbon fuels,
wherein the converting takes place in the presence of an olefin, monofunctional alcohol or mixtures thereof,
wherein the liquid hydrocarbon mixture has increased miscibility in liquid hydrocarbon fuels as a result of step c).
2. The process of claim 1 , wherein the feedstream of step (a) comprises a member selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,-butanediol, 1,3,-butanediol, 2,3-butanediol, 1,4-butanediol and mixtures thereof.
3. The process of claim 1 , further comprising combining the liquid hydrocarbon mixture of step (c) with a liquid hydrocarbon fuel to produce a improved liquid hydrocarbon fuel,
wherein the improved liquid hydrocarbon fuel has improved combustion properties relative to the original liquid hydrocarbon transportation fuel,
wherein said combustion properties comprise a member selected from the group consisting of increased cetane number, decreased emissions of environmental pollutants during combustion and combinations thereof.
4. The process of claim 1 , wherein the contacting of step (b) is conducted at a temperature in the range of about 100° to about 300° C., and at a pressure in the range of about 200 kPa to about 8000 kPa.
5. The process of claim 1 , wherein the contacting of step (b) is conducted at a temperature in the range of about 120° to about 260° C., and at a pressure in the range of about 500 kPa to about 5000 kPa.
6. The process of claim 1 , wherein the contacting of step (b) is conducted at a feedstream flow rate in the range of about 0.1 h −1 LWHSV to about 20 h −1 LWHSV.
7. The process of claim 1 ,
wherein the functions of the first catalyst and the second catalyst are performed by the same catalyst.
8. The process of claim 1 ,
wherein the first catalyst is a microporous molecular sieve selected from the group consisting of crystalline silicoaluminophosphates and aluminosilicates,
wherein said molecular sieve has been chemically treated to prevent catalytic activity outside the internal channels of the catalyst,
wherein the pore diameter of said molecular sieve restricts the catalytic formation of circular products inside the pores of the molecular sieve.
9. The process of claim 1 , wherein the second catalyst comprises an acidic macroreticular ion-exchange resin.
10. The process of claim 1 , wherein the first catalyst comprises at least two elements, one selected from Group 4 of the periodic table, and the other selected from Group 6 of the periodic table.
11. A process comprising the steps of:
(a) providing a biomass-derived feedstream comprising light glycols, wherein said glycols comprise molecules containing two, three or four carbon atoms;
(b) contacting the feedstream of step (a) with a first catalyst in a reactor, wherein the contacting results in an acidic condensation reaction that converts a least a portion of the feedstream to condensation products, wherein said condensation products comprise at least 4 carbon atoms at least one ether functional group, and one or more remaining hydroxyl functional groups;
(c) reducing at least a portion of the remaining hydroxyl groups on the condensation products from step (b) by combining the condensation products with a second catalyst in the presence of hydrogen to produce water and a liquid hydrocarbon mixture suitable for use as an additive for a liquid hydrocarbon fuel,
wherein the liquid hydrocarbon mixture has increased miscibility in liquid hydrocarbon fuels as a result of step c).
12. The process of claim 11 , wherein the feedstream of step (a) comprises a member selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,-butanediol, 1,3,-butanediol, 2,3-butanediol, 1,4-butanediol and mixtures thereof.
13. The process of claim 11 , further comprising combining the liquid hydrocarbon mixture of step (c) with a liquid hydrocarbon fuel to produce a improved liquid hydrocarbon fuel,
wherein the improved liquid hydrocarbon fuel has improved combustion properties relative to the original liquid hydrocarbon transportation fuel,
wherein said combustion properties comprise a member selected from the group consisting of increased cetane number, decreased emissions of environmental pollutants during combustion and combinations thereof.
14. The process of claim 11 , wherein the contacting of step (b) is conducted at a temperature in the range of about 100° to about 300° C., and at a pressure in the range of about 200 kPa to about 8000 kPa.
15. The process of claim 11 , wherein the contacting of step (b) is conducted at a temperature in the range of about 120° to about 260° C., and at a pressure in the range of about 500 kPa to about 5000 kPa.
16. The process of claim 11 , wherein the contacting of step (b) is conducted at a feedstream flow rate in the range of about 0.1 h −1 LWHSV to about 20 h −1 LWHSV.
17. The process of claim 11 ,
wherein the functions of the first catalyst and the second catalyst are performed by the same catalyst.
18. The process of claim 11 ,
wherein the first catalyst is a macroporous molecular sieve selected from the group consisting of crystalline silicoaluminophosphates and aluminosilicates,
wherein said molecular sieve has been chemically treated to decrease catalytic activity outside the internal channels of the catalyst,
wherein the pore diameter of said molecular sieve restricts the catalytic formation of circular products inside the pores of the molecular sieve.
19. The process of claim 11 , wherein the second catalyst comprises a commercial hydrotreating catalyst.
20. The process of claim 11 , wherein the first catalyst comprises at least two elements, one selected from Group 4 of the periodic table, and the other selected from Group 6 of the periodic table.