TRANSPORTATION FUELS FROM BIOMASS OXYGENATES

• US 20130237728A1
• Filed: 03/09/2012
• Published: 09/12/2013
• Est. Priority Date: 03/09/2012
• Status: Active Grant

• Current Assignee: Phillips 66 Company
• Original Assignee: Conocophillips Company (ConocoPhillips)
• Inventors: LOTERO, Edgar, FJARE, Kristi, SHI, TiePan, BAO, Yun, PANSARE, Sourabh
• Granted Patent: US 8,629,310 B2
• Time in Patent Office: Days
• US Class Current: 585/242
• CPC Class Codes: B01J 21/14 Silica and magnesia
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 23/78 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 23/8885 containing also molybdenum
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/638 more than 1.0 ml/g
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/20 Sulfiding
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/304 Pour point, cloud point, cold flow properties
• CPC Class Codes: C10G 2300/307 Cetane number, cetane index
• CPC Class Codes: C10G 2300/308 Gravity, density, e.g. API
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10G 2400/08 : Jet fuel
• CPC Class Codes: C10G 3/44 : characterised by the catalyst used
• CPC Class Codes: C10G 3/45 : containing iron group metals or compounds thereof
• CPC Class Codes: C10G 3/47 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/50 : in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/04 : characterised by the catalyst used
• CPC Class Codes: C10G 45/12 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10G 69/126 : polymerisation, e.g. oligomerisation
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 1/06 : for spark ignition
• CPC Class Codes: C10L 1/08 : for compression ignition
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

Oxygenate feedstocks derived from biomass are converted to a variety of fuels including gas, jet, and diesel fuel range hydrocarbons. General methods are provided including hydrolysis, dehydration, hydrogenation, condensation, oligomerization, and/or a polishing hydrotreating.

Claims

1. A method of converting biomass oxygenates into hydrocarbon fuels comprising:

a) providing a biomass derived oxygenate feed;

b) hydrogenating the oxygenate feed with a hydrogenation catalysts to produce a hydrogenated product;

c) condensing the hydrogenated product with a condensation catalyst to produce a condensed or oligomerized product;

d) polishing the condensed or oligomerized product with a hydroprocessing catalyst (HPC) to produce hydrocarbon range fuel products; and

e) isolating one or more hydrocarbon range fuel products.

2. The method of claim 1, wherein said oxygenate feedstock is derived from a biomass selected from the group consisting of sugars, carbohydrates, lignins, fatty acids, proteins, oils, eucalyptus oil, forest residues, dead trees, branches, leaves, tree stumps, yard clippings, wood chips, wood fiber, sugar beets, miscanthus, switchgrass, hemp, corn, corn fiber, poplar, willow, sorghum, sugarcane, palm oil, corn syrup, algal cultures, bacterial cultures, fermentation cultures, paper manufacturing waste, farming residues, food manufacturing waste, meat processing waste, municipal solid waste, animal waste, biological waste, sewage, and combinations thereof.

3. The method of claim 1, wherein said oxygenate feedstock comprises one or more oxygenates selected from the group consisting of carbohydrates, sugars, pentoses, hexoses, monosaccharides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, levoglucosan, sucrose, manose, glucose, xylose, isosorbide, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, arabitol, mannitol, sorbitol, dulcitol, maltitol, arabinitol, isosorbide, glycerol, glycerin, alcohol, methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), butanol (BuOH), n-butanol, t-butanol, ethers, methyl tert-butyl ether (MTBE), tertiary amyl methyl ether (TAME), tertiary hexyl methyl ether (THEME), ethyl tertiary butyl ether (ETBE), tertiary amyl ethyl ether (TAEE), diisopropyl ether (DIPE), hydroxymethyl-tetrahydrofuran or tetrahydro-2-furfuryl alcohol (THFA), methyl-tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydrofuran, diols, methanediol (H₂C(OH)₂), ethylene glycol, propane diols, 1,2-propanediol, 1,3-propanediol, butanediols, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentane diols, 1,2-pentanediol, 1,5-pentanediol, octanediol, 1,8-octanediol, etohexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, aldehydes, propanal, butanal, 2,5-furan-diacrboxyaldehyde, carboxylates, acetic acid, oxopropanoic acid, acrylic acid, levulinic acid, succinic acid, 2,5-furan-dicarboxylic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, acetylacrylic acid, 4-O-Me-glucuronic acid, gluconic acid, xylonic acid, esters, levuninate esters, lactones, valero lactone, α

-methylene-γ

-valerolactone, angelica lactones, trisaccharides, oligosaccharides, polysaccharides, starch, derivatives, dimers, trimers, and polymers thereof.

4. The method of claim 1, further comprising one or more of the following reaction conditions:

a) wherein said oxygenate is hydrogenated at temperatures between approximately 100 and 400°

C. and pressures between approximately 100-1200 psig, including temperatures of approximately 100°

C., 125°

C., 150°

C., 175°

C., 200°

C., 225°

C., 250°

C., 275°

C., 300°

C., 325°

C., 350°

C., 375°

C., or 400°

C. and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, or 1200 psig;

b) wherein said hydrogenated product is condensed and/or oligomerized at temperatures between approximately 200 and 600°

C. and pressures between approximately 100-1200 psig, including temperatures of approximately 200°

C., 225°

C., 250°

C., 275°

C., 290°

C., 300°

C., 325°

C., 350°

C., 375°

C., 400°

C., 425°

C., 450°

C., 475°

C., 500°

C., 525°

C., 550°

C., 575°

C., or 600°

C. and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, or 1200 psig; and

c) wherein said condensed and/or oligomerized product is polished at temperatures between approximately 200 and 400°

C. and pressures between approximately 100-2000 psig, including temperatures of approximately 200°

C., 225°

C., 250°

C., 275°

C., 290°

C., 300°

C., or 350°

C., and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, 1200 psig, 1400 psig, 1600 psig, 1800 psig or 2000 psig.

5. The method of claim 1:

a) wherein said hydrogenation catalysts is selected from the group consisting of ceria (Ce), magnesium (Mg), nickel (Ni), cobalt.(Co), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and combinations thereof;

b) wherein said condensation catalyst is selected from the group consisting of alumina, silica, silica-alumina, zirconia, titania, ceria, manganese oxide, magnesium, praseodymium oxide, samarium oxide, and combinations thereof;

c) wherein said condensation catalyst has a promoter selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), Iron (Fe), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), and combinations thereof;

d) wherein said polishing catalyst is selected from the group consisting of molybdenum (Mo), tungsten (W), cobalt (Co), nickel (Ni), NiW, NiMo, CoMo, and combinations thereof;

or

e) wherein said polishing catalyst support is selected from the group consisting of carbon, alumina, silica, zeolite, ceramic, Al₂O₃, and the like.

6. The method of claim 1, wherein said hydrocarbon range fuel products are distilled to one or more renewable hydrocarbon fuels selected form the group consisting of gasoline, diesel, and jet-fuel.

7. The method of claim 1, wherein said renewable hydrocarbon fuel products comprise naphthene hydrocarbons and mixtures thereof.

8. The method of claim 1, comprising:

a) hydrogenation selected from one of the following conditions;

i) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is ruthenia-carbon catalyst, said temperature is approximately 100-150°

C., said pressure is approximately 400-1000 psig, or

ii) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is a nickel-based catalyst, said temperature is approximately 200-250°

C., said pressure is approximately 800-1000 psig;

b) condensation selected from one of the following conditions;

i) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

ii) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is magnesia-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iii) wherein said oxygenate comprises tetrahydrofurfuryl alcohol, said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iv) wherein said oxygenate comprises levulinic acid, said condensation catalyst is a noble-metal catalyst, said temperature is approximately 200-340°

C. and said pressure is approximately 1200 psig,

v) wherein said oxygenate comprises sorbitol, said condensation catalyst is a Co/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig, or

vi) wherein said oxygenate comprises a levulinic acid/formic acid mixture said condensation catalyst is a NiCu/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig; and

c) polishing selected from one of the following conditions;

i) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-8380°

C., and said pressure is approximately 800-81800 psi,

ii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-320°

C., and said pressure is approximately 800-1200 psi,

iii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, or

iv) wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-380°

C., and said pressure is approximately 800-2000 psi.

9. The method of claim 1, comprising a product with naphtha, renewable distillate, VGO range fraction comprising naphtha range hydrocarbons with, distillate range hydrocarbon fuel comprising hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable distillate range fraction comprises:

i) approximately 1 to 12 wt % paraffins;

ii) approximately 60 to 80 wt % naphthenes;

iii) approximately 15 to 40 wt % 1-ring naphthenes;

iv) approximately 20 to 40 wt % 2-ring naphthenes;

v) approximately 5 to 15 wt % 3-ring naphthenes; and

vi) approximately 0 to 20 wt % aromatics.

10. The method of claim 1, comprising a product with renewable naphtha, distillate, VGO range hydrocarbons with fraction comprising naphtha range hydrocarbon fuel comprising hydrocarbons, distillate range hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable naphtha fraction comprises:

i) approximately 2 to 30 wt % paraffins;

ii) approximately 50 to 80 wt % naphthenes; and

iii) approximately 0 to 10 wt % aromatics.

11. The method of claim 1, comprising a product with renewable distillate or vacuum gas oil (VGO) fraction comprising distillate range hydrocarbons, VGO range hydrocarbons, and combinations thereof wherein said renewable distillate fuel fraction has:

i) a density between approximately 0.75 and 0.95, including 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, and 0.95;

ii) an oxygen content between approximately 1.00 and 0.01, including 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, and 0.01;

iii) a cetane between approximately 40 and 60, including a cetane selected from the group consisting of approximately 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60;

iv) a cloud point between approximately −

55°

F. and −

75°

F., including a cloud point selected from the group consisting of approximately −

55°

F., −

60°

F., −

65°

F., −

70°

F., and −

75°

F.; and

v) a pour point between approximately −

70°

F. and −

88°

F., including a pour point selected from the group consisting of approximately −

70°

F., −

75°

F., −

80°

F., −

85°

F., and −

88°

F.; and

combinations thereof.

12. The method of claim 1, comprising a product with renewable naphtha fuel comprising naphtha range hydrocarbons wherein said renewable naphtha fuel fraction has:

i) a density between approximately 0.65 and 0.80;

ii) an oxygen content between approximately 1.00 and 0.01; and

iii) a calculated octane between approximately 45 and 65.

13. The method of claim 1 further fuels comprising:

a) providing hydrogen; and

b) separating alcohol from the hydrogenated product prior to condensing the hydrogenated product with a condensation catalyst.

14. The method of claim 13, wherein said oxygenate feedstock is derived from a biomass selected from the group consisting of sugars, carbohydrates, lignins, fatty acids, proteins, oils, eucalyptus oil, forest residues, dead trees, branches, leaves, tree stumps, yard clippings, wood chips, wood fiber, sugar beets, miscanthus, switchgrass, hemp, corn, corn fiber, poplar, willow, sorghum, sugarcane, palm oil, corn syrup, algal cultures, bacterial cultures, fermentation cultures, paper manufacturing waste, farming residues, food manufacturing waste, meat processing waste, municipal solid waste, animal waste, biological waste, sewage, and combinations thereof.

15. The method of claim 13, wherein said oxygenate feedstock comprises one or more oxygenates selected from the group consisting of carbohydrates, sugars, pentoses, hexoses, monosaccharides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, levoglucosan, sucrose, manose, glucose, xylose, isosorbide, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, arabitol, mannitol, sorbitol, dulcitol, maltitol, arabinitol, isosorbide, glycerol, glycerin, alcohol, methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), butanol (BuOH), n-butanol, t-butanol, ethers, methyl tert-butyl ether (MTBE), tertiary amyl methyl ether (TAME), tertiary hexyl methyl ether (THEME), ethyl tertiary butyl ether (ETBE), tertiary amyl ethyl ether (TAEE), diisopropyl ether (DIPE), hydroxymethyl-tetrahydrofuran or tetrahydro-2-furfuryl alcohol (THFA), methyl-tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydrofuran, diols, methanediol (H₂C(OH)₂), ethylene glycol, propane diols, 1,2-propanediol, 1,3-propanediol, butanediols, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentane diols, 1,2-pentanediol, 1,5-pentanediol, octanediol, 1,8-octanediol, etohexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, aldehydes, propanal, butanal, 2,5-furan-diacrboxyaldehyde, carboxylates, acetic acid, oxopropanoic acid, acrylic acid, levulinic acid, succinic acid, 2,5-furan-dicarboxylic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, acetylacrylic acid, 4-O-Me-glucuronic acid, gluconic acid, xylonic acid, esters, levuninate esters, lactones, valero lactone, α

-methylene-γ

-valerolactone, angelica lactones, trisaccharides, oligosaccharides, polysaccharides, starch, derivatives, dimers, trimers, and polymers thereof.

16. The method of claim 13, further comprising one or more of the following reaction conditions:

a) wherein said oxygenate is hydrogenated at temperatures between approximately 100 and 400°

C. and pressures between approximately 100-1200 psig;

b) wherein said hydrogenated product is condensed and/or oligomerized at temperatures between approximately 200 and 600°

C. and pressures between approximately 100-1200 psig; and

c) wherein said condensed and/or oligomerized product is polished at temperatures between approximately 200 and 400°

C. and pressures between approximately 100-2000 psig.

17. The method of claim 13,

a) wherein said hydrogenation catalysts is selected from the group consisting of ceria (Ce), magnesium (Mg), nickel (Ni), cobalt.(Co), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and combinations thereof,

b) wherein said condensation catalyst is selected from the group consisting of alumina, silica, silica-alumina, zirconia, titania, ceria, manganese oxide, magnesium, praseodymium oxide, samarium oxide, and combinations thereof,

c) wherein said condensation catalyst has a promoter selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), Iron (Fe), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), and combinations thereof;

d) wherein said polishing catalyst is selected from the group consisting of molybdenum (Mo), tungsten (W), cobalt (Co), nickel (Ni), NiW, NiMo, CoMo, and combinations thereof;

or

e) wherein said polishing catalyst support is selected from the group consisting of carbon, alumina, silica, zeolite, ceramic, Al₂O₃, and the like.

18. The method of claim 13, wherein said hydrocarbon range fuel products are distilled to one or more renewable hydrocarbon fuels selected form the group consisting of gasoline, diesel, and jet-fuel.

19. The method of claim 13, wherein said renewable hydrocarbon fuel products comprise naphthene hydrocarbons and mixtures thereof.

20. The method of claim 13, comprising:

a) hydrogenation selected from one of the following conditions;

i) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is ruthenia-carbon catalyst, said temperature is approximately 100-150°

C., said pressure is approximately 400-1000 psig, or

ii) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is a nickel-based catalyst, said temperature is approximately 200-250°

C., said pressure is approximately 800-1000 psig;

b) condensation selected from one of the following conditions;

i) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

ii) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is magnesia-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iii) wherein said oxygenate comprises tetrahydrofurfuryl alcohol, said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iv) wherein said oxygenate comprises levulinic acid, said condensation catalyst is a noble-metal catalyst, said temperature is approximately 200-340°

C. and said pressure is approximately 1200 psig,

v) wherein said oxygenate comprises sorbitol, said condensation catalyst is a Co/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig, or

vi) wherein said oxygenate comprises a levulinic acid/formic acid mixture said condensation catalyst is a NiCu/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig; and

c) polishing selected from one of the following conditions;

i) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-8380°

C., and said pressure is approximately 800-81800 psi,

ii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-320°

C., and said pressure is approximately 800-1200 psi,

iii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, or

iv) wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-380°

C., and said pressure is approximately 800-2000 psi.

21. The method of claim 13, comprising a product with naphtha, renewable distillate, VGO range fraction comprising naphtha range hydrocarbons with, distillate range hydrocarbon fuel comprising hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable distillate range fraction comprises:

i) approximately 1 to 12 wt % paraffins;

ii) approximately 60 to 80 wt % naphthenes;

iii) approximately 15 to 40 wt % 1-ring naphthenes;

iv) approximately 20 to 40 wt % 2-ring naphthenes;

v) approximately 5 to 15 wt % 3-ring naphthenes; and

vi) approximately 0 to 20 wt % aromatics.

22. The method of claim 13, comprising a product renewable naphtha, distillate, VGO range hydrocarbons with fraction comprising naphtha range hydrocarbon fuel comprising hydrocarbons, distillate range hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable naphtha fraction comprises:

i) approximately 2 to 30 wt % paraffins;

ii) approximately 50 to 80 wt % naphthenes; and

iii) approximately 0 to 10 wt % aromatics.

23. The method of claim 13, comprising a product with renewable distillate or vacuum gas oil (VGO) fraction comprising distillate range hydrocarbons, VGO range hydrocarbons, and combinations thereof wherein said renewable distillate fuel fraction has:

i) a density between approximately 0.75 and 0.95;

ii) an oxygen content between approximately 1.00 and 0.01;

iii) a cetane between approximately 40 and 60;

iv) a cloud point between approximately −

55°

F. and −

75°

F.; and

v) a pour point between approximately −

70°

F. and −

88°

F.

24. The method of claim 13, comprising a product with renewable naphtha fuel comprising naphtha range hydrocarbons wherein said renewable naphtha fuel fraction has:

i) a density between approximately 0.65 and 0.80, including 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, and 0.80;

ii) an oxygen content between approximately 1.00 and 0.01, including 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.1, 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, 0.03, 0.02, and 0.01; and

iii) a calculated octane between approximately 45 and 65, including a calculated octane selected from the group consisting of approximately 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, and 65.

25. (canceled)

26. (canceled)

27. (canceled)

28. (canceled)

29. (canceled)

30. (canceled)

31. (canceled)

32. (canceled)

33. (canceled)

34. (canceled)

35. (canceled)

36. (canceled)

37. A method of converting renewable hydrocarbon fuel from biomass oxygenates into hydrocarbon fuels comprising:

naphtha range hydrocarbons, distillate range hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable hydrocarbon fuel is produced by a process comprising;

a) providing a biomass derived oxygenate feed;

b) condensing the biomass oxygenates with a condensation catalyst to produce a condensed or oligomerized product;

c) polishing the condensed or oligomerized product with a hydroprocessing catalyst (HPC) to produce hydrocarbon range fuel products; and

d) isolating one or more hydrocarbon range fuel products.

38. The method of claim 37, wherein said oxygenate feedstock is derived from a biomass selected from the group consisting of sugars, carbohydrates, lignins, fatty acids, proteins, oils, eucalyptus oil, forest residues, dead trees, branches, leaves, tree stumps, yard clippings, wood chips, wood fiber, sugar beets, miscanthus, switchgrass, hemp, corn, corn fiber, poplar, willow, sorghum, sugarcane, palm oil, corn syrup, algal cultures, bacterial cultures, fermentation cultures, paper manufacturing waste, farming residues, food manufacturing waste, meat processing waste, municipal solid waste, animal waste, biological waste, sewage, and combinations thereof.

39. The method of claim 37, wherein said oxygenate feedstock comprises one or more oxygenates selected from the group consisting of carbohydrates, sugars, pentoses, hexoses, monosaccharides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, levoglucosan, sucrose, maltose, glucose, xylose, isosorbide, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, arabitol, mannitol, sorbitol, dulcitol, maltitol, arabinitol, isosorbide, glycerol, glycerin, alcohol, methanol (MeOH), ethanol (EtOH), isopropyl alcohol (IPA), butanol (BuOH), n-butanol, t-butanol, ethers, methyl tert-butyl ether (MTBE), tertiary amyl methyl ether (TAME), tertiary hexyl methyl ether (THEME), ethyl tertiary butyl ether (ETBE), tertiary amyl ethyl ether (TAEE), diisopropyl ether (DIPE), hydroxymethyl-tetrahydrofuran or tetrahydro-2-furfuryl alcohol (THFA), methyl-tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydrofuran, diols, methanediol (H₂C(OH)₂), ethylene glycol, propane diols, 1,2-propanediol, 1,3-propanediol, butanediols, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentane diols, 1,2-pentanediol, 1,5-pentanediol, octanediol, 1,8-octanediol, etohexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol, aldehydes, propanal, butanal, 2,5-furan-diacrboxyaldehyde, carboxylates, acetic acid, oxopropanoic acid, acrylic acid, levulinic acid, succinic acid, 2,5-furan-dicarboxylic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, acetylacrylic acid, 4-O-Me-glucuronic acid, gluconic acid, xylonic acid, esters, levuninate esters, lactones, valero lactone, α

-methylene-γ

-valerolactone, angelica lactones, trisaccharides, oligosaccharides, polysaccharides, starch, derivatives, dimers, trimers, and polymers thereof.

40. The method of claim 37, further comprising one or more of the following reaction conditions:

a) wherein said oxygenate is hydrogenated at temperatures between approximately 100 and 400°

C. and pressures between approximately 100-1200 psig, including temperatures of approximately 100°

C., 125°

C., 150°

C., 175°

C., 200°

C., 225°

C., 250°

C., 275°

C., 300°

C., 325°

C., 350°

C., 375°

C., or 400°

C. and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, or 1200 psig;

b) wherein said hydrogenated product is condensed and/or oligomerized at temperatures between approximately 200 and 600°

C. and pressures between approximately 100-1200 psig, including temperatures of approximately 200°

C., 225°

C., 250°

C., 275°

C., 290°

C., 300°

C., 325°

C., 350°

C., 375°

C., 400°

C., 425°

C., 450°

C., 475°

C., 500°

C., 525°

C., 550°

C., 575°

C., or 600°

C. and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, or 1200 psig; and

c) wherein said condensed and/or oligomerized product is polished at temperatures between approximately 200 and 400°

C. and pressures between approximately 100-2000 psig, including temperatures of approximately 200°

C., 225°

C., 250°

C., 275°

C., 290°

C., 300°

C., or 350°

C., and pressures of approximately 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig, 700 psig, 800 psig, 900 psig, 1000 psig, 1100 psig, 1200 psig, 1400 psig, 1600 psig, 1800 psig or 2000 psig.

41. The method of claim 37,

a) wherein said hydrogenation catalysts is selected from the group consisting of ceria (Ce), magnesium (Mg), nickel (Ni), cobalt.(Co), gold (Au), iridium (h), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and combinations thereof;

b) wherein said condensation catalyst is selected from the group consisting of alumina, silica, silica-alumina, zirconia, titania, ceria, manganese oxide, magnesium, praseodymium oxide, samarium oxide, and combinations thereof;

c) wherein said condensation catalyst has a promoter selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co), Iron (Fe), gold (Au), iridium (Ir), osmium (Os), palladium (Pd), platinum (Pt), rhodium (Rh), and combinations thereof;

wherein said polishing catalyst is selected from the group consisting of molybdenum (Mo), tungsten (W), cobalt (Co), nickel (Ni), NiW, NiMo, CoMo, and combinations thereof;

or

e) wherein said polishing catalyst support is selected from the group consisting of carbon, alumina, silica, zeolite, ceramic, Al₂O₃, and the like.

42. The method of claim 37, wherein said hydrocarbon range fuel products are distilled to one or more renewable hydrocarbon fuels selected form the group consisting of gasoline, diesel, and jet-fuel.

43. The method of claim 37, wherein said renewable hydrocarbon fuel products comprise naphthene hydrocarbons and mixtures thereof.

44. The method of claim 37, comprising:

a) hydrogenation selected from one of the following conditions;

i) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is ruthenia-carbon catalyst, said temperature is approximately 100-150°

C., said pressure is approximately 400-1000 psig, or

ii) wherein said oxygenate comprises levulinic acid, said hydrogenation catalyst is a nickel-based catalyst, said temperature is approximately 200-250°

C., said pressure is approximately 800-1000 psig;

b) condensation selected from one of the following conditions;

i) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

ii) wherein said oxygenate comprises gamma-valerolactone (GVL), said condensation catalyst is magnesia-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iii) wherein said oxygenate comprises tetrahydrofurfuryl alcohol, said condensation catalyst is ceria-alumina, said temperature is approximately 400°

C. and said pressure is approximately 800-1000 psig,

iv) wherein said oxygenate comprises levulinic acid, said condensation catalyst is a noble-metal catalyst, said temperature is approximately 200-340°

C. and said pressure is approximately 1200 psig,

v) wherein said oxygenate comprises sorbitol, said condensation catalyst is a Co/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig, or

vi) wherein said oxygenate comprises a levulinic acid/formic acid mixture said condensation catalyst is a NiCu/praseodymium oxide-alumina catalyst, said temperature is approximately 280-400°

C. and said pressure is approximately 800-1200 psig; and

c) polishing selected from one of the following conditions;

i) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-8380°

C., and said pressure is approximately 800-81800 psi,

ii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 240-320°

C., and said pressure is approximately 800-1200 psi,

iii) wherein said polishing catalyst is a sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-350°

C., and said pressure is approximately 800-1200 psi, or

iv) wherein said polishing catalyst is a non-sulfided hydroprocessing catalyst, said temperature is approximately 280-380°

C., and said pressure is approximately 800-2000 psi.

45. The method of claim 37, comprising a product with naphtha, renewable distillate, VGO range fraction comprising naphtha range hydrocarbons with, distillate range hydrocarbon fuel comprising hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable distillate range fraction comprises:

i) approximately 1 to 12 wt % paraffins,

ii) approximately 60 to 80 wt % naphthenes,

iii) approximately 15 to 40 wt % 1-ring naphthenes,

iv) approximately 20 to 40 wt % 2-ring naphthenes,

v) approximately 5 to 15 wt % 3-ring naphthenes, and

vi) approximately 0 to 20 wt % aromatics.

46. The method of claim 37, comprising a product with renewable naphtha, distillate, VGO range hydrocarbons with fraction comprising naphtha range hydrocarbon fuel comprising hydrocarbons, distillate range hydrocarbons, vacuum gas oil (VGO) range hydrocarbons, and combinations thereof wherein said renewable naphtha fraction comprises:

1) approximately 2 to 30 wt % paraffins,

ii) approximately 50 to 80 wt % naphthenes, and

iii) approximately 0 to 10 wt % aromatics.

47. The method of claim 37, comprising a product with renewable distillate or vacuum gas oil (VGO) fraction comprising distillate range hydrocarbons, VGO range hydrocarbons, and combinations thereof wherein said renewable distillate fuel fraction has:

i) a density between approximately 0.75 and 0.95;

ii) an oxygen content between approximately 1.00 and 0.01;

iii) a cetane between approximately 40 and 60;

iv) a cloud point between approximately −

55°

F. and −

75°

F.;

v) a pour point between approximately −

70°

F. and −

88°

F.

48. The method of claim 37, comprising a product with renewable naphtha fuel comprising naphtha range hydrocarbons wherein said renewable naphtha fuel fraction has

i) a density between approximately 0.65 and 0.80;

ii) an oxygen content between approximately 1.00 and 0.01; and

iii) a calculated octane between approximately 45 and 65.