CARBOHYDRATES UPGRADING AND HYDROTREATING TO HYDROCARBONS

• US 20110263916A1
• Filed: 04/19/2011
• Published: 10/27/2011
• Est. Priority Date: 04/27/2010
• Status: Active Grant

• Current Assignee: Phillips 66 Company
• Original Assignee: Conocophillips Company (ConocoPhillips)
• Inventors: BROWN, Ronald E., FJARE, Kristi A., MYERS, Lisa L., SUGHRUE, Edward L. II, BAO, Yun, YAO, Jianhua, SHI, TiePan
• Granted Patent: US 8,809,605 B2
• Time in Patent Office: Days
• US Class Current: 585/254
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/1058 Nickel catalysts
• CPC Class Codes: C01B 2203/107 Platinum catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1247 Higher hydrocarbons
• CPC Class Codes: C01B 3/38 using catalysts
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/4081 Recycling aspects
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 3/49 containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: C10G 3/50 in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• CPC Class Codes: C10G 45/02 to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• CPC Class Codes: C10G 45/30 characterised by the catalyst used
• CPC Class Codes: C10G 45/44 Hydrogenation of the aromatic hydrocarbons
• CPC Class Codes: C10G 45/46 characterised by the catalyst used
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 : using bio-feedstock
• CPC Class Codes: Y02P 30/40 : Ethylene production

Abstract

Technologies to convert biomass to liquid hydrocarbon fuels are currently being developed to decrease our carbon footprint and increase use of renewable fuels. Since sugars/sugar derivatives from biomass have high oxygen content and low hydrogen content, coke becomes an issue during zeolite upgrading to liquid hydrocarbon fuels. A process was designed to reduce the coke by co-feeding sugars/sugar derivatives with a saturated recycle stream containing hydrogenated products.

Claims

1. An upgrading system to convert polyols into hydrocarbons comprising:

a) a feed stream comprising a oxygenate feedstock,

b) a catalytic upgrader comprising a zeolite catalyst,

c) a separator to generate a light gas stream, an aqueous stream and an organic stream,

d) a reformer to convert the light gas stream into a hydrogen stream,

e) a hydrotreater to convert part of the organic stream (c) and hydrogen stream (d) into a saturated hydrocarbon stream, and

a recycle system where a portion of the hydrotreater product containing saturated hydrocarbons is recycled to the catalytic upgrader (a) as a hydrogen donor molecule.

2. The system of claim 1, wherein said oxygenate feedstock comprises oxygenates derived from biological materials including carbohydrates, sugars, pentoses, hexoses, monosaccharaides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, sucrose, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, 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, 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, angelilactones, trisaccharides, oligosaccharides, polysaccharides, starch, their derivatives, dimers, trimers, polymers, and combinations thereof.

3. The system of claim 1, wherein said zeolite catalyst (b) is selected from the group consisting of SiO₂, Al₂O₃, ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38, MFI, Pentasil, HZSM-5, T-4480, and combinations thereof.

4. The system of claim 1, wherein said separator (c) is selected from the group consisting of a gas-liquid, liquid-liquid, three-phase, horizontal, vertical, tubular, rotary, turbine, centrifugal, and combinations thereof.

5. The system of claim 1, wherein said reformer (d) comprises a catalyst selected from the group consisting of nickel impregnated aluminum oxide (Ni/Al₂O₃), nickel impregnated magnesium oxide (Ni/MgO), platinum impregnated aluminum oxide (Pt/Al₂O₃), platinum impregnated magnesium oxide (Pt/MgO), catalyst impregnated ceramic pellets, modified ceramics, metal foils, and combinations thereof.

6. The system of claim 1, wherein said hydrotreater comprises a catalyst selected from the group consisting of nickel, aluminum, halfnium, platinum, palladium, ruthenium Raney nickel, palladium (II) acetate trimer, palladium (II) chloride, sodium tetrachloropalladate (II), tetrakis(triphenylphosphine) palladium (0), dihydrogen hexachloroplatinate (IV), platinum (II) chloride, platinum (IV) chloride, potassium tetrachloroplatinate (II), chloro(1,5-cyclooctadiene) rhodium (I) dimer, Chlorotris(triphenylphosphine) rhodium (I), rhodium (II) acetate dimer, Rhodium (III) chloride hydrate, ruthenium (III) chloride trihydrate, Iridium (III) chloride hydrate, osmium (VIII) tetroxide, rhenium carbonyl Re₂(CO)₁₀, organophosphines, nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated (Cu/Cr), nickel aluminum oxide (Ni/Al₂O₃), palladium aluminum oxide (Pd/Al₂O₃), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), and combinations thereof.

7. The system of claim 1, wherein said recycled hydrotreater product comprises alkanes, naphthas, hexanes, cyclomethylhexane, alkenes, naphthenes, and combinations thereof.

8. An upgrading system to convert oxygenates into hydrocarbons comprising:

a) a feed stream comprising a oxygenate feedstock,

b) a catalytic upgrader comprising a ZSM-5 zeolite catalyst,

c) a separator to generate a light gas stream, an aqueous stream and an organic stream,

d) a reformer to convert the light gas stream into a hydrogen stream,

e) a hydrotreater to convert part of the organic stream (c) and hydrogen stream (d) into a saturated hydrocarbon stream, and

a recycle system where a portion of the hydrotreater product containing saturated hydrocarbons is recycled to the catalytic upgrader (a) as a hydrogen donor molecule.

9. The system of claim 8, wherein said oxygenate feedstock is selected from the group consisting of carbohydrates, sugars, pentoses, hexoses, monosaccharaides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, sucrose, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, 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, 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, angelilactones, trisaccharides, oligosaccharides, polysaccharides, starch, their derivatives, dimers, trimers, polymers, and combinations thereof.

10. The system of claim 8, wherein said separator (c) is selected from the group consisting of a gas-liquid, liquid-liquid, three-phase, horizontal, vertical, tubular, rotary, turbine, centrifugal, and combinations thereof.

11. The system of claim 8, wherein said reformer (d) comprises a catalyst selected from the group consisting of nickel impregnated aluminum oxide (Ni/Al₂O₃), nickel impregnated magnesium oxide (Ni/MgO), platinum impregnated aluminum oxide (Pt/Al₂O₃), platinum impregnated magnesium oxide (Pt/MgO), catalyst impregnated ceramic pellets, modified ceramics, metal foils, and combinations thereof.

12. The system of claim 8, wherein said hydrotreater comprises a catalyst selected from the group consisting of nickel, aluminum, halfnium, platinum, palladium, ruthenium Raney nickel, palladium (II) acetate trimer, palladium (II) chloride, sodium tetrachloropalladate (II), tetrakis(triphenylphosphine) palladium (0), dihydrogen hexachloroplatinate (IV), platinum (II) chloride, platinum (IV) chloride, potassium tetrachloroplatinate (II), chloro(1,5-cyclooctadiene) rhodium (I) dimer, Chlorotris(triphenylphosphine) rhodium (I), rhodium (II) acetate dimer, Rhodium (III) chloride hydrate, ruthenium (III) chloride trihydrate, Iridium (III) chloride hydrate, osmium (VIII) tetroxide, rhenium carbonyl Re₂(CO)₁₀, organophosphines, nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated (Cu/Cr), nickel aluminum oxide (Ni/Al₂O₃), palladium aluminum oxide (Pd/Al₂O₃), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), and combinations thereof.

13. The system of claim 8, wherein said recycled hydrotreater product comprises alkanes, naphthas, hexanes, cyclomethylhexane, alkenes, naphthenes, and combinations thereof.

14. A method for upgrading biomass oxygenates into hydrocarbons comprising:

a) upgrading an oxygenate feedstock with a catalytic upgrader comprising a zeolite catalyst and one or more hydrogen donors,

b) separating a light gas stream, an aqueous stream and an organic stream,

c) reforming the light gas stream into a hydrogen stream,

d) hydrotreating the organic stream (b) with a hydrotreating catalyst and a hydrogen stream (c), and

e) isolating a saturated hydrocarbon stream, and a recycle system where a portion of the hydrotreater product containing saturated hydrocarbons is recycled to the catalytic upgrader (a) as a hydrogen donor molecule.

15. The method of claim 14, wherein said zeolite catalyst is a ZSM-5 zeolite catalyst.

16. The method of claim 14, wherein said oxygenate feedstock comprises oxygenates derived from biological materials including carbohydrates, sugars, pentoses, hexoses, monosaccharaides, dextrose, glucose, α

-D-glucopyranose, β

-D-glucopyranose, α

-D-glucofuranose, β

-D-glucofuranose, fructose, galactose, disaccharides, sucrose, lactose, maltose, fructose, cellobiose, melibiose, raffinose, glyceraldehyde, erythritol, xylitol, sorbitol, 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, 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, angelilactones, trisaccharides, oligosaccharides, polysaccharides, starch, their derivatives, dimers, trimers, polymers, and combinations thereof.

17. The method of claim 14, wherein said zeolite catalyst (b) is selected from the group consisting of SiO₂, Al₂O₃, ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-35, ZSM-38, MFI, Pentasil, HZSM-5, T-4480, and combinations thereof.

18. The method of claim 14, wherein said separator (c) is selected from the group consisting of a gas-liquid, liquid-liquid, three-phase, horizontal, vertical, tubular, rotary, turbine, centrifugal, and combinations thereof.

19. The method of claim 14, wherein said reformer (d) comprises a catalyst selected from the group consisting of nickel impregnated aluminum oxide (Ni/Al₂O₃), nickel impregnated magnesium oxide (Ni/MgO), platinum impregnated aluminum oxide (Pt/Al₂O₃), platinum impregnated magnesium oxide (Pt/MgO), catalyst impregnated ceramic pellets, modified ceramics, metal foils, and combinations thereof.

20. The method of claim 14, wherein said hydrotreater comprises a catalyst selected from the group consisting of nickel, aluminum, halfnium, platinum, palladium, ruthenium Raney nickel, palladium (II) acetate trimer, palladium (II) chloride, sodium tetrachloropalladate (II), tetrakis(triphenylphosphine) palladium (0), dihydrogen hexachloroplatinate (IV), platinum (II) chloride, platinum (IV) chloride, potassium tetrachloroplatinate (II), chloro(1,5-cyclooctadiene) rhodium (I) dimer, Chlorotris(triphenylphosphine) rhodium (I), rhodium (II) acetate dimer, Rhodium (III) chloride hydrate, ruthenium (III) chloride trihydrate, Iridium (III) chloride hydrate, osmium (VIII) tetroxide, rhenium carbonyl Re₂(CO)₁₀, organophosphines, nickel, copper impregnated zinc oxide (Cu/ZnO), copper impregnated (Cu/Cr), nickel aluminum oxide (Ni/Al₂O₃), palladium aluminum oxide (Pd/Al₂O₃), cobalt molybdenum (CoMo), nickel molybdenum (NiMo), and combinations thereof.

21. The method of claim 14, wherein said recycled hydrotreater product comprises alkanes, naphthas, hexanes, cyclomethylhexane, alkenes, naphthenes, and combinations thereof.