# US 9,434,658 B2 · Catalytic conversion of alcohols to hydrocarbons with low benzene content

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- Number: US 9,434,658 B2
- Document ID: US9434658B2
- Status: Granted
- Kind: B2
- Application number: 13/787,112
- Filed: 2013-03-06
- Published: 2014-09-11
- Granted: 2016-09-06
- Earliest claimed: 2013-03-06
- Assignees: UT-Battelle, LLC
- Applicants: Ut-Battelle, LLC
- Inventors: Chaitanya K. Narula; Brian H. Davison; Martin Keller
- Web page: https://patentgrep.com/patent/US9434658B2

## CPC

- C07C 1/22: by reduction
- B01J 29/084: {Y-type faujasite}
- B01J 29/18: of the mordenite type
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/80: Mixtures of different zeolites
- B01J 35/19: {Catalysts containing parts with different compositions}
- C07C 1/24: by elimination of water
- C07C 2/64: Addition to a carbon atom of a six-membered aromatic ring
- C07C 2/66: Catalytic processes
- C07C 2/864: {the non-hydrocarbon is an alcohol}
- C12P 7/06: Ethanol, i.e. non-beverage
- B01J 29/061: {containing metallic elements added to the zeolite}
- B01J 29/088: {Y-type faujasite}
- B01J 29/405: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/46: Iron group metals or copper
- B01J 29/48: containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/7049: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/76: Iron group metals or copper
- B01J 29/78: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 2229/18: to introduce other elements into or onto the molecular sieve itself
- B01J 2229/186: not in framework positions
- C07C 2529/072: Iron group metals or copper
- C07C 2529/076: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C 2529/08: of the faujasite type, e.g. type X or Y
- C07C 2529/14: Iron group metals or copper
- C07C 2529/18: of the mordenite type
- C07C 2529/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C 2529/48: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C 2529/70: of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 30/20: using bio-feedstock
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

## Claims

### Claim 1

A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to an initial hydrocarbon fraction containing a blend of alkanes having at least four carbon atoms and benzene by contacting said alcohol, under conditions suitable for converting said alcohol to said initial hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said initial hydrocarbon fraction, and contacting said initial hydrocarbon fraction with a benzene alkylation catalyst, under conditions that form a further processed hydrocarbon fraction containing alkylated benzene product in addition to said blend of alkanes having at least four carbon atoms.

### Claim 2 (depends on 1)

The method of claim 1, wherein said alcohol is contacted with a mixture comprising said metal-loaded zeolite catalyst and said benzene alkylation catalyst.

### Claim 3 (depends on 1)

The method of claim 1, wherein, in a first step, said alcohol is contacted with said metal-loaded zeolite catalyst to form said initial hydrocarbon fraction containing a blend of alkanes having at least four carbon atoms and benzene, and in a second step, said initial hydrocarbon fraction is contacted with said benzene alkylation catalyst to form said further processed hydrocarbon fraction containing alkylated benzene product in addition to said blend of alkanes having at least four carbon atoms, wherein said metal-loaded zeolite catalyst and said benzene alkylation catalyst are separate.

### Claim 4 (depends on 1)

The method of claim 1, wherein said zeolite is comprised of a pentasil zeolite.

### Claim 5 (depends on 4)

The method of claim 4, wherein said pentasil zeolite is comprised of ZSM5.

### Claim 6 (depends on 1)

The method of claim 1, wherein said metal is selected from alkali metal, alkaline earth metal, copper, iron, vanadium, zinc, titanium, cadmium, gallium, indium, and combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein said metal is selected from copper, iron, and vanadium.

### Claim 8 (depends on 1)

The method of claim 1, wherein said benzene alkylation catalyst is a zeolite catalyst active for alkylating benzene.

### Claim 9 (depends on 8)

The method of claim 8, wherein said benzene alkylation catalyst is selected from zeolite Y, mordenite, and MCM catalysts active for alkylating benzene.

### Claim 10 (depends on 1)

The method of claim 1, wherein said hydrocarbon fraction, after being processed with said benzene alkylation catalyst, has no more than 0.62% benzene by volume of the hydrocarbon fraction.

### Claim 11 (depends on 1)

The method of claim 1, wherein said alcohol is comprised of ethanol.

### Claim 12 (depends on 1)

The method of claim 1, wherein said alcohol is a component of an aqueous solution in a concentration of no more than about 20%.

### Claim 13 (depends on 12)

The method of claim 12, wherein said alcohol is a component of a fermentation stream when contacted with said metal-loaded zeolite catalyst.

### Claim 14 (depends on 1)

The method of claim 1, wherein said hydrocarbon fraction is useful as a fuel or as a blendstock component of a fuel.

### Claim 15 (depends on 1)

The method of claim 1, wherein said method is integrated with a fermentation process, wherein said fermentation process produces said alcohol as a component of a fermentation stream, and said fermentation stream is contacted with said metal-loaded zeolite catalyst.

### Claim 16 (depends on 1)

The method of claim 1, wherein said method is integrated with a biomass reactor that includes a fermentation process, wherein said fermentation process produces said alcohol as a component of a fermentation stream, and said fermentation stream is contacted with said metal-loaded zeolite catalyst.