# US 2020/0399543 A1 · Methods for methanol-to-gasoline conversion with methanol recycling

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- Number: US 2020/0399543 A1
- Document ID: US20200399543A1
- Status: Published application
- Kind: A1
- Application number: 16/903,220
- Filed: 2020-06-16
- Published: 2020-12-24
- Earliest claimed: 2019-06-18
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: ExxonMobil Research and Engineering Company
- Inventors: Mohsen N. Harandi; Suriyanarayanan Rajagopalan; David W. Staubs; Terry E. Helton; Mitch L. Hindman
- Web page: https://patentgrep.com/patent/US20200399543A1

## CPC

- C10G 3/44: {characterised by the catalyst used}
- C10G 7/04: Dewatering
- C10G 7/08: Azeotropic or extractive distillation (refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents C10G21/00)
- C10G 2300/10: Feedstock materials
- C10G 2400/02: Gasoline
- Y02P 30/20: using bio-feedstock
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Methanol-to-gasoline (MTG) conversion may be performed with a methanol recycling. Methanol may be fed to a first reactor where it may be catalytically converted under dimethyl ether formation conditions in the presence of a first catalyst to form a product mixture comprising dimethyl ether (DME), methanol, and water. The DME may be separated from the methanol and the water and delivered to a second reactor. In the second reactor, the DME may be catalytically converted under MTG conversion conditions in the presence of a second catalyst to form a second product mixture comprising gasoline hydrocarbons and light hydrocarbon gas. The methanol and the water from the first reactor may be separated further to obtain substantially water-free methanol, which may be returned to the first reactor. The separation of methanol from the water may be performed using the light hydrocarbon gas to effect stripping of the methanol.

## Claims

### Claim 1

A method comprising:
providing a feed comprising methanol to a first reactor;
catalytically converting at least a portion of the feed in the first reactor under dimethyl ether formation conditions in the presence of a first catalyst to form a first product mixture comprising dimethyl ether (DME), methanol, and water;
separating the first product mixture into a first fraction comprising the DME and a second fraction comprising the methanol and the water;
providing the first fraction to a second reactor;
catalytically converting at least a portion of the DME in the second reactor under methanol-to-gasoline (MTG) conversion conditions in the presence of a second catalyst to form a second product mixture comprising gasoline hydrocarbons and light hydrocarbon gas;
separating the second fraction into substantially water-free methanol and an aqueous effluent; and
returning the substantially water-free methanol to the first reactor.

### Claim 2 (depends on 1)

The method of claim 1, wherein separating the second fraction into substantially water-free methanol and the aqueous effluent comprises passing a stripping gas through the second fraction.

### Claim 3 (depends on 1)

The method of claim 1, further comprising:
separating the light hydrocarbon gas from the second product mixture.

### Claim 4 (depends on 2)

The method of claim 2, wherein the stripping gas comprises at least a portion of the light hydrocarbon gas formed in the second reactor.

### Claim 5 (depends on 1)

The method of claim 1, further comprising:
cooling the first product mixture prior to separating the first product mixture into the first fraction and the second fraction.

### Claim 6 (depends on 2)

The method of claim 2, further comprising:
delivering a first portion of the light hydrocarbon gas to the second fraction to serve as the stripping gas; and
returning a second portion of the light hydrocarbon gas to the second reactor.

### Claim 7 (depends on 6)

The method of claim 6, further comprising:
delivering a third portion of the light hydrocarbon gas to the first product mixture to aid in separating the first product mixture.

### Claim 8 (depends on 1)

The method of claim 1, wherein the feed is provided to the first reactor continuously as part of a flow process.

### Claim 9 (depends on 1)

The method of claim 1, further comprising:
optionally separating the gasoline hydrocarbons from the second product mixture; and
processing the gasoline hydrocarbons.

### Claim 10 (depends on 9)

The method of claim 9, wherein processing the gasoline hydrocarbons comprises passing the gasoline hydrocarbons through a debutanizer.

### Claim 11 (depends on 1)

The method of claim 1, wherein the first catalyst comprises gamma-alumina.

### Claim 12 (depends on 1)

The method of claim 1, wherein the second catalyst comprises a zeolite.

### Claim 13 (depends on 1)

The method of claim 1, wherein an amount of water in the first fraction provided to the second reactor is less than or equal to 5 wt. %.

### Claim 14 (depends on 1)

The method of claim 1, wherein separating the first product mixture takes place by distillation, and the DME is obtained as an overhead product from the distillation.

### Claim 15

A method comprising:
providing a feed stream comprising methanol to a first reactor;
catalytically converting at least a portion of the feed stream in the first reactor under dimethyl ether formation conditions in the presence of a first catalyst to form a first product mixture comprising DME, methanol, and water;
delivering the first product mixture in a first stream from the first reactor to a first separation unit;
separating the first product mixture in the first separation unit to obtain a first fraction comprising the DME and a second fraction comprising the methanol and the water;
delivering the first fraction in a second stream to a second reactor;
catalytically converting at least a portion of the DME in the second reactor under MTG conversion conditions in the presence of a second catalyst to form a second product mixture comprising gasoline hydrocarbons and light hydrocarbon gas;
delivering the second fraction in a third stream to a second separation unit;
delivering at least a first portion of the light hydrocarbon gas to the second separation unit;
separating the second fraction in the second separation unit into substantially water-free methanol and an aqueous effluent using the light hydrocarbon gas to effect stripping; and
returning the substantially water-free methanol in a fourth stream to the first reactor.

### Claim 16 (depends on 15)

The method of claim 15, further comprising:
separating the light hydrocarbon gas from the second product mixture; and
returning a second portion of the light hydrocarbon gas to the second reactor.

### Claim 17 (depends on 16)

The method of claim 16, further comprising:
delivering a third portion of the light hydrocarbon gas to the first separation unit to aid in separating the first product mixture.

### Claim 18 (depends on 15)

The method of claim 15, further comprising:
cooling the first product mixture prior to delivering the first product mixture to the first separation unit.

### Claim 19 (depends on 15)

The method of claim 15, wherein separating the first product mixture takes place by distillation, and the DME is obtained as an overhead product from the distillation.

### Claim 20 (depends on 15)

The method of claim 15, further comprising:
optionally separating the gasoline hydrocarbons from the second product mixture; and
processing the gasoline hydrocarbons.