Process for manufacturing methyl tertiary-butyl ether (MTBE) and other hydrocarbons

Patent metadata

Field	Value
Publication number	US-10364204-B2
Application number	US-201615173042-A
Country	US
Kind code	B2
Filing date	Jun 3, 2016
Priority date	Jun 22, 2015
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

A process for manufacturing methyl t-butyl ether (MTBE) including (A) an optional first step including cracking raw material made from or containing ethane and/or propane, to form ethylene and recovering the residual uncracked raw material, (B) a second step including dimerizing ethylene to form n-butylene, (C) a third step including isomerizing the n-butylene to form isobutylene, (D) an optional fourth step including oxidizing methane to form methanol, (E) a fifth step including etherifying the isobutylene with methanol to form methyl t-butyl ether, and (F) a sixth step including collecting the methyl t-butyl ether is provided. The process can also be used to prepare gasoline alkylate, a higher molecular weight ethylene oligomer, a higher-molecular-weight-ethylene-oligomer-based methyl ether, an isomerized higher molecular weight ethylene oligomer, or an isomerized-higher-molecular-weight-ethylene-oligomer-based methyl ether.

First claim

What is claimed is:

1. A process for manufacturing methyl t-butyl ether (MTBE) comprising:
a first step comprising cracking raw material comprising ethane or propane to form ethylene; and recovering residual uncracked raw material;
a second step comprising dimerizing ethylene to form a n-butylene feed stream, wherein the n-butylene feed stream comprises:
(i) about 30 to 50 wt. % of 2-butene, based on the total weight of the feed stream,
(ii) about 25 to 45 wt. % of 1-butene, based on the total weight of the feed stream, and
(iii) a higher molecular weight ethylene oligomer
wherein the dimerizing step is performed at a temperature of about 10-100° C., wherein the dimerizing step takes place in the presence of a dimerization catalyst, wherein the dimerization catalyst comprises a nickel compound and an aluminum compound, and wherein the catalyst has a Ni:Al ratio from 0.9:10 to 1:2.5;
a third step comprising isomerizing the n-butylene feed stream to form an isobutylene stream using a isomerization catalyst at a weight hourly space velocity (WHSV) of 0.2-4 kg feedstock per kg catalyst per hour at a pressure of about 345-3450 kPa and a temperature of about 40-200° C., wherein the isomerization catalyst is an acidic isomerization catalyst;
recovering unconverted n-butylene;
alkylating isobutylene with isobutane at a pressure of at least 600 kPa to form gasoline alkylate;
recovering gasoline alkylate;
isomerizing the higher molecular weight ethylene oligomer; and
recovering the isomerized higher molecular weight ethylene oligomer;

a fourth step comprising oxidizing methane to form methanol;
a fifth step comprising etherifying the isobutylene stream with methanol to form methyl t-butyl ether;
etherifying the higher molecular weight ethylene oligomer contained in the isobutylene stream with methanol to form a higher-molecular-weight-ethylene-oligomer-based methyl ether;
recovering the higher-molecular-weight-ethylene-oligomer-based methyl ether;
etherifying an isomerized higher molecular weight ethylene oligomer contained in the isobutylene stream with methanol to form an isomerized-higher-molecular-weight-ethylene-oligomer-based methyl ether; and
recovering the isomerized-higher-molecular-weight-ethylene-oligomer-based methyl ether; and

a sixth step comprising collecting the methyl t-butyl ether.

2. The process of claim 1 , wherein the second step further comprises:
recovering unconverted ethylene;
alkylating n-butylene with isobutane to form gasoline alkylate; and
recovering the gasoline alkylate.

3. The process of claim 1 , wherein the second step further comprises:
recovering unconverted ethylene;
dimerizing combinations of at least three ethylene molecules to form a higher molecular weight ethylene oligomer; and
recovering the higher molecular weight ethylene oligomer.

4. The process of claim 3 , wherein the alkylating step is performed at a catalyst:hydrocarbon volume ratio of 1:1 to 4:1.

5. The process of claim 1 , wherein the weight hourly space velocity (WHSV) ranges from about 1 to about 3 kg feedstock per kg catalyst per hour.

6. The process of claim 1 , wherein the n-butylene feed stream is contacted with a caustic solution.

7. The process of claim 6 , wherein the caustic solution is a 20% caustic solution.

8. The process of claim 1 , wherein the fourth step further comprises:
recovering unconverted methane.

9. The process of claim 1 , wherein the cracking step further comprises processing of a cracked product containing hydrogen, ethylene, propylene, a hydrocarbon or pyrolysis gasoline.

Assignees

• Lyondell Chemical Tech Lp

Inventors

• Axelrod Michael G
• Coleman Steven T

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C10L1/06

  for spark ignition · CPC title

• C07C2531/24

  Phosphines · CPC title

• C07C2531/14

  of aluminium or boron · CPC title

• C07C2529/65

  of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 · CPC title