# US 4,393,250 A · Process for producing alcohols and ethers

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- Number: US 4,393,250 A
- Document ID: US4393250A
- Status: Granted
- Kind: A
- Application number: 06/372,804
- Filed: 1982-04-28
- Granted: 1983-07-12
- Earliest claimed: 1981-04-28
- Assignees: Veba Oel AG
- Inventors: Klaus Gottlieb; Hartmut Bruderreck; Friedel-Heinrich Wehmeier
- Web page: https://patentgrep.com/patent/US4393250A

## CPC

- C07C 41/06: by addition of organic compounds only
- C07C 29/04: by hydration of carbon-to-carbon double bonds
- C07C 31/10: containing three carbon atoms
- C07C 31/12: containing four carbon atoms
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A process for producing isopropyl alcohol and isopropyl tert-butyl ether from a mixture of light hydrocarbons containing propane and butane, comprises: (a) separating from the mixture of light hydrocarbons a propane fraction and a butane fraction containing at least n-butane; (b) isomerizing at least a portion of the n-butane in the butane fraction from step (a) whereby a hydrocarbon mixture containing at least n-butane and isobutane is formed; (c) catalytically dehydrogenating the isobutane in the hydrocarbon mixture from step (b) whereby a hydrocarbon mixture containing at least isobutene is produced; (d) catalytically dehydrogenating the propane in the propane fraction from step (a) whereby a hydrocarbon mixture containing at least propene is produced; (e) reacting the propene in the hydrocarbon mixture from step (d) with water, whereby a mixture containing hydrocarbons and isopropyl alcohol is formed; (f) reacting the isopropyl alcohol from step (e) with at least part of the isobutene in the hydrocarbon mixture from step (c) whereby a mixture containing hydrocarbons and isopropyl tert-butyl ether is formed; (g) recycling the hydrocarbons in the hydrocarbon mixture from step (e) to step (d), respectively; (h) recycling the hydrocarbons in the hydrocarbon mixture from step (f) to step (c); and (i) recovering at least the isopropyl tert-butyl ether.

## Claims

### Claim 1

A process for producing isopropyl tert-butyl ether from a mixture of light hydrocarbons containing propane and butane comprising:
(a) separating from said mixture of light hydrocarbons a propane fraction and a butane fraction containing at least n-butane;
(b) isomerizing at least a portion of said n-butane in said butane fraction from step (a) whereby a hydrocarbon mixture containing at least n-butane and isobutane is formed;
(c) catalytically dehydrogenating said isobutane in said hydrocarbon mixture from step (b) whereby a hydrocarbon mixture containing at least isobutene is produced;
(d) catalytically dehydrogenating said propane in said propane fraction from step (a) whereby a hydrocarbon mixture containing at least propene is produced;
(e) reacting said propene in said hydrocarbon mixture from step (d) with water, whereby a mixture containing hydrocarbons and isopropyl alcohol is formed;
(f) reacting said isopropyl alcohol from step (e) with at least part of said isobutene in said hydrocarbon mixture from step (c) whereby a mixture containing hydrocarbons and isopropyl tert-butyl ether is formed;
(g) recycling said hydrocarbons in said hydrocarbon mixture from step (e) to step (d);
(h) recycling said hydrocarbons in said hydrocarbon mixture from step (f) to step (c); and
(i) recovering at least said isopropyl tert-butyl ether.

### Claim 2 (depends on 1)

The process of claim 1 wherein sec-butyl tert-butyl ether is also produced, wherein
in step (c) said n-butane is also dehydrogenated whereby said hydrocarbon mixture formed also contains butadiene and n-butenes;
and said hydrocarbon mixture from step (c) is subjected to catalytic hydrogenation and hydroisomerization whereby said butadiene is selectively hydrogenated and butene-1 in said n-butenes is isomerized into butene-2 thereby forming a hydrocarbon mixture containing at least butene-2 and isobutene;
in a step (j) a first portion of said isobutene in said hydrocarbon mixture from step (c) is reacted with isopropyl alcohol to form isopropyl tert-butyl ether;
in a step (k) a second portion of said isobutene in said hydrocarbon mixture from step (c) is reacted with sec-butyl alcohol to form sec-butyl tert-butyl ether;
in a step (l) said butene-2 in said hydrocarbon mixture from step (c) is reacted with water to form sec-butyl alcohol; and
at least a portion of said sec-butyl alcohol from step (l) is recycled to react with said isobutene contained in said hydrocarbon mixture from step (c).

### Claim 3 (depends on 1, 2)

The process of claim 1 or claim 2 wherein
in step (a) said mixture of light hydrocarbons also contains methane and ethane and in step (a) a fraction containing methane and ethane is separated from said mixture of light hydrocarbons;
in steps (c) and (d) methane, ethane and ethene are formed during said dehydrogenation;
said fraction containing methane and ethane is combined with said methane, ethane and ethene formed in said dehydrogenation steps (c) and (d) to form a hydrocarbon mixture which is then catalytically reformed with steam under a pressure of 40-100 bar and at a temperature of 210.degree.-300.degree. C. whereby methyl alcohol is formed; and
said methyl alcohol is reacted with a portion of said isobutene from step (c).

### Claim 4 (depends on 1, 2)

The process of claim 1 or claim 2, wherein said propane and said butane fractions from step (a) are combined, said combined fractions are dehydrogenated, whereby a hydrocarbon mixture is formed containing C.sub.3 - and C.sub.4 -hydrocarbons, and a C.sub.3 -fraction and a C.sub.4 -fraction are separated from said hydrocarbon mixture.

### Claim 5 (depends on 1, 2)

The process of claim 1 or claim 2 wherein said reaction of step (f) is conducted in the presence of a catalyst at a temperature of 20.degree.-150.degree. C. using 0.5-10 moles of isobutene per 1 mole of isopropyl alcohol.

### Claim 6 (depends on 5)

The process of claim 5 wherein said reaction is conducted at a temperature of 30.degree.-60.degree. C.

### Claim 7 (depends on 5)

The process of claim 5 wherein said reaction is conducted using 1-3 moles of isobutene per 1 mole of isopropyl alcohol.

### Claim 8 (depends on 1, 2)

The process of claim 1 or claim 2 wherein
in step (f) only a portion of said isopropyl alcohol is reacted with said isobutene, whereby said mixture formed also contains unreacted isopropyl alcohol, and said unreacted isopropyl alcohol is separated from said product mixture from step (f) by extracting with water.

### Claim 9 (depends on 1, 2)

The process of claim 1 or claim 2 wherein in step (f) a mixture of isopropyl alcohol and water is reacted with said isobutene in the presence of an acid catalyst at a temperature of 20.degree.-150.degree. C. using 1-20 moles of isobutene per 1 mole of water and 0.1-10 moles of isobutene per 1 mole of isopropyl alcohol.

### Claim 10 (depends on 1, 2)

The process of claim 1 or claim 2 wherein the product mixture of step (e) also contains water and a mixture of isopropyl alcohol and water is separated from said product mixture by rectification,
isopropyl alcohol is separated from said mixture of isopropyl alcohol and water by extraction with a mixture of C.sub.4 -hydrocarbons containing isobutene, whereby an organic phase containing at least isobutene, other C.sub.4 -hydrocarbons and isopropyl alcohol, and an aqueous phase are formed,
said organic phase is separated by distillation into a mixture containing isopropyl alcohol and isobutene and a mixture containing the other C.sub.4 -hydrocarbons,
said mixture containing isopropyl alcohol and isobutene is taken to step (f),
said mixture containing other C.sub.4 -hydrocarbons is recycled to said extraction, and
said aqueous phase is recycled to step (e).

### Claim 11 (depends on 1, 2)

The process of claim 1 or claim 2 wherein said hydrocarbon mixture from step (b) is divided into a n-butane fraction and an isobutane fraction,
said n-butane fraction is recycled to said isomerization step (b), and
said isobutane fraction is dehydrogenated in step (c).

### Claim 12 (depends on 11)

The process of claim 11 wherein
in step (c) only a portion of said isobutane is dehydrogenated whereby
said product mixture from step (c) and said product mixture from step (f) contain isobutane,
said isobutane in said product mixture from step (f) is separated therefrom and combined with hydrocarbons separated from the product mixture of the hydration step (e) and said isobutane fraction separated from the hydrocarbon mixture of step (b), to form a mixture containing isobutane, which is dehydrogenated in step (c).

### Claim 13 (depends on 2)

The process of claim 2 wherein said reaction of sec-butyl alcohol with isobutene is conducted in the presence of a catalyst at a temperature of 20.degree.-150.degree. C. using 0.5-10 moles of isobutene per 1 mole of sec-butyl alcohol.

### Claim 14 (depends on 13)

The process of claim 13 wherein said reaction is conducted at a temperature of 30.degree.-60.degree. C.

### Claim 15 (depends on 13)

The process of claim 13 wherein said reaction is conducted using 1-3 moles of isobutene per 1 mole of sec-butyl alcohol.

### Claim 16 (depends on 2)

The process of claim 2 wherein
in step (k) said reaction of isobutene with sec-butyl alcohol is conducted by reacting a mixture of sec-butyl alcohol and water with isobutene at a temperature of 20.degree.-150.degree. C. using 0.1-10 moles of isobutene per 1 mole of sec-butyl alcohol and 1-20 moles of isobutene per 1 mole of water.

### Claim 17 (depends on 16)

The process of claim 16 wherein said reaction is conducted at a temperature of 30.degree.-80.degree. C.

### Claim 18 (depends on 2)

The process of claim 2 wherein
in step (l), a reaction product mixture is formed containing at least sec-butanol, water and hydrocarbons,
a sec-butyl alcohol-water mixture is separated from said reaction product mixture by rectification,
sec-butyl alcohol is extracted from said sec-butyl alcohol-water mixture by treating with a mixture of C.sub.4 -hydrocarbons containing isobutene, whereby an organic phase containing at least sec-butyl alcohol, isobutene, and other C.sub.4 -hydrocarbons, and an aqueous phase are formed,
said organic phase is separated by distillation into a mixture containing sec-butyl alcohol and isobutene and a mixture containing the other C.sub.4 -hydrocarbons,
said mixture of sec-butyl alcohol and isobutene is taken to step (k),
said mixture containing the other C.sub.4 -hydrocarbons is recycled to said extraction, and
said aqueous phase is recycled to step (l).

### Claim 19 (depends on 2)

The process of claim 2 wherein
in step (l) reaction product mixture is formed containing at least sec-butanol, water, and hydrocarbons,
sec-butyl alcohol is extracted from said reaction product mixture with a hydrocarbon mixture comprising predominantly n-butane and butene-2, whereby an organic phase containing sec-butyl alcohol and hydrocarbons, and an aqueous phase are formed,
said organic phase is separated by distillation into a mixture containing at least sec-butanol and a mixture containing the hydrocarbons,
said mixture containing sec-butanol is taken to step (k),
said hydrocarbons are proportionally recycled to said extraction and to step (l), and
said aqueous phase is recycled to step (l).

### Claim 20 (depends on 2)

The process of claim 2 wherein
isobutene in said hydrocarbon mixture from step (c) is reacted with a mixture of isopropyl alcohol and sec-butyl alcohol.

### Claim 21 (depends on 20)

The process of claim 20, wherein said mixture of isopropyl alcohol and sec-butyl alcohol also contains water.

### Claim 22 (depends on 3)

The process of claim 3 wherein
in step (f) only a portion of said isobutene is reacted whereby said hydrocarbons in said product mixture contain unreacted isobutene,
said hydrocarbons are separated from said product mixture and combined with at least a portion of said hydrocarbon mixture from step (c) to form a combined hydrocarbon mixture, and
said combined hydrocarbon mixture is reacted with methyl alcohol to form methyl isobutyl ether.

### Claim 23 (depends on 2)

The process of claim 2 wherein
in step (k) only a portion of said isobutene is reacted, wherein a product mixture is formed containing sec-butyl tert-butyl ether and hydrocarbons including unreacted isobutene,
said hydrocarbons including unreacted isobutene are separated from said product mixture and combined with at least a portion of said hydrocarbon mixture from step (c) to form a combined hydrocarbon mixture, and
said combined hydrocarbon mixture is reacted with methyl alcohol to form methyl isobutyl ether.