Patentamt

J E u r o p aEuropean
i s c h . e Patent
s
Off ice

Publication number:

Office europ6en des brevets

EUROPEAN

@
g)

Application number: 84104657.6

g)

Date of filing: 25.04.84

Priority: 27.04.83 JP 7471 0/83

0 1 2 4 0 7 8
A 11

PATENT A P P L I C A T I O N
@ Int. CI.3: C 07 C 43/04, C 07 C 4 1 / 0 9 ,
C07C 41/42

@ Applicant: MITSUBISHI CHEMICAL INDUSTRIES

LIMITED, 5-2, Marunouchi 2-chome Chiyoda-ku,
Tokyo 100 (JP)

Date of publication of application: 07.11.84

Bulletin
A/AR
Bimeiin R
on/to

@ Inventor: Murai, Nobuyuki, No. 1400, Oaza-matsumoto,

Yokkaichi-shi Mie-ken (JP)
^ventor: Naka^chL Kazuya, No. 368, Shohmachi,
IVifltSUZ8K9-Snl Mle-KSn (JP)
Inventor: Otake, Masayuki, No. 1305, Nagatsuda-cho Midori-ku, Yokohama-shi Kanagawa-ken (JP)
Inventor: Ushikubo, Takashi, 10-23,
Sagamioono 5-chome Sagamihara-shi, Kanaga-ken (JP)

Designated Contracting States: DEFRGB

(74) Representative: Wachtershauser, Giinter, Dr., Tal 29,

D-8000 Miinchen 2 (DE)

(4) Process for the production of dimethyl ether useful as a propellant.

7 A process for producing dimethyl ether useful as a propellant by dehydrating methanol and recovering dimethyl ether
from the dehydrated product by distillation, which comprises
(A) a reaction step wherein the dehydration reaction of methanol is conducted in a vapour phase under pressure of from 2 to
50 kg/cm2G in the presence of a solid acid catalyst,
(B) a first distillation step wherein the reaction mixture formed
by the above reaction step is cooled and introduced into a
pressurized distillation column under pressure of at least 5 kg/
cm2G; refined dimethyl ether is obtained as a side stream;
substance having a boiling point lower than that of dimethyl
ether is distilled from the top; and the bottom is withdrawn,
and
(C) a second distillation step wherein said bottom is introduced into a second distillation column under pressure lower
than the pressure of the pressurized distillation column; unreacted methanol is recovered as a side stream from the second distillation column; substance having a boiling point lower
than that of methanol is distilled from the top; and the bottom
is withdrawn, whereby
(D) the unreacted methanol recovered from the second distillation step is recycled to the reaction step.

The
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product.

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the

Figure

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Figure

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material

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step

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25

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Figure

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to

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top

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9 or
If

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the

cost

enormous

and

impractical

dimethyl

ether

obtained

as

ccLumn

in

collected
from

the

lower

point

reflux

formed

water

higher

than
the

The

second

the

is

step

column
the

methanol

recovered

via

the

is

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this

from

separation,
distilled

methanol

17.

In

as

condenser

the

9.

point
introduced
12

and

time

the

column,

by-products

than

the

boiling

point

of

a
16

this

of

than

first

into

7 and

stream
a

pure
and

recovery

separation,

having

methanol

at

distillation

almost

side

the

distillation

second
the

second

column

whereby

of

top

lower

tank

distillation

discharged
to

lower

pressure

pressure.

subjected

through

valve

reboiler

comprises

step

under

pressurized

bottom

14

and

time,

13.

distillation

unreacted

methanol

valve

via

step

and

boiling

purged

boiling

10

methanol,

withdrawn

is

ether,

control

atmospheric

column,

having

is

same

control

unreacted

the

distilled

and

the pressure

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is

ether

of

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having

ether

dimethyl

be

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At

substance

of

condenser

11.

5 will

ether

pressurized
ether

gas
than

point

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tank

composed

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dimethyl

distillation

second

of

the

dimethyl

8 and

dimethyl

distillation
pressure

of

bottom

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ether

of

part

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in

is

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by

inert

an

pressure

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column,

that

level

liquid

least

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than

the

dimethyl

condenser

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into

stream

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with

together

side

by

the

since

-23.6oC.

top

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is

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7,

introducing

column.

kg/cm2G,

by

boiling
and

higher

from
points
than

the

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reflux

condenser

formed

water

than

the

and

recycling

pump

methanol

the

to

maintained

the

above,

at

controlling

operation

no

such

and

the

is

the

an

column,

points

higher
via

a methanol

by

whereby

converted

to

the

dimethyl

will

be

apparatus

as

valve

7,

or

be

the

at

whereby

no

when

conducted

of

the

pressure

or

pressure,

under

conducted

of

14

the

pressure,
is required

compressor

time

column

pressure

atmospheric

pump
may

the

required

is

control

control

than

under

distillation

distillation

second

column

conducted

pressure

pressure

the

methanol

system,

be

lower

pressure

distillation

when

The

recycled

can

through

discharged

are

20.

reaction

material

pressurized

even

be

of

boiling

methanol,
pump

purged

bottom

having

will
the

are

yield.

good

distillation

from

of

step

18

mentioned

As

and

discharge

starting

in

ether

by-products

this

by

dimethyl

point

and

19

recovered

is

15,

boiling

reboiler

ether

of

point

simply

introducing

by

the

the

bottom.
to

According
suitable

ether
simply
the

for

produced

in

consumption

also

the

as

use

methanol
the

of

starting

by-product

the

of

can

high

methanol

material,
methanol

propellant

reaction,

extremely

invention,

present

combination

recovered

material

as

for

the

by

the

two

be

can

obtained

be

purification

reused

as

the

whereby

dimethyl

overall

yield

starting
not

dimethyl

pure

only

containing

steps,
starting
ether

relative

material.
synthetic

and

be

can
to

the

Further,
methanol

substantial

amount

but
of

impurities,
of

generated

polyester,

attributable
from

of

as

the

high

purity

of

the

distillation

step

starting

material.

is

the

by

of

distillation

conducted

under

number

movable

of

conventional

Now,
further

the
detail

the

or

pump

providing

low
mixture

mixture

reaction

dehydration

Accordingly,
compared
for

by

is

reaction

required

first

system,

which

as

the

is

with

the

maintaining

minimized.
invention

present
with

by

the

less

lavor

of

compressor

be

of

and

reaction

the

the

superior

degree

by

mixture

pressure.

will
and

be

can

when

atmospheric
parts

made

the

Thus,

pressurized

introducing

step

process,

apparatus

of

separated

produced

reaction

liquefying

means

time

the

at

or

the

necessity

reaction

the

cooling

compression

without

be

can

be

simply

can

readily
methanol.

of

in

conducted

production

practically

dehydration

valve

liquefying

required

the

the

scep

temperature

to

irrespective

control

of

is

ether

dimethyl

pressure control

pressure

recovered

invention

the

by-products

be

can

purity

since

Further,

the

present

whereby

process
in

the

and

of

since

employed,

impurities

ether

always

the

such

to

dimethyl

process

be

may

time

the

at

e.g.

will

reference

to

an

be

described

in

Example.

EXAMPLE:
Into
catalyst
a

reactor

containing

temperature

methanol

packed

of

0.08%

from

pressurized

250
in

with

0.1

by

weight

to

350C

liquid

m3 of
of
by

state

Na20

-alumina
and

a heating
and

heated
medium,

subsequently

to

and

evaporated
and
of

the
11

reaction

and

obtained.

conducted

under

thereby

obtained,

was

of

mixed

liquid

distillation
Raschig

rings,

maintained
In

the

whereby

pressure

ether

time,

distilled

comprising

at

was

of

into

27

kg/hr

atmospheric

purity

of

least

35

kg/hr

(inner
the

height

The

second

distillation

the

and

boiling

whereby

diameter:

column

100

was

high
at

mm,

bottom

flow

column

layer:

methanol

ethane

Further,

introduced

packed

and

dimethyl
and

methane

water

99.9%

stream,

column,

distillation

second

of

of

at

side

the

1 kg/hr.

and

discharged

as

of

top

amounts
of

rate

was

the

column,

the

2.0,

which

3 m)

layer:

having

rings,

of

6 mmo

mm,

of_2.0,

Raschig

ratio

pressurized

100

gas-

ratio

from

pressure

into

of

reflux

of

was

kg/cm2G.

10

unreacted methanol,

by-products

total

mixture

reaction

was

rate

weight

at

certain

containing

by

the

methanol

and

packed

of

of

of

weight

substances,

weight

by

distillation

ether

at

same

the

conducted

dimethyl

obtained
the

of

pressure

was

other

diameter:

(inner

pressurized

distillation

reflux

kg/hr,

cooled,

by

16%

water,

introduced

was

height

under

40%

This

liquefied.

column

of

water

ether,

phases,

of

weight

cooling,

dimethyl
and

by

56.7%

comprising

weight

by

4.8%

this

By

condensed

was

63

was

mixture

22.5%

ether,

methanol

amount

product

reaction

dimethyl

at

of

rate

kg/cm2G.

whereby

was

at

supplied

reaction

dehydration

The

of

is

heated,

rate

under
6 mmo

5 m).

operated
containing

at
no

substantial
side

as

to

the

impurities
stream,

reactor.

column,

top,

and

waste

was

discharged

the

column.

the

recovered
in

Further,

methanol

methylformate

and

recovered

was

containing

is

distilled

water
at

the
a

at

containing
rate

of

17

was

9 kg/hr
recycled

distillation

amount

rate

of

high

boiling

kg/hr

of

rate

methanol

second

certain
a

at

of

1 kg/hr

from

the

from

the

by-products
bottom

of

1.

for

A process

propellant

from
which

distillation,
(A)

reaction

is

methanol
from

2 to

the

and

recovering

product

dehydrated

as

by

comprises
wherein

step

conducted
kg/cm2G

50

useful

ether

dimethyl

methanol

dehydrating

by
ether

dimethyl

producing

in
in

the

under

phase

vapour

the

reaction

dehydration

presence

of

of

pressure

solid

of

acid

catalyst,
(B)

first

mixture

distillation

formed
into

introduced
pressure

of

at

obtained

as

lower

point
the

top;

(C)

second

introduced

into

distillation
stream

substance

is

withdrawn,
the

than

is

the

from

the
a

boiling

distilled

of

from

the

from

and

is

under

pressurized
is

recovered

as

column;
than

lower
top;

boiling

bottom

column

distillation

the

that

the

of

bottom

is

whereby

step

methanol
is

recovered

recycled

to

the

is

ether

distilled

said

methanol

point

under

and

distillation
pressure

is

wherein

step

second

dimethyl

ether

and

cooled

column

having

withdrawn,

unreacted

column;

refined

dimethyl

second

unreacted

distillation

of

bottom

having

methanol

(D)

that

is

step

distillation

substance

stream;

distillation

lower

pressure

side

side

reaction

the

reaction

5 kg/cm2G;

least

the

above

pressurized

than

and

the

by

wherein

step

from

the

reaction

second
step.

2.
acid

The

catalyst
3.

is

catalyst

The

other

an

than

dehydration

reaction

from

450C.

4.

120
The

to

reaction

3 to
5.

30
The

6.
(B),

The
the

in

to

(B),

The
the

8.

The

methanol

the

Claim

conducted

to

is

silica

wherein

1,
at

Claim

conducted

that
is

to

1,

the
of

temperature

wherein

under

then

the
of

pressure

from

to

Claim

mixture

is

cooled

condensed,

10

1,

wherein

to
and

distillation

and

evaporated

90%

by

1,

weight

of

the
into

a
reaction
the

Claim

mixture

is

introduced

column

1,

without

wherein
into

in

is

according
by-product

to

Claim

methanol.

1,

step

the

pressurizing

mixture.
process

step

column.
to

distillation

such

under

introduced

then

in

wherein

according

reaction

is

methanol

step.

according

from

process

Claim

state,

reaction

reaction

pressurized
reaction

is

liquid

process

pressurized
7.

to

according

process

condition
mixture

and/or

catalyst

solid

the

kg/cm2G.

pressurized
supplied

wherein

1,

zeolite.

according

process

dehydration

alumina

according

process

Claim

to

according

process

wherein

the

the