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i s c h . e Patent
s
Office

0 1 5 0
A2

Publication number:

Office europeen des brevets

EUROPEAN

PATENT A P P L I C A T I O N
Int. CI.4: C
c
C
//

@ Application number: 85300448.7

<a
@

9 8 2

n *

Dateoffi.,ng:23.01.85

Babcock-Hitachi K.K. 3-36, Takara-machi, Kure-shi

Hiroshima-ken (JP)
inventor: Arikawa, Yoshijiro of Kure Research Lab., of
Babcock-Hitachi K.K. 3-36, Takara-machi, Kure-shi
Hiroshima-ken (JP)
Inventor: Kuwahara, Takanori of Kure Research Lab., of
Babcock-Hitachi K.K. 3-36, Takara-machi, Kure-shi
Hiroshima-ken (JP)
Inventor: Tanimoto, Hirotoshi of Kure Research Lab.,
Babcock-Hitachi K.K. 3-36 Takara-machi, Kure-shi
Hiroshima-ken (JP)
Inventor: Nishimura, Yasuyuki Kure Research Lab.,
Babcock-Hitachi K.K. 3-36 Takara-machi, Kure-shi
Hiroshima-ken (JP)
Inventor: Kaku, Hlroyuki Kure Research Lab.,
Babcock-Hitachi K.K. 3-36 Takara-machi, Kure-shi
Hiroshima-ken (JP)

Priority: 27.01.84 JP 12144/84

08.03.84 JP 44469/84
Date of publication of application: 07.08.85
Bulletin 85/32
@

Designated Contracting States: BE CH DE FR QB IT LI

Applicant. BABCOCK-WTACH1 KABUSHIKI KAISHA,

6-2, 2-chome, Ohtemachi Chiyoda-ku, Tokyo (JP)

Inventor: Kamiguchi, Taiji of Kure Research Lab. of,

Babcock-Hitachi K.K. 3-36, Takara-machi, Kure-shi
Hiroshima-ken (JP)
Inventor: Yamada, Mutsuo of Kure Research Lab., of

07 C 49/08, C 07 C 4 5 / 3 5 ,
07 c 45/27, C 07 C 4 5 / 2 8 ,
07 C 4 5 / 3 0
C07F15/00

Representative: Pendiebury, Anthony et al, Page, White

&Farrer5 Plough Place New Fetter Lane, London
EC4A1HY (GB)

Process for producing acetone.

@A A process for producing acetone selectively and with a
high yield by oxidizing propylene by means of the combined
oxygen in an oxygen complex under milder conditions and at a
single stage is provided wherein a composite catalyst comprising as catalyst components, a transition metal complex with
the metal ion of which oxygen molecule can coordinate to form
an oxygen complex, and another kind transition metal complex
with the metal ion of which propylene can coordinate to form
a propylene complex is employed, and propylene activated by
the complex formation is oxidized by the combined oxygen
3 activated by the complex formation to thereby obtain acetone.
N
8

O
ft

@0.10
E
E0.08

|^0.06
Q. =L
o Q02
~ ?
c Jj
o
g-e
a
20c

ACTORUM AG

PhCN/hmpa
Propylene

partial

WCfc/fchCN/hmpa
pressure;

1 atm

and more

by o x i d i z i n g
is

Acetone
nitrocellulose,
solvent

for

resins,

and f u r t h e r

isobutyl
ketene,

as

products

carbninol,
etc.;

chemical

thus

classified

as

it

has

processes

in

an oxygen
ketone

in

etc.

camphor,

amount,
the

an

and has

been

but

also

as

isopropanol

(2)

cumene

(3)

propylene

presence

for

for

many

ketone,

bisphenol

important

producing

dehydrogenation

process,

methyl

A and f u r t h e r

position

in

acetone

may be r o u g h l y

process.

dehydrogenation

conditions

of 300 to

of a d e h y d r o g e n a t i o n

isopropanol

process,

and

oxidization

conversion

and

process

500C

pharmaceuticals

isobutyl

methacrylate,

complex.

acetylcellulose,

raw m a t e r i a l

as methyl
occupied

for

a large

producing

follows:

(1)

severe

and the

such

of

aliphatic

as a s o l v e n t
etc.

for

a process

by means

a synthetic

methyl

The i s o p r o p a n o l
the

to

acetone

producing

industries.

Commercial

under

only

acetylene,

fats,

intermediate

relates

propylene

not

for

to a p r o c e s s

a representative

commercially

field,

it

particularly

acetone

used

relates

invention

This

has

been

operated

and 3 atm p r e s s u r e i n
c a t a l y s t such as ZnO, Cu, e t c .

the

to

selectivity

90%,

respectively

page

266,

translated
Further,

Teruaki

by
cumene

cumene

is

pheric

pressure

salt

like

as

oxide,

which

is

then

60 -65C

into

on

cumene

is

is

60%

phenol

been

of

wherein

been

chloride

processes

for

265).

obtained

water
this

to

of

by

but

used

is
form

reaction

acid

shown

most

by

divalent

(CH3COCH3).
in

the

products

and

at

the

and

is

above

Cu (2 )Cl2
is

palladium
Water

following

process

palladium
employed
among

literature,

a composite

0 -2)

have

single

Wacker

characteristic

process,

(pH:

based

producing

(Cu (2)Cl2 )

(see

at

processes

for

material

Pd (2)Cl2 and

solution

acetone
as

is

the

so-called

chloride

to this

oxidized

raw

acetone

producing

These

conditions
the

hydroper-

H2S04

of

Co

Cu,

selectivity

a process

as

~2%

proportion

is,

process

dissolving

The

acetone.

that

is

0.1

atmosof

cumene

prepare
with

reaction

According

a hydrochloric
propylene

40%

noted,

This

presence

the

(Pd (2)Cl2 ) -cupric

catalyst.

page

and

propylene

the

acetone.

and

90%

milder

under
has

stage

and

operated,

currently

acetone

as

about

in

decomposed

phenol

the

under

to

wherein

process

and

(1978)).

Dojin

Kagaku
a

and

Arpe

120'C

phase

catalyst

to

and

98%

as

Chemistry,

H.J.

Tokyo

directed
at

liquid

the

or

is

oxygen-oxidized
in

and

Mukaiyama,

process

regarded

Organic

Weissermel

K.

by

been

Industrial

(see

written

have

acetone

as

catalyst

catalyst

First

employed.
(Pd (2) )

and

participates
equation:

in

in

As
into

metal

necessary
for

from

seen

to

coexistent

reaction

this

and

making

prevent
by

therewith,

time

is

oxygen-oxidized

in

according

to

the

following

in

of

the

the

equation:

and

at

byproduced

coexistence

equation

Pd(2)

Cu(2)Cl2

following

Cu(1)Cl,

is

into

Pd(O)

amount

large

soluble

difficultly

Further,

oxidize

reduced

It

precipitates.

also

shown

as

is

Pd(2)

equation,

which

(Pd (0) )

palladium

regeneration

that

this

of

returned

HCl

to

Cu(Z)Cl2:

described

As

and

Pd(2)/Pd(O)
is

propylene
is

not

above,

made

oxidation-reduction
is

the

resistant

of

of

is

Still

in

is

since

reactivity,

the

reaction

and

14

atm.

In

of

choice

hence

and

140C

Cu(1)Cl

required.

oxygen

this

water

the

Further,
formed

HC

aqueous

low,
the

has

since

midway
solution

a corrosionsince

further,

conditions
it

complicated

are

of

higher

addition,

constitutes

reaction.

concentration
and

molecule

Pd (2)/Pd(0)-Cu (2)/Cu(1)

above,

the

and

raised,

must
the

used

material

solubility
be

Pd(0)

a high
is

0 -2)

the

of

of

oxygen

but

propylene,

described
step

soluble

reaction,

(pH:

the

as

rate-determining

difficultly

with

of

system

oxidation

since

However,

reaction

utilized

continuous

possible.

reacted

a redox

employing

Cu(2)/Cu(l),

directly

system

by

its

solubility

olefin,
are

been

as

the
severe

regarded

lower
as
that

under

such

the

higher,

or

is

265).

into

have

to
a

works

at

relatively

conditions

The

means

and

and
and

of

In

provide

ion
an

coordinate

to

any

of

stage

(Revised

complete

et

milder

produced

under

has

desired.

been

invention
for

is

producing

to

an

complex

transition

metal

form

a propylene

metal

molecule
another

ion

the

the

is

catalyst

and

by
under

stage.

invention

oxygen

selec-

acetone

in

single

these

solve

oxygen

oxygen

out

thus

pressures;

propylene

al,

carried

been

oxidizing

complex,

by

hence

by

with

activated

explosion;

yield

present

which

propylene

Kihara

by

has

and

present

at

as

is

excess

(1978)).

be

can

in
with

necessary

process

a composite

oxygen

complex

propylene

the

components,

metal
form

and

such

of

literature,

mixed

edited

a process

a high

wherein

catalyst

the

is

Kogyosha

a single

combined

short,

it

above

is.99%
2 -4%

and

dissolved

oxygen

temperatures

of

with

the

a process

metal

at

the

(see

sheet,

acetone

conditions

milder

the

high

object

problems
tively

flow

above,

wherein

a process

92%

becomes

Kagaku

described

As

is

troubles

thereto

296,

p.

acetone

phase,

of

production

II,

propylene

if

gas

a possibility

of

Vol.

to

the

countermeasure

of

produced

Furthermore,

discharged

conversion
to

selectivity

propionaldehyde
page

the

conditions,

of

to

comprising
complex

as

with

coordinate

can
kind

which

complex,

complex

directed

transition

propylene

is

formation

employed,
is

can
and

oxidized

combined

by

the

to

thereby

aqueous

ohtain

system.

the

present
for

a process
in

propylene

containing

the

as

of

the

IV -VII
X,

phorus

compound;

L',

organic

of

such

the

and

the

in

the

Embodiments
described

by

accompanying

compounds;

way

of

of

the

of

example
in

from

the

n,

the

n',

to
Table;

group
and

each

n',

above

each
l

phos-

compounds

n and

l',

l,

organic

Periodic

the

m',

Periodic

belonging

fluorine

and
m',

m,

range

drawings

of

m,

and

transition

the
l'

number
each

are

1 ~ 4.

present
only

which:-

of

groups

the

of
an

metal

valences of

anion;

above

L,

the

I,

VIII

group

organic

Xn'L'l')

coordination

by

group

selected

compound

above

The

the

VIII

group

by the

(M'm'

of

M means

halogens;

as

nitriles,

metals

the

(Mm Xn.Ll)

by c o o r d i n a t i o n

complex

a transition

M',

determined

preferably

in

catalyst

a complex

catalyst,

to

non-

catalyst,

a composite

wherein

oxygen-oxidizing

a complex

belonging

phosphorus

ligands.

and

propylene

group

number

of

complex

propylene ,

in

group

consisting

a metal

coordinating

of

oxygen

anion

Table;

platinum

by

an oxygen complex c a t a l y s t

iron

an

acetone

complex

in

in

producing

metal

metal

or

resides

the

with

transition

invention

formation

complex

conditions

mild

employing

forming

complex

under

presence

with

of

the

by

comprises

forming

complex

capable

the

process

capable

acetone

solvent

Namely

which

activated

oxygen

invention
with

will

reference

now
to

be
the

1 shows

Fig.
absorption

a view
of

spectra

complexes

ultraviolet

the

illustrating

in

employed

the

present

invention.

studies
to

formation

to

oxygen

oxidizing

various

copper

of

Metal

Proteins,

(1983)).

However,

out

on

stable

utilizable

for

presentative
of
phoramide
oxide;

19013

monoxide
with

oxygen.

and

oxygen

scale

are

very

based
of

on

chloride

(Chemistry
Kohdansha

reactions

of
carried

complexes,

organic

research

extensive

metal

substrates.

of

compounds,
In

(Cu(1)C.l,hmpa), a
with

on

recomplex

hexamethylphos-

tris(dimethylamino)phosphine

denoted

exhibits

made

Yamanaka,

transition

(Cu(1)Cl)

name:

proposed

been

of

few.

made

have

a solution

laid-open

(CO),

etc.

of

example,

(1982))

heme-protein,

by

oxidation

hereinafter

have

oxidation

means

reaction

studies

of

( other

application

of

according

oxidation

the

Ohtsuka

by

inventors

cuprous

for

iron

complexes

oxygen

results

constituting

examples

commercial
present

of

capable

various

edited

substances

The

complex,

propylene

effective

heme-protein,

of

compounds,

on

organic

the

complexes

agent

organic

illustrating

method.

absorption

As
an

the

on

gas

a view

2 shows

Fig.

hmpa)

as

56-118720

Sho

No.
as

an

(Japanese

absorbing

a deep

green

patent

(1981)
solution

color

when

and
for

Sho

57-

carbon

contacted

Such a complex
above c a s e ,
Ti(3)

M is Cu,

the

hmpa

monovalent
oxidized

that

the

to

green

was

found

did

not

occur.

In

solutions.

Fig.

1,

plex

(solvent:

spectra
in

the

the

of

above

complex
From

the

Cu(1)Clhmpa

is

or

e.g.

V(3)Cl3'

absorbs

the

following
considered
in

also

occur
its

oxygen,

oxygen-

initially

might

color

the

might

this

absorption

spectra

of

results,

it

the

solution,

was
even

found
of

1 of

(numeral

solution

it

was

solution

the

from

described

as

(numeral
spectra

solution
confirmed
when

of

2 of

that

comthe

absorbed

Fig.

1)

were

divalent

the

in

was

3 of
the

in

shown

and

oxygen

we

respec-

as

1)

(numeral

oxygen

the

Cu(1)Cl-hmpa

having

by

above
point,

that

Fig.

it

thus

red;

clarify

obtained

complex

dark

was

divalent

of

further

to

ethanol)
solution

hmpa

reaction

a result
of

solution

complex

with

(Cu(2)Cl2(hmpa)2)

these

Further,when

usually
in

a result

as

of

order

As

different

entirely

is

shown

as

oxidation

spectra

and

ultraviolet

tive

valence

reaction

(Cu(2)Cl2)
the

the

anion

compound

inventors

present

color

that

measured

the

l=1 .

In t h e

color:

the

compound

and

Cu(l)

copper

solution

However,
copper

the

n=1 and

m=l,

Ti(3)Cl3hmpa

of

lower

oxidation

same

Cu(1)Cl.hmpa
change

of

formula Mm Xn.Ll.

l =1),respectively.

divalent

hence

equation;

is

solution

copper
into

and

hmpa,

metal

complex

n=3

when

Now,

L is

a central

resulting
( m=1,

by the g e n e r a l

expressed
X is Cl,

is

V(3)

or

Cl ,

is

copper
Fig.

case

absorbed,

1).
of

the

not

consumed

oxygen

was

into

Cu(2),

but

so-called

oxygen

complex

tion

in

the

form

of

Definite
solution
oxygen

was

1:

formed

Such

2 and

oxidation

not

eliminated

reduced
is

oxygen
free

Accordingly,

complex,

unreacted

the
by

is,

Cu(l)

in

is

the

the

amount

found

that

that

oxygencombined

of

coordinated

the

oxygen

absorption

to

phase

part

excess

reaction

combined
to

the

reduced

oxidation

the

complex

remove

under

oxygen

avoid
of

under
reaction

form

to

easily

possible
gas

degassed

Cu(1)Clhmpa
air

is

oxygen

or

or

oxygen

feature

specific

heated

of

Cu(l)

complex

oxygen

is

the

to

of

reported.

the

degassing

means
it

been

the

oxygen

of

case

complex

equation:

after the

or

an

means

by

possible

since

oxygen

it

with

is

was

stable

that

when

heating

in

the

with

absorbed

oxygen

yet

so

of

was

Further

is

that

it

substrate

organic
oxygen

by

is

100C.

contacted

of

not

Cu(2)

Thus,

complex,

oxygen

has

into

even

solu-

of

coordinated

it

following

complex

irreversible.
is

the

at

the

form

Cu(1)Cl.hmpa

complex

complex

pressure,

solution

amount

complex

boiling

of

a result,

the

Cu(l)

oxygen

as

to

it

the

measurement

resulting

oxygen
of

requires
this

of

the

oxygen

This

of

and

according

an

wherein

to

subjected

ratio

in

present

in

Cu(l)

molecule.

oxygen

absorbed,

molar

was

concentrations

were

the

it

oxidize

to

pressure.
of
in

the
the

remaining
the

reactor,

the

is

complex

since

Further,

complex

oxygen
is

the

acetone

by

as
other

described
form

of

next

Thus,
of

of

group
as

Pd(2)Cl2
in

VIII

dissolves

in

same
air

oxygen,

activated

then

it

by
as

compound,
activated

be

into

will

in

become

oxidation

the

possible
at

reaction

lower

extensive

made

metals

of

the

to

belonging

Periodic

the

research

hmpa

platinum

Table.

example

comgroup
chloride

Palladium

forms

a complex

equation,

where-

with

coordinated

are

following

on

and

well

therein:

this

M'm'

xn' .L' l,

the

central
the

complex
then m'=1,
metal

ion

resulting

is

is

and

m' = 2,

n'

and

l'=2

Pt(2)

or
is

complex

=3

by

expressed

n'=2

Ir(3)2(SO4)3(hmpa)2- and
former

the

pressures.

molecules

shown

Pd(2)Cl2 as

all

oxidized

is

metal

instant

have

of

pure

oxygen

can

a representative

two

S042- ,

the

transition

plexes

combined

complex,

we

of

safety.

invention

form

to

propylene

transition

lower

and

air

of

aspect

present

case

propylene

easily

temperatures

If

the

propylene
out

when

the

if

above,

carry

the

of

the

the

source.

hand,

with

coordinating

in

that

the

from

oxygen

oxygen

means

of

complex

as

sufficient
On

to

the

absorbs

selectively

in

advantageous

very

m' =1,
and

l'

the

general

in t h i s

case.

Ir(3)

and

Further
the

Pt(2)SO4.(hmpa)
n' =1
=2

in

and
the

l'

formula

=2

latter.

if

anion
or
in

the

is

It
method

first

was

whether

coordinates

measured

was

change

in

amount

was

vent.

Thus,

the

example,
ing

was

result,

it

(an

benzonitrile
were
to

absorbed,
the

are

As

the

(A),

but

complex
complex

the
is
of

nitriles

when
is

as

sol-

stable

a more

of

of

becomes

with

to

amount

as

a modify-

a Pd (2) Cl2
of

of

the

of

propylene

a hmpa/

since

these

in

it

is

propylene

the

evident
was

(CH3CN)

shown

in

systems
is

absorbed

ligand

gas

absorbed,

propylene

propylene

of

amount

are

larger

hence

to

results

figure,

amount

representative

solutions

The

acetonitrile

added

no

absorption

hmpa

forming

the

solvent-modifying

ion

the

was

a hmpa/benzonitrile/Pd(2)Cl2

amounts

this

from

amount

Pd(2)

and

solutions.

the

there

agent)

measurement

the

further present;

Namely,
of

to

of

case

absorbed

a nitrile

adding

respective

subjected

the

propylene

in

in

that

increased

system

non-aqueous,

in

the

by

(PhCN)

seen

of

complexing

solution

respective

2.

Fig.

found

was

compare

Pd(2)Cl '

and

two,

capable

obtained

Namely,

studied.

auxiliary

complex

and

a result,

dissolved

physically

complex

absorbed.

of

the

a system

(hmpa)2

system

between

complex

of

complex.

propylene

system

amount
As

Pd(2)

ligand

the

comparison.

one

a new

solution

hmpa

amount

the

propylene
As

for

form

to

solution,

complex

(hmpa)2

absorption

gas

Pd (2} Cl2. (hmpa) 2 complex

propylene

single

to

according

this

not

or

with

with

Namely,

studied

large

system
system

(B) w h e r e P d ( 2 )

that

stable

formed.
as

a representative

Pd(2)Cl2(hmpa)2 complex

solution,

the

following

When

new

is

propylene

propylene

is

complex

is

complex

formed:

passed

formed

therethrough,
in

shown

as

stable

the

following

equation:

With

such

stable

complex,

is

propylene

notably

activated.
As
ion
is

in

described
the

form

oxidized

the

short,

hmpa

complex

same

time

such

as

and

form
if

an

by

this

is

a single

and

passed

oxygen

followed
form

complex

vicinity of

oxygen

passing

is

to

almost

is

the

at

obtained

removed

propylene

which

adequate

oxidized
at

acetone.

gas

oxygen-containing

complex.

complex

40C

is

under

Pd(2)Cl2 CH3CN

solution
an

in

system

produce

hmpa

an

the

oxygen

formation

in

the

by

or

having

a propylene

in

liquid

through

complex

and

complex
in

to

thereby

oxygen

solvent

stage

oxygen

excess

oxygen
the

at

dissolved

are

necessary,

to

a non-aqueous

Pd(2)

activated

combined

in

Cu(1)Clhmpa

a ligand,

air

degassing,
complex

and

and

complex

above-mentioned

complex,

with

coordinated

propylene

propylene

the

conditions
In

to

of

by

oxygen

mild

above,

low

concentration,
by heating

through

Propylene
by

above

the

or
oxygen

activated

the combined

temperature

quantitatively

such
form

as

acetone.

This

following

equation:

In

the

oxidation

with

oxidized

oxygen

and

by

thereby

in

valences

plexes.

the

different
tion

in

separating

of

solution

propylene

and

(8)

and

it

is

thereafter

reaction,

the

oxygen

and

solution

also

the

to

produce
even

water
and

propylene
to

when

can
as

attain

the
be

the

of

to

the

gas

comple-

air

through
through

complex
(5)

equations
to

of

the

equation

propylene

limit
Further,

substrates
rate

solution

after

oxygen

explosion

a reaction

a great

propylene

obtained.

reaction

like

catalyst

according

a mixed

oxida-

the

passing

passing

acetone

entirely
an

or

has

the

again

according

is

no

com-

a procedure

repeat

regenerate

outside

range

effectiveness

possible

then

complex

addition,

and

and

distillation

as

the

utilizing

such

and

same

of

operation

resulting

the

is

an

the

in

there

from

catalyst

oxygen

hence

product

the

In

to

complex

process

processes,

possible

Cu(l)

resulting

the

(9).

is

ion

is

with

metals

a process

Pd(2)

propylene

thereby

the
of

means

it

central

production

from

of

way

activated

acetone;

the

conventional

that

advantage

tion

by

in

as

process

of

mechanism

reaction

form

the

by

a manner,

coordinated

instant

the

Thus,

to

expressed

such

and

complex

molecule

activated

change

by

Pd(2)

is

in

invention,

present

coordinated

reaction

are

superior

is

with

passed,
since

activated,
to

those

of

the

the

reaction
of

amount

As

in

the

small
later

complex

Ti,

Zr

of

the

group

IV,

V,

the

group

VI,

Mn of

the

group

of

VIII

group

the

halides

these,

of

preferable.
pounds

represented

phosphoramide,
reaction
the

of

di-

mono-,

and

phenylphosphinous

as

phosphorous
these,

larly

preferable.
the

other

(M'm'Xn'L'l')

acid

of

hand,

as

the

by

of

W of

Ni

of

or

oxide,
formed

among

com-

hexamethylby the

ethanol

or
dimethyl-

methyl

of

reaction
the

etc.

in
the

are

and
phos-

like,
acid

etc.,

preferable,

(hmpa)

the

the

particularly

triphenylphosphine,

forming

Mo,

Cr,

dimethylphosphinic

M'm'Xn'

I,

phosphoric acid,

ethanol

esters,

group

phosphorus

methanol,

derivatives,

capable

are

organic

hexamethylphosphoramide

among

On

with

formed

methanol,

acid

V(3)

triesters

derivatives

as

triethylphosphine,

esters,

L,

system

preferable, and

are

and

the

Co,

Fe,

of

capable

V,

group

methylphosphonate,

triesters

with

acid

phorous

and

be

can

catalyst

of

Ag

and

VII,

ligand

acid

dimethyl
each

Cu,

the

Table

di-

phosphoric

phosphinate,

composite

triphenylphosphine

by

mono,

and

like,

the

(MmXnLQ)

of

Ti(3)

Cu(l),

for

As

the

Nb of

Periodic

selectivity

Examples.

salts

invention,

present

tem-

the

conditions,

the

catalyst
in

complex

oxygen

in

since

further,

mild

and

at

pressure

Still

under

out

is

the

atmospheric

40C.

carried

described

as
MmXn

forming
the

is

the

about

as

byproducts

improved,

of

low

as

perature

under

art

prior

is

and

particu-

complex

propylene

each

catalyst

complex,

salts
to

of

lower

platinum

valence

these,

larly

preferable.

acetonitrile,
the

fluorine

ly

etc.

the

Ir(3)

and

preferable,

such

as

tolunitrile,
and

compounds,

fluorinated

and
particu-

are

nitriles

benzonitrile,

as

belonging

preferable,

or

L',

phosphorus

such

are

Pt(2)

ligand

metals

benzotri-

toluene,

nitriles

organic

particular-

are

preferable.
As
in

out

solvents

of

Examples

such

L or

L'

liquid,

same

time.

Further,

it

catalyst
carbon,

acetone
complex.

dissolve

time

means

of

least

in

the

cyclo-

also

possible

to

have

carrier

a porous
glass,

combined

itself

the

such

oxygen

in

the

etc.
ligand

solvent

composite
active

as

propylene

the
as

having

polymers

oxidize

ethanol,

where

case
use

the

selected

tetrahydrofuran,

to

and

kind

carbonate,

propylene

pyridine,

from

preferable.

toluene,

possible

etc.

are

one

carried

composite

cyclohexanone,

acetate,

porous

the

mmHg)

n-hexane,

ketone,

is

separable

is

on

structure,

as

reaction

easily

at

Further

it

is

is

56C/760
are

such

butyl

silicates,

by

which

solvents

supported

reticular

those

(b.p.

thereof.

is

the

the

chlorobenzene,

mixtures

and

where

isobutyl

glycol,

chloroform,

case

same

solvents

methyl

ethylene

the

acetone

various

hexane,

the

state,

at

the resulting

from

in

solution

catalyst and

at

are

VIII

Pd(2),

organic

compounds

transition

group

of
As

of

propionitrile,

above

fluoride,

the

halides

among

etc.,

of

group

ions

a macrointo

oxygen

rate
are

If

the

reaction

is

also

hence

low;
and

preferable

is

temperature

loo

low,

the

of

40C

or

temperatures

those

of

60 -

80C

are

reaction
higher

particularly

preferable.
As

to

the

reaction

the

higher

the

oxygen

the

amount

of

the

concentration

reaction

absorption
in

propylene

is

rate

activated

of

obtained

the

and

rate,
solution

the

and

the

under

pressure,

larger

also

the

higher

a sufficient

but

propylene,

even

the

the higher

pressure,

atmospheric

pressure.
In
as

the

sulfolane,

formamide,
solution
is

used

or

to

possible

as

notably

is

etc.

solvent

such

solvent

dimethylsulfoxide,

dimethylsufolane,

trimethylmethane,

a basic

when

invention,

present

for

the

the

promote

added

to

complex

the

dimethylcatalyst
it

itself,

formation

acetone

reaction.
In

addition,

invention

is

reaction
an

may

amount

in

A novel
production
above.
more

therein

is

the

carried

out

range

where

reaction
the
by

its

on

of

in

the

no

the

present

system,

the
in

presence

of

water

precipitate

is

formed.

invention

will
The

and

have

complex

standard

the

of

a non-aqueous

Examples.

the

reaction

characteristics

using

present

way

based

in

out

complex,

Next
detail

carried
be

the

although

be

values

state.

been

described

described
of

of

examples

gas

in
volume

Example
Into
were

fed

hmpa

(325

(330

(1.3

to

g)

stopper

into

another

fed

were

7 mmols)

g,

(Cu(1)Cl)

and

to

then

were

0.1

of

mol/l
Air

the
14

was

was

nitrogen

passed,

the

reactor

and

tion

were

removed.

oxygen

However,

in

the

and

elimination

of

oxygen

the

oxygen

the

degassing
oxygen

complex
or

the

absorption

was

of

not

the

this

observed
it

was

oxygen

ml)

containing

25C

at

under
(340

oxygen

but

thereafter

the

gas

of

in

combined
even

by

solu-

the

present

(0.011
oxygen

way

of

mol/l),
in

heating,

that

the

formation

was

confirmed

complex

in

part

m was

260

ml ,

when

phase

complex

oxygen

from

thus

like;
by

form

oxygen

reactor

capacity

dissolved

physically

solution

in

in

the

Pd(2)Cl2 .

a result,

oxygen

Both

ml).

(500

solution

absorbed,

apparently
was

gas

As

pressure.

prepare

(Cu(1)Clhmpa/

of

mol/

the

to

1 l

system)

0.015

through

passed

atmospheric
mmols)

and

Cu(1)Cl,

with

(Pd(2)Cl2)

(170

solution

and

solution

tube

test

g)

stopper

mmols)

complex

(130

into

transferred

Pd(2)Cl2CH3cNhmpa/hmpaCH3CN

50

g,

ml,

solution

catalyst

ground

chloride

acetonitrile

a complex

prepare

500

palladium

a Pd(2)Cl(CH3CN)2 complex
solutions

(5

a Cu(1)Cl,-hmpa

prepare

Further,

with

tube

test

capacity

chloride

cuprous

ml).

ground

500

irreversible.
After
at
700

25C
ml

these

under
was

operations,

the

absorbed

propylene

atmospheric
in

the

pressure.

solution

and

l,)

(1

was

passed

As

a result,

the

propylene

concentration

in

the

solution

thereafter,

the

solution

was

carried

out

for

the

resulting

As
The

and

product

reaction

of

is

in

this
of

the

formed

is

regulated
Thus,

combined

oxygen

Example

of

40C
case

and
of

propylene

notably

As

0.31

and

respectively,

of

yield

of

amount
of

80%

was

present

the

based

in

acetone

oxygen
on

the

complex.

oxygen

and

(5.3
the

acetone

the

reaction

into

is

the

the

case

gas

and

the

propylene

complex

the

oxidation

rate

the

acetone

of

the

reaction

carry

out

the

acetone

was

and

4.3

yield
of

90C.

temperature

it

uselessly

yield.

to

90C,

mmols)

in

that

except

a result,

67%

confirmed,

temperature

repeated

40C

minutes.

amounts

the

the

1 was
was

temperature

of

in

the

(9)

equation

is

complex

hence

oxygen

above

concentration

acetone

the

Example

30

the

by

the

complex.

propylene

complex;

oxygen

the

formed.

was

with

complex
to

reaction

analyzing

by

mmols)

according

the

Example,

excess

for

out

and

chromatography.

gas

8.8

g,

propylene

carried

60C

to

to

Just

mol/IL.

followed

minutes,

(0.51

the

heated

was

according

acetone

a result,

complex

30

0.06

was

in

phase

found

was

raised,
the

part

the

solution

propylene

was

reaction
in

formed
(7.4

mmols),

48 %

in

the

Particularly
of

90C,

of

the

that

if

in

elimination
reactor
the

lowers

was

reaction

concentration

increases,

case

of

although
to

reduce

In
to

addition,
the

keep

stant

1 was

Example
replaced
mmols)

the

3 was

was

40C.

Example

1 was

was

replaced

complex

solution.
the

same

was

82%.

Example

a result,

by

changing

acetonitrile
acetone

to

was

(0.57

acetonitrile

increased

yield
up

The

from

g,

to

80%

in

90%.

that

except

acetone

yield

pure

that

in

Thus,

of

the

reaction

reached

85%.

in

in

as
the

unnecessary

the

tem-

be

to

that

no

signifi-

a result,

propylene
was

carried
The

1.

of
in

complex

acetone

but

oxygen,

the
the

under

out

the

invention,

pure

except

concentration

the

Example

present

operation
As

reaction

the

conditions

the

oxygen.

observed

was
and

in

repeated

Further,

is

be

As

repeated

by

difference

source

con-

Example

oxygen

solut ,n

perature

may

acetone

that

except

and

acetonitrile

Example

cant

repeated

formed,

was

of

case

Example

air

the

raised.

was

temperature

benzonitrile.

by

benzonitrile,
the

in

possible

was

Example

9.9

the

it

pressure,

concentration

propylene
when

even

the

raising

by

yield

oxygen
cheap

air

sufficient.
6

Reaction
and

conditions

the

amount

benzonitrile

of

carried

was
as

those

hmpa

was

was

8 g

under

out
in

50
(0.1

Examples
g

(0.3

mol)

the

1 and

g mol)

and

same

3 except

and

further

composition

that

that

of

sulfolane

2.0

mols)

was

formed.

This

the

yield

(240

g,

based

complex.
the

represented
the

carried

same

0.03

g,

It

is

in

terms

the

byproducts

evidenced

are

98%
in

oxygen

of

10.8

also

basic

effective

very

of

oxygen

was

that

mmols)

for

below

solvents
improving

Example

when

The

as

acetone

in

Example

replaced

Pd(2)Cl2 was

carried

was

that

6 except

The

(Cu(l)Br).

Cu(1)Cl,
acetone

yield

was

99%.

under

the

same

by

6 were

Pt(2)Cl2

was
yield

out

Cu(1)Cl
acetone
by

replaced
was

was

conditions

replaced

yield

96%.

was
iodide

cuprous

by

as

cuprous
Further,

(Cu(l)I),

97%.

Example

Reaction

was

was

Pt(2)Ck2

The

outlas

carried

replaced

Cu(l)Br.

by

acetone

in

Pt(2)Br2
yield

was

Example

and

7 except

further,

that

Cu(1)Cl,

97%.

10

Example
The
except

that

mol).

reaction

and

operation

bromide

The

amount

sulfolane

except

Reaction

by

the

limit.
by

out

Example

the

combined

g,

to

corresponds

the

(0.63

The

in

on

Acetone

yield.

Example

(8

amount

Further,

detection

added.

was

same

that

acetone

operation

as

benzonitrile
yield

was

in

was

93%.

Example
replaced

6 was
by

carried

out

benzotrifluoride.

11

Example

Reaction
hmpa

used

was

solvent.
in

Example

12

In
limit

at

reaction

solution

Example

and

same

time

of
of

6,

sulfolanewere

added

is,

almost

of

as
the

explosion

catalyst
of

passed/amount

gas
of

76%

the
the

through

passed

h-1.

30

outside

propylene

amount

tion

oxidized

was

propylene

same

that

solution

solution

out

as
in

added

was

in

12.

in

that

operation

of

the

significant

propylene

instant

shown

as

reactor.
Further,

No

conversion

the

the

to

obtained.

Example

apparent

stepwise

in

into

producExample

required.

oxygen

operation

Cu(1)Cl

(500

mol/

combined

same

benzonitrile

hmpa,

14

The
except

time

is

the

always

Example

0.015

it

Thus,

process,
not

the

at

observed

was

acetone.

Pd(2)Cl2,

carried

was

difference

Cu(1)Cl,

a uniform

a result,

reaction

an

was

that

92%,

was

g)

13

In

is

yield

(275

that

3 except

Example

acetone.

Example

As

toluene

air

rate

in

as

3.

6,

the

at

out

and

acetone

Example

solution,

and

85

Example

were

into

in

The

as

same

carried

was

ml)

of

of
and

in

Example

replaced

containing

Pd(2)Cl2

complex
oxygen)

was

as

was

0.014

0.1

by

mol/

a propylene

(160

carried
and

V(3)Cl3

prepared.
mol/

6 was

of

V(3)Cl3

As

ml,

complex

out

a catalyst
and

result,

in

terms

of

of

0.057 mol/l,

were

formed.

40C

for

The

Thereafter
minutes

30

acetone

The

that

Ti(3)Cl3

of

0.036

in

as

(0.32

5.5

g,

mmols).

39%.

was

oxygen

and

As

by

14.

an
of

complex

acetone

oxygen

the

yield

out

the

and

0.057

under

together
The

carried

was

Ti(3)Cl3

result

a propylene
reacted

14

Example

replaced

mol/l.

Example

of

a macroreticular

m2/g;

ml)

were

ing

the

oxygen

followed

amount

complex

mol/

were

condi-

same
42%.

was

of

tube
60C,

exit

the

product

on

propylene

passing
and

succeeding
the

was

two

acetone
Further,

yield

contain-

in

Example

a particulate

filled

in

a hard

glass

followed

diameter,

gas

alone

hours.

Co.)

obtain

at
the

analyzing

4% s i n c e

Organo

to

inner

acetone

was

shown

area,

suction

was

to

by

solution

catalyst

composition

propylene

according

gas

70%.

in

mm

surface

specific

manufactured

the

the
by

catalyst

h 1)

the

recycled,

filtering

20

then

1,200

with
of

complex

This

1 mm;

XAD-4

impregnated

styrene-divinylbenzene

type

diameter,

Amberlite

by

catalyst.

reached

was

0.1

were

(50

the

in

(particle

800

(SV:

as

at

together

16

copolymer

to

operation

was

Beads

tion

combined

V(3)Cl3

They

Example

6,

on

mol/

formed.

700 -

acetone

based

yield

same

of

tions

obtain

to

reacted

were

15

Example

except

these

the

of

a rate

resulting

the

product

Thereafter
based

propylene

acetone

of

start

on
feed

the
when

the
was

heating

by

l/min.

a result,

yield

based

reaction
the

oxygen
once

in

As

chromatography.
and

reac-

exit

t i l l
gas

complex
stopped

was

and

air

the

reaction,

was

the

combined

regenerate

followed

under

experiment

to

passed

by

again

above

similar

obtain

to

by

oxidation

the

repeating

conditions,

consumed

02

results.
From
the
a

complex

in

oxygen

carrier,

carbon,
method

of

in

carried

as

in

the

this

the

Comparative

Pd(2)Ck2
solution

was

(1.3
of

same
g)

combined
as

active
the

as

treating

such

calcination

filtering

as
are

suction.

by

solution
3 and

compound
were

of

as

was

all
that

operation

except
not

less

that

added.

than

nitriles

a modifying

coordinated
and

11

and

0.1%.
and
modified

ligand

metal

contributed

As

ions

to
to

greatly

propylene.
2

example
the

addition,

methods

evidenced

complex

of

In

various

Examples

compounds

propylene

the

and

above

on

of

usable,

catalyst

yields

properties

activation

Into

it

fluorine

physical

stable

acetone

result

the

supported

silicates,

as

temperature

fluorine

organic

or

means

when

even

example

the

organic

to

of

result,

the

addition

out

are

low

gas,

Preparation

nitrile

From

etc.

such

impregnation,

heated

Comparative

carriers

glass,

by

that

was

advanced.

complex

oxygen

the

invention

reaction

the

clarified

was

present

porous

after

employable

the

porous

passing

were

of

the

it

foregoing,

carrier,

porous

the

the

reactor

and

hmpa

as
(325

in
g)

Example
to

Pd(2)Cl2(hmpa)2 complex.

1 were

prepare
No

fed

a hmpa

oxygen

was

form

passed
the

through

same

operation

the

under

of

in

in

as

followed

(60C,

30

minutes).

oxidized.

Further

not

metal

palladium

(Pd(0))

the

oxidation

by

Comparative

example

the

complex

solution

To

2 was

example
solution
out

of

the

2.

not
to

As

oxygen

Comparative
Into

out

the

the

2.

thereby

added

solution

was

reaction

instant

precipiit

was

did

not

a catalyst

prepare

in

as

by

Comparative

oxidation
it

the

carrying

was

was

utterly

necessary

complex.

oxygen

prepared

too,
not

in

Comparative

followed
in

as

since

by

carrying

Comparative

oxygen

was

not

passed,

observed.

Comparative

oxidation

no

result,

Comparative

followed

reaction

and

case,

example

was

the

to

that

benzonitrile,

this

propylene

in

g)

reaction

form

As

oxidation

Comparative
In

to

complex

In

propylene

(5

evidenced

was

in

prepared

propylene

It

operation

same

example

a result,

example

3 was

example

and

operation

observed.
pass

Cu(l)C&

reacting

by

ion

Pd(2)

in

system.

Cu(1)Cl/Pd(2)Cl2/hmpa,

same

example

added

of

means

passed

thus

formed;

was

solvent

non-aqueous

was

1,

entirely

that

propylene

Example

was

evidenced
occur

and

solution,

same conditions

propylene
tate

this

2,

example

utterly
by

system.

not

oxygen

reacted.

means

of

free

was

This

but

passed,
evidences

oxygen

does

not

that
occur

evident
from

above

the

From

that

the

using

the

Pd(2) Cl,-Cu(2)Cl,

into

the

catalyst

As

invention

is

in

as

the

different

from

wherein

of

the

activated

is

the

of

the

present

directed

to

activated

by

and

propylene
oxidized

combined

by
to

complex

oxygen

same

Examples.

art

is

the

passed
the

that

prior

complex

formation

by

evidenced

combined

propylene

with

respective

the

system.

4 was

formed

was

above

it

foregoing

process

formation

acetone

different

containing

example

is

propylene,

redox

solution

Comparative

result,

the

From

oxygen

in

complex

efficiency

a new

from

it

3,

entirely

acetone

producing
the

propylene
oxygen.

is

catalyst,

Further,

high

of

2 and

examples

invention

present

process

as

Comparative

produce

acetone.
According
not

contact

transition

together
whereby
at

low

under
a high
process

means
is

with

ion
of

the

in

the

subsequent

purification
selectively

the

produce

the

the

the

to

since

production
is

room

selectively

according

step

simplified.

absorbed

even

of

when

free

with

reacted

catalyst

objective

of

vicinity

form

are

thereby

composite

invention,

present
small,

activated

specified

Further,

is

is

and

the

coordinated

each

oxygen

pressure,

byproducts

oxygen

and

does

propylene
in

each

oxygen,

to

atmospheric

yield.
of

possible

temperatures

invention,

present

propylene
metal

by
it

the

directly
but

molecule,

to

system,

acetone

temperature,
and

with

production
the

amount

including
In
air

of
the

addition,
is

used

since
as

an

oxygen

source,

of

of

case
since

the

possible
formation
very

use

pure

oxygen
to
of

all

easily
the

advantageous

the

effectiveness

same

oxygen

is

obtained.

absorption

is

remove

excess

oxygen
in

the

complex;
aspect

as

Still

free
hence
of

oxygen
the

safety.

the

further,
it

irreversible,

in

is

after

process

is

1.

in

propylene
metal

forming
with

the

complex

catalyst,

a first

a propylene

complex

with

the

VIII

group

phosphorus
platinum

of
in

group

nitriles,

compound s e l e c t e d

valences

of the

and l and

l',

above

each

number

from

the

group

metals

metal
L, an o r g a n i c
to
L',

of

consisting

phosphorus

determined

and the

in

group

Table;

and o r g a n i c

a number

of

by t h e

above

anion;

of l i g a n d s .
acetone

producing
and l'

n', t

m, m',

Periodic

of

second

belonging

the

each

as

complex

and iron

X, an anion;
metal

compounds

n',

of the

of

transition

the

for

A process

wherein

n and

m, m',

first
capable

IV ~VII

Table;

VIII

group

fluorine

the

a transition

M means

a transition

M',

of

(M'm'Xn'L'l')

groups

Periodic

the

organic

compounds;

2.

the

the

I,

group

compound;

coordinating

wherein

containing

(MmXnLl-) c a p a b l e

complex

by c o o r d i n a t i o n

complex

propylene,
the

complex

which

catalyst,

catalyst

by c o o r d i n a t i o n

complex

forming

to

complex

a composite

and a second

belonging

of a metal

by o x y g e n - o x i d i z i n g

employing

an oxygen

oxygen

acetone

producing

presence

comprises

process
the

for

A process

each

are

according
in

the

to Claim 1 ,

range

of from 1 t o

4.
3.

wherein

X is

consisting
4.

of Ct-,

1 to 3,

ligands

L and

L'

acid

is

one anion
I-,

at

said
least

of a l k o x y ,
or

according

selected

Ch3C0-,

BF4-,

acetone

producing

wherein

consisting

phosphoric

Br-,

for

A process

acetone

producing

least

at

Claims

group

for

A process

organic
alkyl

phosphorous

from the

phosphorus

to

group

any one

compound as

selected

and amide

acid.

1 or 2 ,

PF6 and S 0 4 2 - .

according

one compound

to Claim

from t h e

derivatives

of

of
said

5.
the

A process

6.
the

L'

ligand

according
is

7.

according

phosphorus
for

A process
wherein

Claim,

an oxygen

froming

a propylene

group

halogen
8.

for

wherein

said
9.

the

wherein

is

hexamethylphosphoramide.

acetone
for

and said

first

second

least

at

aliphatic,

complex

one

organic

for

acetone
L'

each

the

at

of forming

capable

acetone

producing

solution

said

of

each
time

and a p r o p y l e n e

any f o r e g o i n g

liquid

and t h e s e

as a s o l v e n t

used

an oxygen

to
to

and t h e s e

and

complex
complex.

any f o r e g o i n g

and p r o p y l e n e
catalyst

complex

used.

is

to

according

composite

organic

compounds

a propylene

gas

from

and a r o m a t i c

according

same

of

selected

compounds,

are

of

capable

capable

compound

of forming

capable

any f o r e g o i n g

complex

alicyclic

L and

ligands

to

according

said

an o x y g e n - c o n t a i n i n g

complex

oxygen

3,

producing
are

complex

wherein

through

of

complex

A process

Claim,

1 to

complex,

for
said

first

second

of Claims

any one

and n i t r o g e n - c o n t a i n i n g

themselves

said

to

solvent

complex

compounds

ligands

wherein

oxygen-containing

A process

Claim,

3,

producing

consisting

hydrocarbons,

1 to

compound

the

as

forming
the

of Claims

nitrile.

A process
organic

to any one

are

passed

form an

two are

reacted

together.
10.

for

A process
1 to 8,

Claims
solution

of

propylene

is

wherein

said

and p r o p y l e n e

producing

passed

oxidized

catalyst,

through

with

the

according
is

carrier

a porous

composite

are

acetone

the

to

with

impregnated

an o x y g e n - c o n t a i n i n g
resulting

combined

oxygen

material,
in

of

any one

said

the

gas
and

oxygen

complex.
11.
Claim,

A process
wherein

for
at

producing

least

acetone

one b a s i c

according

to

any f o r e g o i n g

(electron-donative)

compound

selected

from

the

said

to

12.

A process

transition
Ag of Group

composite

metal
I,

W of Group VI,
VIII

of

the

A process

metal

M is

14.

A process

Pt and

Ir.

metal

any f o r e g o i n g

selected
the

from the
IV,

Group VII,

Claim,

the

consisting

of Cu,

Group V, Cr,

Mo a n d

group

V, tlb of

wherein

Co and Ni of Group

and Fe,

Table.

according

selected

to

Zr of Group

Mn of

Periodic

13.

transition

Ti,

is

catalyst.

according
M is

sulfolane,
and d i m e t h y l f o r m a m i d e

dimethylsulfoxide

dimethlysulfolane,
added

of

consisting

group

from

according
M' is

to Claim
the

group

12,

wherein

consisting

to any f o r e g o i n g

selected

from the

the

of Cu,

Claim,

group

transition
Ti

and V.

wherein

consisting

the
of P d ,