Patentamt
© Publication number:
Office
J3 E u r o p European
a i s c h e Patent
s
117
146
A1
Office europeen des brevets
EUROPEAN
0
PATENT
© Application number: 84301079.4
^ Date of
@
filing: 20.02.84
© Priority: 22.02.83 US 468527
© Date of publication of application:
29.08.84 Bulletin 84/35
© Designated Contracting States:
BE DE FR GB IT NL
APPLICATION
© Int. CI.3: C
C
C
C
07 C 5 1 / 2 1 5
07 C 51/25, C 07
07 C 5/333, C 07
07 C 45/35, C 07
C 57/04
C 11/06
C 47/22
© Applicant: THE HALCON SD GROUP, INC.
2 Park Avenue
New York, N.Y. 10016(US)
© Inventor: Khoobiar, Sargis
750 Ridge Road
Kinnelon New Jersey 07405(US)
© Inventor: Porcelli, Richard V.
287 Crestwood Avenue
Yonkers New York 10707(US)
© Representative: Cropp, John Anthony David et al,
MATHYS &SQUIRE 10 Fleet Street
London, EC4Y1AY(GB)
(54) Conversion of propane to acrylic acid.
Propane is converted to acrylic acid in an integrated
three-stage process. Propane is dehydrogenated in a first
stage to propylene, hydrogen, and by-products. The reaction
effluent is passed into a second stage-where propylene is
oxidized to acrolein without significant oxidation of the
hydrogen and by-products. The effluent from the second
stage may be passed as feed to a third stage for the oxidation
of acrolein to acrylic acid. The acrylic acid is recovered as the
primary product, while the unconverted propane may be
separated and recycled to the first stage for dehydrogenation.
The
tion
of
the
to
is
phase
over
considered
oxidation
However,
and
to
for
if
this
would
be
the
present
in
causing
contamination
present
process
acid
the
tions
of
relates
the
before
reacted
of
propylene
process.
the
present
was
if
p r o c e s s e s
as
propane
a
acrylic
before
of
way
to
a
of
propane
produced
to
a c i d .
oxidation,
acrolein
preparing
and
is
oxide
used
so
that the
low,
to
the
acid
of
and
propane
base
quite
whict
the
out.
acrolein,
sufficient
with
acrylic
propylene,
metal
in
process
carried
1,340,891
The
product.
purification
is
is
end
to
propane
are
without
combined
propylene
Patent
of
cannot be
propylene,
is
propane
used
generally
integrated
an
oxidation
prepare
not
ultimate
separation
the
variety
of
the
resulting
British
conversion
of
been
little,
preparing
are
use
of
intermediate
over
has
dehydrogenation
the subsequent
In
are
of
by-products
dehydrogenation
propylene
of
purified
processes
because
without
methods
be
acrylic
dehydrogenation
from
and
oxygen
acrylic
Since
catalysts.
high
net
result
a
the
acid.
acrylic
oxidation
form
since
inert
uneconomic
an
in
hydrocarbon
propylene
must
propylene
oxygen
process
Known
known
oxidation
this
an
over
oxygen
second
a
to
for
propylene
effluent
catalyst
saturated
prepare
the
to
molecular
essentially
art
prior
reactor
passed
feed
Any
Integrated
the
then
occurred.
used
feedstock
then
the
to be
three-
a
molecular
The
different
olefin.
unsaturated
be
is
a
Generally,
could
acrolein.
produce
the
with
phase
vapor
it is reacted with
step where
acid.
of
processes
acrolein
containing
vapor
the
in
acid
acrylic
prepara-
invention
the
specifically
of
the
to
generally
propane.
typical
to
catalyst
any,
from
in
reacted
More
preparation
process
In
relates
acid.
acrylic
relates
stage
invention
concentra-
amount
in
a
of
practical
U.S.
direct
for
single
to
again
step,
the
of
to
propane
using
low
a process
in
acid
acrylic
of
amounts
large
relatively
discloses
in
propane
conversion
of
a
order
to
propane
product.
The
since
the
above
one-step
conversions
substantial
of
typically
necessary
for
do
and
iron,
for
of
have
not
recycling
order
fed.
to
the
Also,
life
useful
long
commercial
phosphorus
in
feed
the
economic,
require
propane
operations.
have
been
developed
In
U.S.
Patent
propylene.
oxidative
the
the
processes
propane to
cobalt,
useful
of
and
unreacted
satisfactory
A number
converting
of
proportion
catalysts
low
not
are
processes
quite
are
amounts
convert a high
a
also
4,260,822
oxidation
overcome
the
Patent
is
catalyst
3,784,483
disclosed
of
dehydrogenation
for
as
to
propane
propylene.
In a
4,083,883
on
a
a
group of
is
support
Another
a
in
U.S.
Many
tion of
U.S.
in
to
steps
in
a
second
acrylic
acid.
over
and
on
zinc
zinc
over
have
disclosed
acrylic
acid,
processes
such
as
EP
to
obtain
the
best
from
propylene
step
over
the
promoted
a
promoted
reaction
aluminate.
titanate
4,176,140.
order
vapor-phase
effluent
shown
processes
dehydrogenate
generally
in
the
is
these
are
first
paraffins,
Patents
processes
In
the
of
These
acid.
the
In
platinum-tin
4,144,277
propylene
3,954,855.
two
of
U.S.
used to
are
propane
patents
in
taken
4,041,099.
steam
catalyst
of
metals
promoter
dehydrogenation
is
and
of
Dehydrogenation
catalysts
the
with
U.S.
by
paraffins.
4,005,985
over
propane
combined
approach
quantities
large
for
used
normal
particularly
3,692,701,
metal
precious
exemplified
patents
is
molybdenum
is
yields
oxidized
molybdenum
passed
catalyst
with
to
for
oxida-
0000663
and
carried
out
of
to
acrylic
acrolein.
catalyst
added
and
oxygen
produce
Based
assemble
which
propylene,
to
acid
acrylic
ever,
this
acid.
As
not
be
be
seen,
may
will
acid
the
without
first
of
removed
integrated
of
or
catalysts
their
to
acid.
the
explosive
be
in
the
acid
Acrylic
integrated
in
without
the
a
first
is
acrylic
to
converted
the
Alternatively,
and
effluent
may
water
stream
to
be
followed
which
on
For
oxidation
by-products
oxidation
the
exposure
cannot
of
the
produce
acrylic
should
not
create
an
Invention
from
followed
to
of
the
separated
that
a
oxygen
second
effluent
before
stage.
oxidation
to
propylene
of
in
dehydrogenation
by immediate
propane
addition
acrolein
oxidation
of
an
immediately,
purification
by
in
propane
dehydrogenation
and
an
reactors.
effluent,
the
the
conditions
hydrogen
propylene
in
example,
quality
is
the
the
molecular
processes
and
prepared
condensed
enters
but
hydrogen
of the
and
dehydrogenation
of
art
The
of
stage
lower
in
the
which
separation
oxidation
cooled
stage
in
process
propylene
stage.
How-
substantial
prior
oxidation
Summary
and
to
pertains
be
accommodated
oxidizing
presence
mixture
the
effect
reduce
of
amounts
performance.
which
from
way,
produce
produces
product,
adverse
an
by-products
Also,
the
must
contaminants
is,
fed
intermediate .
an
propane
in
acrolein.
to
have
not
the
this
converted
propane may
small
which
from
process
propylene
should
of
and
hydrogen
hydrocarbons,'
be
would
In
invention
purifying
of
Dehydrogenation
weight
and
purified
product.
propylene
amounts
produce
to
way
present
which
by
process
to
known processes.
economic
an
oxygen
is
fed
propane
might
dehydrog-
process.
combining
merely
by
integrated
acrylic
acid
acrylic
one
is
and
separated
above,
propane
of
presence
be
all of the
substantially
an
would
conventional
a
the
discussed
wherein
process
without
or
art
prior
multi-step
a
with
enated
the
on
The
of
may
be
the
oxidation
the
in
acrolein
third
or
the
to
or
hydrocarbon
it
from
the
is
recycled.
be
scrubbed
to
natively,
from
oxygen
the
The
carried
out
on
a
base
or
by
zinc
be
may
without
on
promoter,
carried
kg/cm2
about
10
steam
ratio
of
to
out
gauge
about
acid
acrylic
such
molybdenum
oxide-based
1
of
the
to
to
to
are
remove
removed
is
aluminate
400
with
suitable
a
suitable
catalyst
a
a promoter
noble
and
with
platinum,
the
to
is
propylene
without
or
other
about
dehydrogena-
700°C
and
up
t
to
propane
to
be
carried
metal
acrolein
out
oxides,
over
and
of
suitable
especially
catalysts.
of
the
is
a
block
is
a
simplified
Drawings
diagram
showing
the
process
invention.
Figure
embodiment
of
2
the
invention.
o
1/10.
propylene
base
Description
Figure
may
Alter-
dioxide
over
with
zinc
may
mixed
catalysts,
as
of
which
employed
propane
the
at
1/0.5
acid
acrylic
carbon
reaction
pressure,
oxidation
The
acrolein
of
or
a
propane
solvent.
support
When
be
will
and
platinum
catalysts.
be
to
water
unreacted
propylene,
may
gases
vapor-phase
aluminate
metal
tion
a
in
heavy
oxida-
and
dehydrogenation.
oxidation
dehydrogenation
which
catalyst,
and
for
suitable
a
in
plus
and
unreacted
depleted
stage
residual
with
scrubbing
least
at
also
light
and
by-products
scrub-
oxygen,
absorbed
be
may
propane
selective
a
and
dehydrogenation
acid
gases
first
the
to
the
lighter
recover
a
being
by
which
effluent
miscellaneous
of
Residual
in
recovered
before
recovered
propylene,
Thereafter,
components.
is
stage
and
Acrylic
be
may
effluent
product
propane,
by-products
acid
acrylic
acrolein
stage
third
oxides
reactions.
recycled
acid
the
to
oxidation.
for
acrylic
carbon
separate
the
second
stage
unreacted
hydrogen,
feed
the
quenching
contains
tion
in
third
The
bing
effluent
stage
Alternatively,
stage.
concentrated
fed
by
second
the
flowsheet
showing
one
is
3
Figure
embodiment
alternative
the
In
integrated
to
be
desired.
is
shown
particularly
12
the
before
of
the
effluent
it
to
of
of
lower
molecular
be
oxidized
affecting
the
of
hydrogen,
tion
of
and
of
i s
step
process
of
the
would
have
must
of
affecting
or
found
in
of
by-products
amounts
markedly
acrolein
to
sig-
quantities
without
We
of
propylene
significant
10
the
small
the
be
step
Since
as
methacrolein
adversely
familiar
production
well
as
hydrogen.
and
One
12.
the
propylene
to
reaction
dehydrogenation
step
art
prior
dehydrogenation
propylene
by-products,
of
the
oxidation
hydrocarbons,
oxidized
not
the
hydrogen,
presence
propane,
while
step,
of
of
acrolein.
involves
weight
oxidation
be
acid
propane
complete
the
the
oxidation
the
oxidation
may
a
that
expect
propane
the
propane,
propylene
unreacted
from
to
propylene
from
hydrogen,
the
acrylic
those
to
directly
would
in
of
dehydrogenation
with
effluent
art
quantities
propylene
such
fed
be
nificant
causing
of
the
that
dehydrogenation
the
view
in
feeding
and
the
prior
separated
product
to
contrasts
may
The
recycled
process
conversion
for
with
10
of
an
1.
Figure
The
reaction
steps.
is
dehydrogenation
oxidation
the
A schematic
in
the
by-products
and
recovered
if
two
the
from
separated
may
in
acid
invention
the
aspect,
with
an
Embodiments
Preferred
combining
propylene
acrylic
the
showing
invention.
the
principal
process
to
propane
of
of
Description
flowsheet
simplified
a
the
that
presence
the
dehydrogena-
the
oxidation
process.
After
lein,
the
the
entire
may
be
the
acrolein is
sent
effluent
effluent
directly
of
to
separated
at
while
lower-boiling
the
to
oxidized
oxidation
16.
from
the
step
Purified
been
has
propylene
the
second
acrylic
14
oxidized
first
oxidation
acid.
components
acid
are
acro-
oxidation
is
14'where
step
condensed
the
separated
12.
step
the
Thereafter,
is.partially
acrylic
to
and
product
at
18.
Waste
unreacted
be
normally
is
may
be
acrolein
recovered
another
oxidation
step
acrolein,
which
second
12
be
may
is
and
level
will
if
by-products,
that
so
a
acrolein
then
oxidation
the
to
recycled
fed,
effluent
to
the
from
f i r s t
the
concentrate
with
air
or
oxygen
Recovery
may
be
made
along
14.
step
such
liquids,
Unreacted
acids.
the
to
the
separated
then
oxidation
carboxylic
returned
acrolein
remains,
and
aspect,
absorption in suitable
lower
lower
a
and
selectively
Although
acid
Alternatively,
shown.
as
In
the
of
removed
acrylic
at
kept
amount
optionally
to
10.
step
be
may
recycled.
converted
significant
14
oxides
while
discharged
are
to
recycled
gases
conversion
stage
by-products
is
carbon
remaining
the
heavy
propane
and
oxygen
the
and
gases
dehydrogenation
will
propane
10
step
and
water
as
to
by
the
be
shown.
as
Example 1
of'Propane
Dehydrogenation
A catalyst
on
zinc
a
aluminate
of
sample
reactor
50
having
a
aluminate
zinc
bed.
for
2 mols
hourly
3.5
space
kg/cm2
held
at
a
temperature
A gas
A.
steam
The
reflecting
An
of
fed
to
hr-l
4000
inlet
to
the
to
the
reaction.
of
a
with
a
tubular
of
cc
a
pressure
bed
the
endothermic
nature
The
are
the
the
propane
at
reactor
catalyst
results
% In
above
reactor
under
temperature,
the
to
250
1 mol
the
1 wt
A c a t a l y s t
additional
containing
was
and
Pt
was · charged
added
stream
predetermined
dehydrogenation
Table
was
velocity
gauge.
i.d.
mm
wt %
prepared.
3 mm e x t r u d a t e
25.4
of
0.4
was
support
support
catalyst
each
as
cc
of
composed
gas
of
was
outlet
of
given
the
below
in
The
of
the
from
carried
into
of
Oxidation
the
the
acrolein
along
with.propylene
oxygen
pylene.
Also,
undesirable
it
has
carried
oxidation
in
ing
the
with
A and
220
of
cc
of
gas
oxygen
was
of
was
1000-1200
catalyst
hr-1
having
have
was
chromatography
designated
in
about
of
Tests
However,
with
substantially
in
seen
which
no
be
can
the
has
follow-
not
been
effect
significant
2
and
of
4.7 mm
having
an
volume
the
the
effluent
3-6
of
Table
gases
A.
12.7
in
placed
mm.
% steam
space
The
gauge.
A charge
was
vol
hourly
catalyst.
kg/cm2
1.76
of
20
Reference
Si02.
pellets
propylene,
a
to
method
80%
20%
i.d.
the
to
according
corresponding
as
at
Acrolein
to
Propylene
composition
5 vol%
over
be
propane
prepared
0000663
passed
the
propylene.
catalyst
containing
in
propylene
will
to
generate
acrolein.
of
as
reactor
single-tube
pro-
hot-spots
K0.1Ni2.5Co4.5Fe3Bi1P0.5Mo12Oxand
of
of
hydrogen,
A catalyst
Catalyst
oxidation
hydrogen
appears
hydrogen
would
would
hydrogen
of
the
it
of
of
EP
the
contam-
since
undesirable
oxidation
Oxidation
in
which
Oxidizing
Example
described
compounds
create
presence
by-products
reaction.
presence
also
oxidation
other
oxidation
production
that
The
example.
of
could
the
of
dehydrogenated
on
and
the
no consumption
be
would
interfere
and
found
out
to
weight
before
separated
and
hydrogen
molecular
lower
not
avoided.
be
lower
been
is
mol
one
additional
and
some
subsequent
must
heat
and
catalyst
of
by-products
inate
consume
the
produces
propane
propylene
propylene
oxidation
subsequent
of
mol
formation
When
by-products.
are
each
for
hydrogen
hydrogen
of
dehydrogenation
A f e e d
and
velocity
12%
of
pressure
in
the
Analysis
by
gas
gave
the
a
results
After
with
established
to
the
feed
would
the
to
gas
was
added
in
oxidation
reaction
same
results
from
The
of
that
seen
essentially
no
hydrogen
was
with
shown
the
as
tests
same
that
propylene
in
results were
propane
and
in
was
was
not
Tests
t h e
Table
the
oxidized,
reactor.
oxidation
the
The
added.
A.
obtained
Again
as
affecting
not itself
was
being
and
propane
11-13
the
as
It
was
discontinued
4 vol %
with
3-6.
Tests
with
An
propane.
substantially
conditions
operating
supplied
shown
are
in
hydrogen
indicating
results
as
the
substantially
be
of
achieved
were
continued
are
The
it will
A.
that
fed.
when
included
was
which
conditions
the
part
hydrogen
Table
oxidation
hydrogen
of
in
3-6,
feed,
4 vol %
7-10
results
been
dehydrogenation
previously
reaction
had
by
mixture
judging
catalyst
produced
additional
concluded
propylene
simulate
the
to
pertain
propylene
only
the
of
performance
being
in
Tests
t h e
oxidized.
These
in
the
of
presence
be
may
that
and
the
that
and
and
additions to the
the
effect
feed
of
of
to
the
was
A 73
cc
sample
reactor
ing
and
45
3000
above
the
feasible.
Acid
Acrylic
of
acrolein
and
to
propane
carried
were
to
corresponding
U.S.
3,954,855
The
there.
reactor
vol
% steam.
and
by
the
atmospheric.
6-8
The
average
The
4.7
as
and
o u t
the
according
composi-
catalyst
a
bath
mm p e l l e t s
12.7
having
predetermined
was initially
hr-1
the
2.
catalyst
surrounded
was
reactor
of
tubular
a
uniform
a
propylene.
Mo12V4.8Sr0.5W2.4Cu2.2Ox.
in
placed
1 of
procedure described
tion
is
experiments
prepared
Example
of
hydrogen
Example
A catalyst was
composition
of
gas,
which parallel those
to
oxidation
the
to
principal
3
Acrolein
illustrate
acid
acrylic
of
two
propane
reactions
Example
To
of
integration
oxidation
Oxidation
the
propane,
oxidized
be
can
propylene
dehydrogenation
concluded
denydrogenation
show
hydrogen
the
of
components
It
results
mm i . d .
vol
% acrolein,
volumetric
reactor
results
The
thermostatically
temperature.
space
pressure
are
shown
The
51
was
provid-
feed
vol
to
% air,
velocity
was
slightly
in
Table
the
B.
As
was
added
The
results
then
and
(propane).
of
acrolein
ferences
Although
is
Tests
among
significant.
the
tially
The
15,
is
process
known
with
quenched
acid
solvent
extraction
The
be
and
the
whereby
with
effluent
from
suitable
a
purified
liquid,
by
ethyl
e.g.
distillation
by
solution
aqueous
solutions
acid-solvent
acrylic
be
may
solvent.
point
the
by
U.S.
example,
to
may
produce
the
invention
dehydrogenation
and
two oxidation
has
been
uct
stream
and
propane
desirable
can
to
the
to
be
be
not
significant
to acrylic
without
ever
stream.
In
propane,
it
In
unreacted
process
with
to
will
a
gas
necessary
combination
of
propylene
resulting
amounts
it
and
recycling
will
be
so
propane
converts
propane
of
by-products
pure
propylene
containing
to
propylene
then
cases,
propylene
by-prod-
of
purposes,
many
after
a
quantities
substantially
recycle
be
the
substantially
minor
only
producing
order
other
required.
recycle
acid
for
used
integrated
separation
If
stages
acid,
Such
the
includes
acrylic
recycled.
possible.
containing
is
is
to
intermediate
an
shown
gas
converted
propane
without
process
is
propane
which unreacted
of
an
done
be
may
for
reactor
removed
broadest
of
integration
that
substan-
that
form,
its
In
the
is
acid.
acrylic
of
dif-
the
considered
acid
(16)
high-boiling
a
resulting
separated
that
15
and
and
concluded
See
art.
acid
or
be
can
14
not
acrylic
be
conversion
the
Tests
are
acid
acrylic
acrylic
Acrylic
acetate.
to
may
prior
water
17
and
(H2)
temperature
and
propane.
feasible.
of
the
to
The
3,926,744.
to
it
in
% hydrogen
with
16
Test
from
clear
16,
Again,
Separation
methods
B as
selectivity
same.
integrated
is
vol
4
replaced
difference
some
sensitive
very
was
Table
it
appears,
conversion
hydrogen
in
first
2,
Example
the
shown
are
17
in
done
was
remove
large
and
amounts
hydrogen
in
produced
the
oxidation
In
steps.
ducts
addition,
desired
of
reactor.
the
they
be
economically
stream
heavy
ethane,
and
liquid
ferred
Fresh
stream
24
exchanger
28
required
that
acrolein.
to
for
a
combined
the
for
amount
as
the
of
subsequent
is
not
in
steps,
the
light
methane,
at.temperatures
acrolein
or the
distillation.
by
the
in
by-products
of
Separation
of
the
might
propane
be
oxidation,
catalytic
phase
adsorption.
flowsheet
with
showing
a
combined
propane
is
26
the
acrylic
with
recycle
and
vaporized
then
oxidation
heated
combined
of
preferably
of
the
in
in
with
o b t a i n e d
temperature
dehydrogenation
used
process
to
when
that
such
a pre-
complete
substantially
steam
be
be
boil
separated
(30)
will
Since the
of
stream
steam
up
may
such
those
temperature
suited
build
butenes
is
the
oxidation
or
removed.
principally
amount of
The
propylene.
suitable
The
20
monoxide
or
amine
maintain
to
they
invention
feed
containing
22.
which
gas
converted
propane
exchanger
will/be
or
all
or
materials
to
simplified
a
is
propane
acid.
the
is
order
these
as
of
carbonate
a
purged.
such
by-pro-
scrubbing
by
dehydrogenation
methods
2
be
may
the
by
be
heavy
dehydrogenation
containing
embodiment of the
whereby
the
all
Removal
Carbon
of
from
absorption
Fiaure
in
and
may
amounts
phase
in
art
in
butane,
streams
various
with
by-products,
they
formed
by
done
permitted
different
Alternatively,
hydrogen
be
economically
ethylene,
and
light
dehydrogenation
hydrocarbon
concentrated
three
would
level
a
hydrocarbons,
done
the
to
significantly
C3
in
taken.
presence
either
and
formed
be
dioxide
to
conveniently
oxides
dioxide.
critical
recycle
from
will
the
carbon
Since
may
oxygen
stream
in
carbon
to
excess
of
purge
recycle
known
level
converted
a
typically
is
as
carbon
impurities
the
of
solution
and
step,
dioxide
portion
step,
dehydrogenation
feed
and
carbon
a
the
propane
to
is
propylene
to
As
shown
If
this
here,
is
56.
in
ratios
molar
is
kg/cm2
0-10
to
reactor
32
to
propylene,
about
with a
prior
art
for
which
the
reaction
use
platinum-based
4,005,985.
catalysts
in
this
is
Of
support
catalysts
which
and
promoters,
on
zinc
or
in
have
the
provides
aluminate.
combination
found
such
as
Other
in
the
or
disclosed
is
in
U.S.
on
noble
of
dehydrogenation
platinum
supported
metals,
known
zinc
a
other
indium
and
under
a
include
effective
supports
the
the
on
disposed
VIII
in
conditions
shown
rhenium
converted
more.
performance,
Group
various
on
application
been
is
depend
tin
and
good
gauge,
usefulness
type
about
to
up
the
will
out
platinum
have
and
to
1/1
400-700°C,
been
have
process
of
75%
the
steam
preferably
propane
of
is
of
and
propane
kg/cm2
the
particular
catalyst
aluminate
of
carried
bottom
pressures
0
stream.
reactions
the
about
near
50%
of
Although
other
at
feed
the
1/10,
selectivity
selected.
catalyst
and
preferably
where
A number
and
between
temperatures
gauge,
in
containing
1/0.5
600°C,
fresh
a
from
system
stream
about
as
produced
the
between
at
particularly
water
feed
A
fed
supplied
from
purged
stripper
1/5,
then
done,
eventually
is
steam
to
the
propane
alone
art
may
to
propylene.
Other
other
alkaline
aluminates
lead,
earth
and
antimony,
such
magnesium
and
3,784,483
4,144,277
sidered
to
as
thallium
chromium,
oxides
vanadium
or
the
also
might
be
limited
may
zinc
be
to
Promoters
such
as
be
Base
metal
and
used.
zirconium,
as
shown
The
specific
alumina,
earth
titanate of
used.
include
rare
aluminates,
lanthanum.
the
would
supports
metal
including
catalysts
and
potential
in
titanium,
U.S.
U.S.
invention
catalyst
tin,
3,479,416
4,176,140
is
not
and
con-
formulations.
It
will
be
that
in
this
must
be
regenerated
will
be
operated
dehydrogenation
50-200°C
lower
affected
by
the
is
endothermic
reactor
32
will
the
inlet
of
amount
and
catalyst,
the
the
operations
invention.
and
the
order
temperature.
This
steam
the
employed,
of
severity
of
be
will
condition
reaction
the
The
tempera-
on;the
be
and
frequent
such
the
of
part
art
process
that
of
reaction
than
the
so
details
the
deactivates
rapidly
reactors
The
in
skilled
Typically,
multiple
considered
the
leaving
catalyst
possible.
not
those
by
frequently.
with
is
however,
ture
the
process
regeneration
are,
understood
of
conditions
chosen.
T h e
exchanger
34
oxidation
reactor
36
stream
in
be
from
reactor
The
reaction
to
be
used,
catalyst
tion.
will
amounts
of
32
be
is,
also
until
which
be
converted
acrylic
tubular
inside
90-95%
acid,
cool
the
to
tubes
conditions
the
of
the
to
about
velocities
on
the
base
type
which
are
metal
acid,
The
reactor
pelleted
surrounded
heat
feed
along
and
oxides,
the
the
propylene
0-5
catalyst
where
of
acrolein,
acetic
about
of
of
38.
typical
of
range
the
of
pressures
removal
the
from
reactor
molybdenum-based.
are
for
not
adjustment
oxidation
a mixture
of the
fluid
space
A suitable
typically
be
in
300-350°C,
hourly
gas
Although
oxidation
under
out
of
air
or
condensed
permit
temperatures
about
so.
is
in
the
to
oxidation
the
possible
water
carried
hrs-1.
Typically,
reactor
is
it
in
cooled
inlet
oxygen
do
to
used
placed
transfer
economic
is
oxygen-containing
in
enriched
ratio
will
is
for
propylene
those
typically
feed
would
and
2000
suitable
water
usually
gauge,
an
the
that
especially
heat
of
would
art,
200-600°C,
will
for
with
if
flowsheet,
steam
of
temperature
Air
this
the
order
a
used,
Removal
kg/cm2
effluent
joined
and
acrolein.
shown
the
38
to
might
gases.
suitable
a
provide
alone
of
to
to
propylene
effluent
reactor
dehydrogenation
less
of
to
with
by
a
reac-
the
minor
significant
of
quantities
the
is
propylene
without
burned
intermediate
to
composition
gas
converted
to
in
tures
the
where
acid.
The
reaction
pressures
hourly
space
suitable
of
velocities
base
metal
acrolein
fed
acid,
oxides,
and
other
to
The
fed
to
an
mixture
at
is
in
all
of
the
containing
up
to
is
sent
acid
is
solution
acrylic
of
stream
solvent
to
and
a
is
54
impurities.
the
56
bottom
for
the
extraction
for
via
line
of
as
46
to
the
via
to
the
the
stream
hydrocarbons
steam
two
and
Substana
solution
This
the
where
recirculating
The
acetate.
ethyl
to
line
48
stripper
a
50.
additional
Acrylic
columns
52
heavier
is
process
and
then
44
stream
in
a
and
and
acid-water
46
by
via
47
cooled
be
acid.
passed
lighter
in
produced
column
as
recycle
51
of
is
75-80%.
30-50°C.
column
such
acid
selectivity
aqueous
acrylic
the
carbon
acid,
recovered
extracted
solvent,
solvent
removal
recirculated
to
separation
of
mol %
acrylic
Water
is
35
with
to
may
about
about
selectively
passed
for
of
acid
acrylic
an
converted
the
are
be
of
recirculating
range
a
90-98%
acrylic
an
A
which
will
about
mixture
where
a
the
suitable
rich
recover
acid
in
condensed
temperatures
tially
42
be
would
gaseous
quench-tower
hrs-1.
those
Overall,
250-
gas
typically
acetic
of
by-products.
resulting
be
will
tempera-
about
and
2000
Typically
40
acid
is,
usually
used,
the
carried
be
that
of
be
amounts
acrylic
is
configuration
38.
reactor
acrolein
especially
reactor
minor
and
propylene
oxides,
of
gauge,
order
will
reactor
the
to
acrylic
of
of
to-that
the
or
adjustment
art,
kg/cm2
0-5
on
The
the
with
would
200-600°C,
catalyst
molybdenum-based.
similar
about
about
oxidation
of
of
water.
fed
the
40,
of
range
and
exchange
typical
and
is
38
reactor
reactor
acrylic
300°C,
mixture
heat
conditions
under
out
from
oxides
of
Some
by-products.
carbon
to
effluent
The
heavier
and
lighter
removed from
sent
to
disposed
dehydrogenation
stripper
of
step.
or
The
tower
they
acid.
include
paraffin
solvent
Suitable
from
vented
rich
In
absorber
content
42
is
could
consumed
selective
This
be
oxidation
out
the
the
valuable
C3
at
oxygen
returned
to
the
slip
stream
dioxide
C3's
from
An
flow
sheet
scrubbed
oxidation
the
of
in
mols/hr
is
dehydrogenation
streams
26
are
560
mol/hr
of
low
suitable
can
carry
is
and
propane
recycle
heated
steam
and
the
to
be
may
after
carbon
separate
purged.
of
operation
the
follows:
4
of
feed
a
in
vaporized
reactor
propane
gas
remove
steps
as
that
temperature
oxidized
are
oxygen
present.
over
which
practical
2
Figure
fed
a
the
hydrogen
out
24.
from
gases
where
the
which
the
99%
of
the
The
line
to
hundred
mols/hr
via
been
containing
the
20
preferably
Example
to
reactor
reactor,
example
One
they
dehydrogenation
by-products,
shown
where
the
by
light
60
consumed
having
produced
gases
column
not
been
Light
58.
alumina,
are
employed
tower
sufficiently
has
be
to
of
carried
on
are
gases
top
with
be
hydrocarbons
the
a
may
with
content
C3
may
reactor
a
reaction
a
Once
lost.
to
platinum
as
to
along
conversion
embodiment,
passed
oxidation
such
catalysts,
returned
by
the
the
to
passed
quench
These
which
from
the
hydrogen,
hydrocarbons.
alternative
an
oxides,
further
solvents
is
and
out
for
process
C3's
propane
of
recovery
aromatic
the
in
stripped
are
for
of
top
impurities.
returned
or
of
carbon
light
58
be
to
are
acrylic
are
and
absorber
the
quantities
propylene,
nitrogen,
to
passed
leaving
gases
large
of
amounts
oxygen,
if
contain
42
lesser
light
along
24.
to
about
675°C
(30)
which
may
be
22
exchanger
32,
stream
20
stream
(28)
The
and
provided
with
and
240
combined
mixed
by
with
and
recycling
The
combined
reactor
with
promoted
in
platinum
being
about
the
acrolein
to
selectivity
catalyst.
the
the
effluent
gauge
second
oxidation
acid.
acrylic
1.0
kg/cm2
140°C
and
and
The
absorber
with
a
42
crude
is
paraffins
to
C3
content.
The
hydrogen,
in
% acrylic
by-products
and
other
of
column
60
recycled
via
240
1.4
to
270°C
and
cooled
to
where
water,
acrolein,
absorbed
35°C
58
all
light
about
recir-
a
exchanger 43.
of
top
it
is
contacted
of
the
of
by-products,
enriched
of
to
the
containing
mol/hr
The
24
in
where
250
mol/hr
in
the
mol/hr
58.
line
and
about
at
leaving
and
325°C
is
i.e.
column
and
molybdenum
(40)
250
gases,
88%
acrolein
substantially
nitrogen,
top
with
where
38,
propane
are
is
liqu'd
is
dehydrogenation
32.
An
mol
the
and
recovered
reactor
waste
oxygen,
from
stripped
recover
reactor
of
about
of
stream
recirculating
(36)
oxygen
conversion
absorber
to
125°C
the
and
gas
at
to
42
to
recycle
passed
C8
vented
cooled
44,
32
passed
reactor
condensed
are
stream
culating
for
of
about
at
are
tower
quench
acid
38
a
about
to
mol/hr
effluent steam
the
enters
acrylic
40
the
cooled
promoted
gases
reactor
gauge
a
reactor
Leaving
is
converted
over
Leaving
kg/cm2
is
propylene
over
reactor
oxidation
the
to
the
is
fed
propylene
152
56.
stripper
dehydrogenation
Leaving
with
the
propane
to
stream
mixed
supplied
of
93%
and
the
the
selectivity
effluent
34
exchanger
to
of
29%
catalyst.
the
600°C,
before
80%
fed
is
29
about
where
32,
converted
about
stream
from
49
stream
vaporizing
aqueous
acid,
such
as
oxygenated
stream
along
acetic
of
with
550
acrolein
maleic
acid,
compounds
mol/hr
is
passed
containing
and
acid,
to
12
miscellaneous
formic,
extractor
a c i d ,
46
where
it
solvent
line
(ethyl
50.
column
acetate)
Water
and
46
stream.
bottom
of
solvent
48
overhead
crude
to
withdrawn
from
the
52
via line
acid
heavy
via
line
distilled
as
sent
from
away
sidestream.
a
maleic
acid
High
of
70
in
48
The
is
and
Light
distilled
via
the
line
purified
55
where
and
bottom
of
is
such
as
column
54
sent
are
it
withdrawn
materials
materials
light
overhead
Partially
waste
from
mol/hr
remainder.acetic
by-products
boiling
residual
Any
56.
54
heavy
withdrawn
are
disposal.
column
the
50.
column
the
are
column
to
to
distilled
line
by-products.
and
is
of
enriched
recovered
via
with
acid,
any residual water
acid
46
stream
and
acrylic
is
the
51.
% acrylic
53
is
a
from
The
of
light
as
(49)
and
which
bottom
impurities
passed
withdrawn
46
column
the
where
disposal.
solvent
acrylic
and
or
bottom
the
56
withdrawn
via
tower
is
from
and
column
to
leaves
acetate
ethyl
reuse
the
acid
column
to
is
water
acid
mol
47
lean
mol/hr
of
acrylic
overhead
for
crude
The
90
line
recirculated
column
comprises
via
separate
and
to
acid,
is
overhead
acrylic
sent
raffinate
column
passes
column
the
Stripped
the
base
of
distilled
are
by-products
the
all
passed
190
versus
entering
Substantially
absorbed.
waste
countercurrently
passes
for
column
to
56.
3
Figure
alternative
recovered
before
quench
by
a
oxidized
steps
effluent
tower
the
of
is
from
39A
recirculating
to
of
showing
invention
where
acrolein
effluent
38
is
acrolein
aqueous
and
is
stream.
this
In
cooled
reactor
reactor
dehydrogenation
pertinent.
reactor
of
acid in
acrylic
the
still
where
sheet
the
purified from
discussion
oxidation
the
and
flow
simplified
a
embodiment
being
previous
is
and
scrubbed
Gases
an
is
38
40.
The
first
embodiment,
then
led
from the
which
are
to
a
gases
n o t
absorbed
of
the
may
gases
returned
to
in
39A,
tower
39B
to
the
is
separated
line
in
reactor
40
via
oxidation
to
acrylic
An
is
acid
of
the
of
oxidized
120°C
and
fed
scrubbed
out
by
to
rich
by
absorbent
with
39C
to
is
the
flow
Figure
does
as
the
the
shown
process
32
is
column
oxidation
the
39B
64
the
is
cooled
is
The
water.
by
supplied
vapor
acrolein,
sent
are
40.
The
same
as
the
to
of
mol/hr
reactor
4
Example
returned
are
then
acrolein
with
by-products
substantially
of
effluent
contact
while
of
amounts
the
where
gases
and
propylene
38
contain-
stream.20
line
via
remainder
that
shown
of
in
2.
directed
propane,
to
it
recovered
reactor,
light
reactor
Although
is
to
39A,
in
stripped
second
sheet
of
feed
a
reactor
absorber
The
minor
the
2,
conditions
the
countercurrent
dehydrogenation
along
under
to
reboiler.
the
from
5
dehydrogenated
leaving
upon
as
acid
the acrylic
operation
mols/hr of
acrolein
to
that
except
is
propane
out
added
follows:
as
One hundred
99%
is
oxygen
Figure
tower
acid.
acrylic
Example
ing
or
carried
in
as
in
second
the
to
and
absorbed
being
stripped
Air
39C.
proceeds
example
is
3
Figure
line
like
the
After
is
content
C3
or
acrolein
Recovery
effluent
reactor
24.
absorbent
rich
described.
absorption
by
via
stream
the
preferably,
enriched
the
purification of
in
or
32
reactor
previously
the
purged
provide
oxidation
and
be
the
should
from
as
product
of
various
end
the
shown
the
in
principal
of
preparation
be
understood
effluent
in
process
uses,
its
such
of
3
Figure
acrylic
that
the
for
the
acid
acrolein
first
example,
invention
from
can
be
oxidation
and used
acrolein
is
needed
preparation
of
allyl
where
as
aspects
as
f o r
alcohol.
a
1.
from
propane
(a)
in
A process
dehydrogenation
with
stage
said
mixture
to
with
oxidation
a
third
effluent
oxygen,
(d)
to
(e)
the
ratio
400-700°C
and
said
a
The
1/0.5
pressure
support.
VIII
noble
up
stage
metal
or a
to
and
from
1 wherein
said
a
about
or
metal
propane
and
kg/cm2
claim
said
steam
gauge.
2 wherein
a catalyst
oxide
and
about
temperature
10
of
effluent;
(a).
employs
base
acid,
step
and
claim 1
(a)
p r o d u c e
effluent
propane
with
fed
to
to
acrylic
said
from
claim
1/10
process of
dehydrogenation
a Group
to
(b)
second
a
acid-depleted
is
of
oxides;
effluent
(a)
propane,
stream
acrolein,
unreacted
of
process
stage
about
3.
the
and
selected
and
acid
acrylic
stream
over
oxygen
carbon
acid-depleted
The
of
an
least
at
returning
dehydrogenation
a
and
conditions
oxides;
effluent
propane
steam
the
at
propylene
comprising
acrylic
produce
2.
and
passing
effluent
the
stream
hydrogen,
acrylic
stream
oxides
catalyst
conditions
at
propylene,
recovering
(c)
over
optionally
and
carbon
additional
catalyst
unreacted
and
passing
stage
and
(a)
unreacted
hydrogen
optionally
of
second
a
acrolein,
third
a
steam,
effluent
an
carbon
oxidation
produce
oxygen,
in
form
oxygen
stream
first
a
over
comprising
(c)
of
presence
to
to
propane
hydrogen,
mixing
effluent
selected
and
acid
acrylic
propane;
second
a
the
catalyst
propylene,
unreacted
in
in
optionally
comprising
(b)
of
preparation
dehydrogenating
stage
propylene,
a
the
comprising:
first
a
for
comprising
on a
in
4.
is
cooled
from
of
and
before
4 characterized
as
carbon
an
claimed
that
of
stream
(a)
there-
separated
enters
the
second
in
one
of
said
stream
gaseous
and
propane,
and
solution,
aqueous
any
of
effluent
therefrom
water
effluent
propylene,
stage
and
acid
forming
is
a
unreacted
comprising
acrolein,
is
(c)
acrylic
thereby
1
claims
and
oxygen
oxides.
6.
that
A process
the
residual
solvent
and
that
said
residual
oxygen
returned to
7 characterized
contact with
oxidation
of
by
said
a
said
suitable
said
in
that
solvent
and
catalyst.
is
5 characterized
passed
with
over
a
conditions
hydrogen
for
and
(a).
claimed
the
a solvent
effluent
claim
oxidation
reaction
step
as
in
stream
selective
A process
content
from
claimed
gaseous
said
8.
is
as
at
thereafter
in
of
(a).
catalyst
of
acrolein
absorbed
are
5 characterized
claim
and
recovered
A process
suitable
removal
stream
step
7.
in
propane,
thereafter
to
claimed
as
propylene,
gaseous
returned
(b)
and
stream
as
in
condense
to
residual
to
effluent
condensed
A process
recovered
in
is
the
claims
of
one
any
(b).
cooled
in
that
effluent
said
5.
to
in
water
in
claimed
as
3 characterized
to
,1
A process
in
any
effluent
to
stream
increase
passing
one
of
stream
the
over
claims
of
1
step
acrolein
said
second