Note: Descriptions are shown in the official language in which they were submitted.
0~ ~9~ 9694~1
Back~round of the ~nvention
Field of the Invention
The invention relates to the vapor phase
catalytic oxidation of alpha,beta-unsaturated monoolefins
to the corresponding alpha-beta unsaturated carboxylie
acids and alpha-beta unsaturated aldehydes.
Descrip_ion of the Prior Art
The use of oxidation catalysts containing
molybdenum and bismuth, alone, or with other selected
elements, for the gas phase oxidation of alpha,beta
unsaturated monoolefins such as propylene to the corre-
sponding alpha-beta unsaturated acid and/or aldehyde~ 3~C~ ~S
acrylic acid and acrolein, has been known.
In these reactions a gaseous reaction mixture
which usually contains the olefin, molecular oxygen an~
water, as steam, is brought into contact with the catal~t,
- by continuously pa~sing a stream of the reaction mix~re
through a bed of the catalyst. Such known catalyst
systems would include those disclosed in the following
.- 20 United States Patents: 3,171,859; 3,387,038; 3,445,521;
3,522,29g; 3,636,066; 3,6429930; 3,679,603 and
3,691,0g6.
For commercial purposes this group of catalysts
usually comprise the elements Mo, Bi, Fe and Ni and/or
In order to improve on the efficiency and/or productivit~
of such catalyst compositions, and/or the selectivi~y o~
.: - the pro~uct~ made with s-lch catalyst composi~ion.s .it ~r.las
:IL046~9~ 9~gf~
been desirable~ as di~closed in some of the above noted
patents, to add additional elements to the catalyst
composition.
A review of the prior art and the present
applican~' wo~k~ ~s illu~.trated in the ex~mples disc~c~sed
below, indicates that the selection of additional elements
to be used in combination with the Mo-Bi-Fe-Ni and/or Co
based catalyst composltions, to provide the above ment;oned
lmprovements, is not an obvious procedure.
The terms % conversion, productivity and
% sPlectivity or efficiency which are employed herein
with respec~ to the present i~ention are defined as
follGws ~ased on the composition of the gas exiting
from the catalyst bed):
I % con~ersion = A - B x 100
whexe A - ~otal mol equivalents of olefin fed ~o
the catalyst bed
B - ~ol equivalents of unconverted olefin in
2Q gas exiting from the catalyst bed
.. ~ II Z E.-Lciency C x 100
where .A a~d B are as def.ined abo~e and
C ~ the mol equivalents of olefin which are presen~
in the alpha,beta unsaturated carboxylic acid
a~d al~ha,be~a unsaturated aldehyde which ~r~
producedO
. 3
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9S94-~
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III pro~uc~ivity - pounds of alpha-beta ~Isa~urated ~-
aldehyde and/or alpha beta unsaturatec~
c~boxylic acid produced per cllbic
foot of cata:Lyst (in the catalyst bed.)
per hour of reaction time.
Alpha,beta-unsatura~ed aliphatic carboxylic ac~ds
and alpha,beta unsatura~ed aliphatic aldehydes are produce~
with relatively hi~h % conversion, % ef~iciency and
productivi~y b~ oxidizing the corresponding alpha,be~
u~saturated aliphatic monoolein in the vapor phase by s,
- . co~tactillg the olefin, i~ the pr~sence of molecular oxyge~ '!i
and steam with certain catalyst compositions cont~L~in~
Mo, ~i, Fe, Si, and Ni and/or Co and Ru and/or Sb, a~
`. optionally, Cl. ~ `
. . An object of the present invention ~s to pr~vlde ,
~ovel oatalyst compositions for the vapor phase ox-lda~.o~
o ~lpha,beta unsaturated aliphatic monoolefins to ~he
coxresponding alpha,beta u~saturated aliphatic carboæ~lic
20 acid and alpha,be~a unsaturated aliphatic aldehyde~ 3~
A ~ux~her o~jec~ o~ the present inven~ion is ~
provlde a pr~cess whereby alpha,beta unsaturated ali~tic
monoolefins can be oxidized In the gas phase so as to ~
produce the corresponding alpha,beta~ satura~ed alip~at:~G ~L
carboxylic acld and alpha,be~2 unsaturated alipha~ic
aldehyde with a rela~ively high level of % conversion,
70 e~1ciency and productivity~ .,
.
. .
~ 969/l 1
A further objec~ o the present invelltion is to
provide a process whereby alpha,beta unsaturated monoolefins
can be oxidized in the gas phase in the presence o~ amrQOnia
. to F.roduce tlle corresponding alpha,beta unsaturated nitril~,
wlth a relatively high level of % conversion, % ef:~iciency
and. produc~ivity.
-These and other object:s o the present invention
are achieved by using as such a catalyst in such processes
a composition comprising the elements Mo, Bi, Fe, Si and ~
and/or Co ~nd Ru and/or Sb, and, optionally, Cl, i.n the ra~-io ''
a g,
wherein T is Ni and/or Co,
X is Ru and/or Sb,
a i~ iO, ~ - :
b is 0.1 to 5.0, and preferabl-y 0.5 to 1.5, ~:
c is d/3 to d/5, and preferably d/3.5 to d/5.0~ is
d is 2.0 ~o 9.0 a~d preferably 4.û to ~0~ ~
e is 1 to 20, and preferably 5 to 10, ~ :
f is û.l to 1.0, and preferably û.2 to 0.8
g is 0 to 5, and preferably 1.2 to 5.
: The ~umerical values of a, b, c$ d, e, f and ~,
xep~esent the relative gram-atom ratios o~ the elements
Moj Bi, Fe, T, Si~ X and Cl, respectively, which are ~`
initially added to the catalyst composition. After calcina
tio~ of the composition, as disclosed below, the amounts o~
the Mo, Bi, ~e, T, Si and X elements re~uains ~he sa~e, bu~
only trace a~ounts, i.e. ~ O to about < 0.1 weight pe~ce~t~
,
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of the Cl is still. ~esent. ~le Si which is used iIl
forming t.he catalyst ~omposition, in the ratios noted a~o~e~ :
is other than that which may be pxesent in any suppor~ o~
which the catalyst may be employed, as disclosed below.
~h~ y~
e elements Mo, Bi, Fe, T, Si and X are p~esen~
i.n the catalyst composi~ion in combination with oxyge~
the form, it is believed, of various oxides.
The catalyst is preferably prepared from a solu~
tion o~ soluble compounds-(sal~s, complexes or o~her
compounds) of each o the elements Mo, Bi, Fe, T3 X, a~ld ~:
~i or, i~ ~he case of Si, also a colloidal silica sol. ~e ~;
Cl is provi.ded in the form o a soluble sal~, and p~efer~hLy
'i in the form ~ 711~ri~ of one o~ the metals Fe~ T .~
.`. . The solution ls preferahly an aqueous system having ~ pE Q
~7~ and preferably 0.5 to 3.0, at a tempexa~ure of about
20 to 100C. The solution of the element containing
compounds is prepared by dissolving sufficie~t quant~tie~
o~ soluble compounds o~ each of the elements, so as ~Q
p~ovide the desired a:b:c:d:e:f:g gram-atom ratios of ~he
elements Mo~ B~ Fe, T, Si, X and Cl7 respectivelyO ~Q t~e
ex~ent possible the selected compounds of the var-;ou~ e1~J~en~S
should be mutually soluble. ~le S~ compo~mds axe ~s~
added in ~he form of a colloidal silica sol. Wher~ an~ o
th~ selected compounds o such elements, other th~n 51D ~
not mNtl~ll.y soluble with the other compounds, they c~ ~e
added las~ ~o the sol~tion system. The cat~lys~ co~os~:to~
. 6.
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9694-1
~ 4~
is then prepared by removing the water or other solvent
from the m~xture of the compounds in the solution system.
The water or other solvent can be removed by
evaporation from the mixture resulting r~m the combina-
tion of all the compounds and solvents.
Where the catalyst is to be used on a support,
the compounds of the desired elements are deposited on a
porous ~upport usually having a surface area of about 0.1
to 2 syuare meters per gram. The support has an apparent
porosity of 30 to 60%; at least 90% of the pores ha~e a
pore diameter in the range of 20-1500 microns. The
support is usually used in the form of particles or
pellets which are about l/8 to 5/16 inch in diameter.
The deposition is accomplished by immersing the support
in the ultimate mixture of all the compounds and then
evaporating off the major portion of the solvent~ and
then drying the system at about 80 to 140~C. for 2 to 60
hours. The dried catalyst is then calcined by being heated
to 400 to 550C. for 2 to 24 hours to produce the desired
MoaBibFecTdsiex~clg
composition, with the understanding, again, that the Cl
content of the calcined support is 0 to C~0.1 weight percent.
The Cl need only be present during the calcination of the
catalyst, it need not be present during the use of the
catalyst ln the oxidation of the monoolefin to the unsatura~ed
acid and aldehyde.
7.
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9694-1
~0~4'3~
The supports whi'ch may be'used include silica,
aluminum oxide, silicon car~ide, zirconia, titania and
mixtures thereo~. '
~ hen used on a support, the supported cat~lyst
usuall~ comprises about 10 to 50 weigh~ % of the'catalyst
i compos~tion, and about 50 to 90 weigh~ % of the'support.
T~e molybaenum is prefera~ly introduced into
solution in the form-of ammonium salts thereof such as
.
ammonium-paramoly~'date, and organic acid ~alts of
molyb'aenu~ such as acetates, oxalates, mandelates and
gl~colates. Other wa'ter soluble molybdenum compounds
which may b'e used are partially water soluble molybdenum
oxides, molybdic acid, and t~e nitrates and chlorides of
~nolybdenuTn .
The'bismuth, iron, nickel, co~alt, and
ruthenium, when used, are preferably introduced into
'-; solution in the form of nitrates. Other water soluble
compounds of these elements which may ~e used are the
water soluble chlorides and organic acid salts such as
the acetates, oxalates, tartrates, lactates, salicylates,
formates and carbonates of such elements.
The antimony is preferably introduced into
the catalyst system in the form of a water insoluble
oxide. A water soluble compound of this element which
may be used is antim~ny trichloride.
8.
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!.,
96
~hen sllicon is used it is pre~erably introduce~ ~
~,..... .
i~to the catalyst system in the ~o~m o~ an aque.ous col.l~idal
.~ silica (SiO2) sol~
The ~~ono-ole~.ins ?
.... _ ~ :
The alpha beta unsa~urated monoolefins wllich are
;~ oxldized in the process of ~he present in~ention are C3
,to C4 monoolefins such as propylene, 2-butene and
. i~obutylene. These ole~ins may be oxidized ;ndiviau
or ~n combinat;ons thereo~. ~
. 10 The principal oxidation products of these ~ :
~le1ns in the process of ~he prese~t invention are ~s
- f~llows:
~ .
Oxidized R
. OLeiin ~ c Acid A ~ '`
- propylene acrylic acid - acrolein . ~
2-butene crotonic acid crotonaldehyde ~ :
~:
isobutylelle methacrylic acid methacrole:2~
' tf
Where an ~mmoxida~ion reaction is conduc~ed
- che resultiIlg ni~ile products are as ~ollows:
..
,, . '
,,,
~ 90
~6 ~ 9~ 969~-~
A~oæi.dlæed
Ole~in Nitrile
propylene acryloni.trile
2-butene crotononitrile
isohut~lene methacrylonitrile
The Reaetlon ~ixture
The components o th~ reaction mixtures which
are employed in the oxidation process of the present
lnvention, and the rela~ive ratios of the components
quch mixtures, are the following:
1 mole of monoolefing
0.5 to 3 moles of molecular oxygen (as pure
oxygen or in the ~orm of air), and
0.5 to 20 moles of water (in the orm of stea~O
The water9 or steam, can be used as.a reac-tLc~
diluent and as a heat moderator or ~he reactions. ~her
diluents whi~h may be used are inert gases such as
nitrogen, C02 and gaseous saturated hydrocarbons.
The components of the oxida~ion reaction
mixture3 are u~iformly dmixed prior to being introduce~
into the reaction zone. The components are preheated~
; lndividually or after being admixed~ prior to their be~ng
introduced into the reaetion zone, ~o a temperature o~
~ about 200 ~o 300C.
I~ the ammoxidation reaction the reactants
inclu~e ammonia plus the other reactan~s noted above..
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3 ~ 9~ 9
Reaction Condit;ons
. ~
; The preheated oxida';i.on reaction mixture is ~;
. brought into contact with the catalyst composition, i.~
the reaction zone, under the ~ollowing conditions: .
p~essure of about 1 to 10, and preer~b~.y o~
about 2 ~o 4 atmosph~res,
~emperature of about 350 to 450C., and
.pr~ferably of about 360 to 410C.,
contact time ~reaction mixture on cataly~) o
about 0.1 to 10; and pre~erably of about 0 S
to 3~ seconds, and a space velocity of a~ou~
~ - lO00 to 10,000 h ~, preferably lS00 to 5000 h~. ~
.: The am~loxidation reaction is conducted ~nder i
~imil~r c~nditions.
The contact time may also be defined as ~he rati~
betwcen the apparent volume of the-catalyst bed and t~e
volume of the gaseous reaction mixture fed to the cata.ly~
- bed under the giveIl.reac~ion conditions in a U~lit 0~ t:Ime~
The reaction pressure is ini~ially provided ~
the eed of gaseous reactants and diluents, and a~ r ~e
reaction ~s commenced, the pressure is ~aintained~
preferably, by the use of suitable back-pressure
co~rollers placed on the gaseous efluent side of the
. . catalyst bed. :
The reaction temperature is preerably pr~i~e~ ~
by placiIlg the ca~alyst bed within a tubular conver~er .
~ wh~s~ walls are im~ersed in a suitable hea~ trans~er
,~,.. , , , .
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9694-1
medium, such as tetralin~ molten salt mixtures, or other
suitable heat transfer agent, which is heated to the
desired reaction temperature.
The following exampLes are merely illustrative of
the present invention and are not intended as a limitation
upon the scope thereof~
The examples provided below disclose the prepara-
tion of various catalyst compositions 9 and the use of such
compositions in the oxidation of propylene to acrylic acid
to acrolein.
The activity of ach experimental catalyst was
determined in a jacketed 1.049 inch (internal diameter)
stainless steel reactor or converter tube 78 inches long
equipped with a 1/8 inch central thermowell. The
jacket contained Dowtherm* which served as a heat transfer
medium. These experimental reactions were conducted under
one of two sets of conditions, i.e., Test Condition A and
Test Condition B, which conditions are described below.
.;. .
Test Condition A
The center portion (about 57-58 inches) of the
reactor tube was charged with about 800 ml of catalyst.
The catalysts were tested at about 40 psig with a
space velocity of about 4580-4600 hr 1 or contact time of
about 0.5 seconds, and an inlet feed composed of 3.5 mole
% propylene, 9.0 mole % oxygen, 20 mole % steam, and 67.5
mole % nitrogen.
The activity of the catalystswas tested by adjust-
ing the temperature of the reactor tube jacket to produce a
maximum temperature (hot spot) of 360C. in the catalyst
bed, while the oxidation reaction was occurring.
~ Trade Mark 12.
. .
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~J'~ 1
~e~t ConditiGn B
Tes~ Condl~ion B were the same as that of Tes~
Condition A except as ollows:
pressure, psig: 22-24 lbs/in2
~olume of ca~alys~ used: 815 ml
spa~e veloeity: 3400 hr
mol % of propylene in inlet feed: 6~2 ~ 6.5 ¦~
mol % of oxygen ln inlet feed: 12.0 - 12.5
mol % of H20 (as steam~ in inlet feed: 36-37
,~
mol 70 o~ ~itrogen in inle~ eed: 44-45.8
~cket temperature: 360C. I
ho~ spot temperature: 391-407C,
Space velocity is calculated by determini~g ~e
total reactor outlet gas equivalents (l~ters) of the 'o~al
effluen~ evolv~d over a period of one hour. This ~oom
teDpera~ure vol~me is converted to the volume cf O~C~
760 mm ~g.
Space Velocity - liters of outlet gas
equivale~ts/hour ~;
~ n ~ f
,.- ~v liters o~ catalyst in reactor
~ '
hours a~ 0 C. and atmospher~c ~'
pre~sure
~!'
~atalyst Emyloyed~ MoloFel~sNi6sbo.ssiloclo.6~u~o2
A~ F~f~y~four grams of bismuth nitrate pen~a~y~rate ~`
` (0.1122 gra~ atoms Bi) ~as dissol~ed in ~9 ml ~ '`
.. ' `
~ wat~r containing 6 ml o~ concentrate.d nit~iG acld.
: .
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9694-1
~Ci 4~
B. Sixty-eight grams of ferric nitrate nonahydrate
(0.168 gram atoms Fe) was dissolved in 45 ml
water.
C. One-hundred ninety-six grams of nickel nitrate
hexahydrate was dissolved in 95 ml of water.
D. Six and twenty-two hundredths grams of hydrated
ruthenium trichloride containing 36~5% Ru,
(0.0224 gram atoms Ru) was dissolved in 100 ml
of water.
E. The bismuth nitrate solution (A) was added to
the ferric nitrate solution (B) and then added
to the nickel nitrate solution.
F. One-hundred ninety eight grams of ammonium
paramolybdate (1.122 gram atoms Mo) was dissolved
in 300 ml of water while stirring at 60-80 in
a steam-jacketed stainless steel vessel (12-3/8
inch diameter by 5-3/4 inch deep evaporating dish).
Eight and two-tenths grams of antimony trioxide
; (Sb203) powder (0.0561 gram atoms Sb) was added
to the molybdate solution to form a suspension
while stirring.
The Bi-Fe-Ni solution (E) and the ruthenium
chloride solution (D) was then separately and simultaneously
fed to ~he Mo-Sb mixture (F) over a period of 10 minutes
at 50-60C., while stirring.
The above slurry was diluted with 400 ml of
water and 225 grams of LUDOX "AS"* (ammonium stabilized
*Trade mark or trade name 14.
: .. . . .. .. .. .
:... . . . . . ,: ~, . . :
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96g4-1
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colloidal silica containing 1.122 gram atoms Si) was
; added while stirring.
Seven-h~ndred seventy grams (~ne lit~r) of Norto~
SA-5205 9 l/4 inch silica-alumina spheres was added ~o the
above slur~y and the pH was adjusted to 1/3 at 59C. with
NH40H and the salts were depo,sited onto the suppor~ by
evaporating o:Ef ~he water while stirring manually on a
steam ba~h.
; The partially dried impregnated spheres were
10 removed rom ~he evaporator znd dried overnight at 115-
120C., and calcined at 450C. for 6 hours ln the presence
of air.
The finished cata~yst contained 22.0% oxides
~ncluding the colloidal silica which amounts to 4.4% of
~he catalyst. Approximately 66% of the theoretical
amount of oxides applied in the ~rm of various salts,
; adhered to the support. The gram atom ratio of the
components o~ the catalyst prior to calcining, the weight %
of oxides in the calcined catalyst, and the calcining
temperature ~re tubulated below in Table I.
When used to oxidize propylene under Test
~ Condition A noted abo~e the catalyst provided conversio~,
: efficiency al~d productivity results as shown below i~
Table II.
EXAMPLES 1 AND 3-12
The catalysts or Examples 1 and 3-12 were prepared
in a manner analogous to the procedure used in Example 2 with
~5.
,
9G ~34 - 1
adjustmellts in the amounts o the element~s (other th~n
and Mo) employed to give the gram-atom ratios requirecl,
o~ by deletlon of certain elements as required. I~le. g~a~ .
atom ~atio~ of the component,s of catalys~s 1, 3~1~ p~i~r ~o
calcining, the weight 70 of the oxides i.n the calcined
catalyst, and the calcining te~perature used for each
ca~alyst are tabulated below in Table I. Catalysts 1, 3-1
were also evaluated in Tes~ Condition A and the tes~
resul~:s are also sh~ in Table II.
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f~ f ~ fJ c~ c~ c~l f~f C~ C~f.~C'`l f'--` C~ C~l C~i N ~-
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- ~694~1
The catalysts of Examples 1, 2, 7, 10 and 12
represent catalyst compositions of the present inventionD
The cata~yst compositions of Examples 3-6, 8-9 and 11 are
comparative materials. A comparison of the oxidatio~ test
results listed for catalysts 1 12 in Table II shows the
advant~ges, in terms of % conversion, % efficiency and
productivity of the catalyst compositions of the present
invention, in comparison to the corresponding results
obtained with the co~parison catalyst systems.
~
The catalysts for Examples 13-22 were prepared in
a manner analogous to the procedure used in Example 1 wi~h
adjustments in the amounts of the elements (other ~han ~o~
employed to glve the gram-atom ratios required, or by
deletion of certaill elements as required. The gram-atom
- ratios o t~e components of catalystsl3-22 prior to
calcining, the ~eight % of the oxides in the calcined
catalyst, and the calcining temperature used for each
catalyst are tabulated below in Table III. Ca~alysts
13-22 were also evaluated -Ln Test Condition B and the ~es~
- results are sho~n below in Table IV.
, 19.
il'
969~- 1
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rl a~ ~ Ir) ~ ~~ ~ ~J ~ ~ ~
.~ ~
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!~1 ~ J~ ~ CJ~CO 1~ CO CO ~ ~ I~
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1 a
O C~
H H
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The catalysts of Examples 15 to 22 represent
catalyst compositions of the present invention. The
catalyst compositions of Examples 13 & 14 are comparative
materials. A comparison of the oxidation test results
listed for catalysts 13-22 in Table IV shows the
advantages in terms of % conversion, % efficiency and
productivity of the catalyst compositions of the present
invention, in comparison to the corresponding results
obtained with the comparison catalyst systems.
For the purposes of further definition, the
following terms employed in the catalyst evalua~ion are
given (basis of calculation = outlet gas composi~ion):
% Conversion =
(Total C3H6 Equivalents) - (Unconverted C3H6) 100
(Total C3H6 Equivalents)
% Efficiency =
~C3H6 Equivalents of Acrolein and Acrylic Acid3 100
- (Total C3H6 Equivalents) - (Uncoverted C3H6)
Productivity =
(Gms of Com onent/Hr~28 32 D Lbs/Hr-Ft
~453.~) (Catalyst Volume in Tube~ Liters) Catalyst
The catalyst of the present invention contains
the elements Mo, Bi, Feg X9 T, and Cl in the ratio
MoaBibFecTdsiexfclg
whereîn, as noted above, inter alia, c has been given a
value of d/3 to d/5, and, preferably d/3.5 to d/5.
Calculating the value of c, however, for Examples 16, 17,
18, 20 and 21 as presented above in Table III, indicates
that in Example 16, c is d/5.2 and in Examples 17 and 21,
c is d/5.51, and in Exc~mple 18, c is d/5.01 and in Example
20, c is d/5.1.
22.
