Note: Descriptions are shown in the official language in which they were submitted.
BACICGR( ~D O_ TIIE ~~IVE~ITION
Belgian Patent No. 828,074 ~:eaches the use of a
catalyst containing phosphorus, molybdenum, bismuth, copper,
at least one of Fe, Ni, Co and K, ancl optionally, Li, Na,
Rb, Cs, Be, Mg, Ca, Sr, or Ba in the preparation oE maleic
anhydride ~rom butene-l, butene~2, butadiene, pentane,
pentadiene, cyclopentadiene and benzene. Comparative Example
4, at pages 20 and 21 of -this patent exemplifies that use
of a catalyst having the formula Pl 00~Il2Bio.36CU0.5439.6
in the oxidation of butene-l gave a 27.9~ yield of maleic
anhydride, based on the amount of butene-l fed.
.. . . .
,. ~ . . .
: ~ .
~' ' , : :
~ -
. ~ ,: ' ' . , .
.'.:;' .- . : '
.. .
, .
6 1 )
(Ll~63)
( l~96L~ )
3~ ~ 5 (4~65)
~rench Patent No. 1,601,955 teaches use of a
catalyst having the composition AO3-B2O5-M2O5-NX0-R2O
wherein A is Cr, Mo, W or U; B is V or Nb; M is P, Asg Sb or
Bi, N is Cu, Ag, Fe, Co or Ni; R is Li, Na, K, Cs or Rb.
Preferred composition is 15-55 atomic ~ A, 30-70% B, 0-15%
M, 0.1-20% N, and 0-15% R.
The present invention is a result of a search fo-r
more efficient catalysts for use in the oxidation of n-
butane, n-butenes and 1,3-butadiene.
The catalysts employed in the present invention
are unexpectedly advantageous in the production of maleic
anhydride from n-butane, n-butenes and 1,3-butadiene.
Especially desirable yields are obtained from 1,3-butadiene
or n-butenes usin~ catalysts of the invention.
SUMMARY OF THE INVENTION
. It has now been discovered according to the pre-
sent invention in the process for the production of maleic
anhydride by the oxidation of n-butane, n-butenes, 1,3-
butadiene or mixture thereof, with molecular oxygen in the
vapor phase at a reaction temperature of about 250C to
about 600C in the presence of catalyst, and optionally in
the presence of steam, the improvement whlch comprises using
as a catalyst a catalyst described by formula I
Mol2PaBibCucxdOf
~l 25 wherein X is a halogen selected from the group con-
'l sisting of chlorine, bromine or iodine;
~l and wherein a, b and c are numbers ~rom 0.001 to 10;
~:,
d is from 0.001 to 5;
f is a positive number of oxygens required to
satisfy the valence states of the other
elements present; or
i~
. .
f;
( l~'361 )
6 3 )
(4964)
~ 8 3~ S (~965)
using as a catal~st a catalyst described by formula II
~CaMol2Pb~ScOx
wherein X is at least one element selected from the
group consisting of Sn, rare earth metal, Zr,
Rh, Mn Re, Ru, Cu, Pb, Zn, Ti, Cr, Nb, Al,
Ga and alkaline earth metal;
and wherein a is a positive number less than about 20;
b and c are numbers from 0.001 to 10;
x is the number of oxygens re~uired by the
valence states of the other elements present;
or
using as a catalyst a catalyst described by formula III
a 3 b x
wherein X is at least one element selected from the
group consisting of As, Rb, Pd, Cd, Cs, Tl
and In;
and wherein a is a positive number less than about 10;
b is a positive number less than about 3~
x is the number of oxygens required to sat-
isfy the valence states of the other elements
present; or
using as a catalyst a catalyst described by formula IV
XaMl2PbRbcOx
wherein X is at least one element selected from the
group consisting of Sn, rare earth element,
Ni, Zr, Ba, Fe, Rh, Mn, Re, Ru, Co and Cu;
and wherein a is a positive number less than about 20;
b and c are numbers from 0.001 to 10;
x is the number of oxygens required by the
valence states of the other elements present.
Especially high yields and selectivities of maleic anhydride
are obtained from four-carbon hydrocarbons in an efficient,
convenient, and economical manner at a relatively low temp-
erature. The exotherm of the reaction i5 low, thereby
allowing easy reaction control.
The most significant aspect of the present inven-
tion is the catalyst employed. The cai,;alyst may be any of
~831~S
the catalysts delineated by formulae I to I~. The catalysts
of the invention have prefer~ed limi-tations on their composi-
tion.
When catalysts within formula I are employed, pre-
ferred are catalysts wherein a, _, and c are numbers from O.Ol
to 5 and d is from O.OOl to lØ Also preferred are catalysts
wherein a is O.S to l.5, catalysts wherein _ is O.l to l.0,
catalysts wherein c is O.l to l.0, and catalysts wherein d
is O.Ol to 0.5. Catalysts of particular interest are described
wherein d is 0.005 to O.l. Especially preferred are catalysts
wherein X is chlorine.
When catalysts within formula II are employed, pre~
ferred catalysts are described wherein ~ is a positive number
;i .
less than about 12, catalysts wherein b is O.Ol to 5, and
catalysts wherein c is O.Ol to 5. Highly desirable results ~ -
are obtained wherein b is 0.5 to l.5 and c is O.l to lØ ~ ~
Preferred catalysts are described wherein each element de- ~ -
lineated by X is separately incorporated into the catalyst.
Especially preferred catalysts are described wherein X is
copper in combination with at least one of the remaining
elements, also delineated by X.
When catalysts within formula III are employed,
preferred catalysts are described wherein a is a positive
number less than about 7, and catalysts wherein b is a
positive number less than about 2. Highly desirable results
are obtained wherein a is O.Ol to 3 and b is O.Ol to lØ
Catalysts of special interest are described wherein X is at
least one element selected from the group consisting of
rubidium, cesium, thallium and indium. E~cellent results
are obtained wherein each element delineated by X in the
catalytic formulais separately incorporatec1 into the catalyst.
-- 4 --
( 1! 9 6 1 )
( ~! 9 6 3 )
( 1! 9 6 4 )
( L, 9 6 5 )
~0~33~L~S
When catalysts withln formula IV are employed,
preferred catalysts are described wherein a is a positive
number less than about 12; catalysts wherein b is 0.01 to 5;
and catalysts wherein c is 0.01 to 5. Especially preferred
catalysts are described wherein b is 0.5 to 1.5 and c is 0.1
to lØ Highly desirable catalysts are described wherein X
is at least one element selected from the group consisting
of Ni, Cu, Sn, and a rare earth element.
~he methods of preparing the catalysts of the
present invention may vary widely. A number of techniques
are known to those skilled in the art. Methods of catalyst
preparations such as coprecipitationg evaporative drying, or
o~ide mixing, followed by calcining the resulting catalysts
may be successfully employed.
The preferred procedure ~or preparing catalysts
within formulae I to IV involves preparing the catalysts in
an aqueous slurry or solution of compounds containin~ molyb~
denum and phosphorus, adding the remaining components; and
evaporating this aqueous mixture. However, when catalysts
within formula II are prepared, the preferred procedure
involves preparing the catalysts in an aqueous slurry or
so]ution of compounds containing molybdenum, arsenic and/or
phosphorus and then adding the remaining compounds. Suit-
able molybdenum compounds that may be employed in the prep-
aration of the catalysts delineated by formulae I to IVinclude molybdenum trioxide, phosphomolybdic acid, molybdic
acid, and ammonium heptamolybdate. Excellent results are
obtained using catalysts of the invention wherein at least
part of the molybdenum employed in the preparation of the
3 catalysts is supplied in the form of molybdenum trioxlde.
Suitable phosphorus compounds that may be employed in the
-5-
( 1-' 9 ~
(11963)
6 4 )
( 1!965)
10831~5
preparation of the catalysts include orthophosphoric acid,
metaphosphoric acid, triphosphoric acid, phosphorus halides
or oxyhalides. ~he remaining components of the catalysts
may be added as oxide, acetate, formate, sulfate, nitrate,
carbonate, halide and oxyhalide.
It is important to note that when catalysts within
formula I are prepared, especially preferred are catalysts
wherein bismuth is supplied in the form of a bismuth halide ~ -~
or oxyhalide. It is not clearly understood where the halo-
gen atom is located in the catalytic structure. Infra~red
analysis reveals that the catalysts are mostly phospho-
molybdate-based and that the halogen is most probably
present as a molybdenum oxyhalide.
Excellent results are obtained by refluxing phos-
phoric acid and molybdenum trioxide in water for about 1.5 -
to 3 hours, however, commercial phosphomolybdic acid may be
effectively utilized; adding the remaining components to the
aqueous slurry and boiling to a thick paste, where at least
one of the components is added as a halide or oxyhalide; and
drying at 110C to 120C in air. Howe~er, when catalysts
within formula II are prepared, the best results are obtained
when the catalysts are calcined following the drying step.
he catalysts within formulae III and IV may also be prepared
by mixing the catalytic components in an aqueous slurry or
solution, heating the aqueous mixture to dryness; and calcining
the resulting catalysts.
; With the exception of catalysts within catalyst
II, by the preferred procedure of the in~ention calcination
is not generally required to obtain desired catalysts.
.....
,
(~1961)
63)
,~. ( 4964 )
(l~965)
~8 3~ ~ S
However, calcination may be accomplished by heating the dry
catalytic components at a temperature of about 300C to
about 700C, ~ith preferred calcinatioll being accomplished
at a temperature of 325C to 450C. The hydrocarbon reacted
may be n-butane, n-butenes, 1,3-butadiene or a mixture
thereof. Preferred is use of 1,3-butadiene, n-butenes or a
mixture of hydrocarbons that are produced in refinery streams.
The molecular oxygen is most conveniently added as air, but
synthetic streams containing molecular oxygen are also
0 suitable. In addition to the hydrocarbon and molecular
oxygen, other gases may be added to the reactant feed. For
example, steam or nitrogen could be added to the reactants.
The ratio of the reactants may vary widely and are
not critical. The ratio of the hydrocarbon to molecular ;
oxygen may range from about 2 to about 30 moles of oxygen
per mole of hydrocarbon. Preferred oxygen ratios are about
4 to about 20 moles per mole of hydrocarbon.
The reaction temperature may vary widely and is
~ dependent upon the particular hydrocarbon and catalyst
employed. Normally~ temperatures of about 250C to about
~; 600C are employed with temperatures of 250C to 450C
belng preferred.
The catalyst may be used alone or a support could
be employed. Suitable supports include silica, alumina,
Alundum, silicon carbide, boron phosphate, zlrconia, and
titania. The catalysts are conveniently used in a fixed-bed
reactor using tablets, pellets or the like or in a fluid-bed
reactor using a catalyst preferably having a particle size
of less than about 300 microns. The contact time may be as
low as a fraction of a second or as high as 20 seconds or
., . j
, .. .. .. .. , , . . ;
, . ........... ........ . . .
. ,, , , , . "
(1~961)
(11963)
,, (~1964)
~831~5 ( 4g65)
more. The reaction may be conducted at atmospheric, super-
atmospheric or subatmospheric pressure.
Excellent results are obtained using a coated
catalyst consisting essentially of an inert support material
having a diameter of at least 20 microns and an outer sur-
face and a continuous coating of said active catalyst on
said inert support strongly adhering to the outer surface of
said support.
By use o~ these coated catalysts in the reaction
to produce maleic anhydride, a very low exotherm is realized
allowing for better control of the reaction. High single
pass yields are exhibited and the elimination of undesirable
byproducts is obtained.
The special coated catalyst consists of an inner-
support material having an outside surface and a coating ofthe active catalytic material on this outside surface.
These catalysts can be prepared by a number of different
methods.
The support material for the catalyst forms the
inner core of the catalyst. This is an essentially inert
support nad may have substantially any particle size of
shape although a diameter of greater than 20 microns is
preferred. Especlally preferred in the present invention
for use in a commercial reactor are those supports which are
spherical and which have a diameter of about 0.2 cm. to
about 2 cm. Suitable examples of essentially inert support
materials include: Alundum, silica, alumina, alumina-
silica, silicon carbide, titania and ~irconia. Especially
preferred among these supports are Alundum1 silica, alumina
and alumina-silica.
. ' ' ', ' ' ' ' , ,
('119~1)
6 3 )
fj 4 )
33~5 ( ~ 5 )
The catalysts may contain essentially any pro-
portions of support and catalytically active materlal. The
limits of this relationship are only set by the relative
ability of the catalyst and support material to accommodate
each other. Preferred catalysts contain about 10 to about
100 percent by weight of catalytically active material based
on the weight of the support.
The preparation of these coated catalysts can be
accomplished by various techniques. The basic method of
preparing these catalysts is to partially wet the support
material with a li~uid. The support should not be wet on
the outside surface of the total mass. It should appear to '~
be dry to the touch. If the support is wet, then the active ~,
catalytic material may agglomerate into separate aggregates , ,~
when coating of the support is attempted. These partially
wet support3 are then contacted with a powder of the cat-
alytically active material and the mixture is gently agitated
until the catal~st is formed. The gentle agitation is most
conveniently conducted by placing the partially wet support
in a rotating drum or ~ar and adding the active catalytic
material. This is very economically done.
Using the catalysts of the invention in the prep-
aration of maleic anhydride, excellent yields are obtained
in a convenient reaction with low amounts of byproducts.
SPECIFIC_EMBODIME~TS
Examples 1 to 60: Preparation of Maleic anhydride Vsing
Yarious Catalysts of the Invention.
F,xamples l to 5: Preparation of r~laleic Anhydride Using
Catalysts Des~ribed Within Formula I.
_ g_ :,
.. . . ..
~ ' , . . " , .
.. . . . . . . .
(~1961)
~ 63)
(4961l)
(4~65)
3~ 5
Example l
A catalyst of the formula Mol2Pl.32Bio.5cuo~25
Clo 06f was prepared as follows: A slllrry was prepared
of 86.4 grams (0.60 mole Mo) of molybdenum trioxide and 7.6
g. (o.o67 mole P) of 85 % phosphoric acid in 500 mls. of
distilled water; boiled with stirring for three hours to
form phosphomolybdic acid which was yellowish green in
color. To this surry was added 2.5 g. (0.0125 mole Cu) of
copper acetate; no change in color, followed by the addition
of 7.9 g. (0.025 mole Bi) of bismuth chloride dissolved in
4.0 ml. of concentrated hydrochloric acid. The mixture was
boiled to dryness; dried overnight at 110C in air. The
catalyst was ground and screened to lO/30 mesh fraction.
A portion of the catalyst partlcles were charged
to a 20 cc. fixed-bed reactor equipped with a l.02 cm.
lS inside diameter stainless steel tube.
The reactor was heated to reaction temperature
under a flow of air and a feed of l,3~butadiene/air, as
indicated below, was fed over the catalyst at an apparent
contact time of 3 to 4 seconds and the performance evaluated
by collecting and analyzing the products.
The results of these experlments appear in TABLE
I. The following deflnitions are used in measurlng the
carbon atoms in the feed and in the product: -
% Single pass yield = M~Oles-oof MydrOcarbnhondrindteheReFeovdred x lO0
Total Conversion Moles Of HYdrocarbon in the peed x lO0
Selectivity = Single Pass Yield x lO0
~otal Conversion
--10--
': " - ' , ';,
1~33~
Examples_2 to 5
T~E I -~
Preparation of Maleic Anhydride From - -
1,3-butadiene Using the Catalyst
Mol2P1 32Bio sCU0.25C10.06f
Feed
Temp.C. Ratio Results, %
Exc~le Bath Exotherm Air/HC Ibtal Acid Mal_ic Anhydride Selectivity
2 301 310 23~.31 6.97 83.9
3 317 329 ~148.10 44.09 91.7
: ~- . . .
4 333 351 3453.47 47.88 89.6
3~9 379 2752.67 47.07 89.4
In the same manner catalysts containing different
amounts of phosphorus, bismuth, copper and chlorine are used
to prepare maleic anhydride from 1,3-butadiene.
Also, in the same manner, various catalysts of the
invention are promoted with elements such as Mn, Rh, Ru, Ti,
Zn, Re, Pb, rare earth element, In, Sn, Zr, Cr, Pd or mix-
ture thereof to produce desirable yields of maleic anhydride
fron n-butane, n-butenes, 1,3-butadiene or mixture thereof.
Examples 6 to 23: Preparation of Maleic Anhydride Using ;~
Catalysts Described Within Formula II
_xamples 6 to 8
Various catalysts described within formula II ~''4 ' "',;.
.:.' . '
were prepared as follows: ;
'' `'i',
MoI2P1 32As0~5Cuo-25 x
A slurry consisting of 317.8 grams of ammonium
heptamolybdate, ~NH4)6Mo7O24 4H2O and 1500 mls. of dis-
-- 11 --
;''' ' ','' : .
.-, ' ' ~ :
.
(11961)
_ (l196~)
831~;5 (4965)
tllled water was boiled with stirring. To this slurry was
added 11.91 grams of ammonium arsenate~ NH4H2AsOL~ and
heating was resumed for 20 minutes; the color was white.
Upon the addition of 7.5 grams of copper acetate, the color
changed to light blue. To this mixture was added 22.8 grams
of phosphoric acid, H3P04 (~,5~ solution)~ and 10 minutes
later 7.5 grams of hydrazine were added to give a dark blue
solution which was evaporated to a thick paste, dried over~ -
night at 100C to 120C and ground and screened to less than
50 mesh. The resulting catalyst was calcined l hour at
371C in 40 mls./minute air.
Example 7
~lol2pl.32Aso.5cuo.2oc-4ox
; A slurry was prepared consisting of 105.9
grams of ammonium heptamolybdate, 700 mls. of 60C distilled ~;
water and 3.97 grams of ammonium arsenate as solution in 25
mls. water; a white precipitate formed which was heated to
boiling for 45 minutes. To this mixture was added 15.2
grams of chromium oxide; 15 minutes later 2.4 grams of
copper acetate were added; and one-half hour later 7.6 ~rams
of 85% phosphoric acid was added. The solution was boiled
to a thick paste; dried in an oven overnight at 110 to
120C; and ground and screened to less than 50 mesh size.
Calcination was the same as described in Example 2.
Example_8
25%M12Pl.32Aso.sCu0.2oCr4~x + 75% Alundum (coated)
This catalyst was prepared in the same manner
described in Example 3, except the dry catalytic particles
-12-
' '' ' ' ' ' ,
( ~l9til )
(43
( 11 9 ,~
~ ( 4 9 ~; 5 )
were coated on 1/8" SA5223 Alundum balls by taking 50 grams
of Alundum, partially wetting the Alundum with 1.8 grams of
water and adding 16.7 grams of active catalyst prepared ~
above in five equal portions. During and after each addi- -
tion, the Alundum was rolled in a glass ~ar. The powder was -
evenly coated onto the surface of the Alundum and the final
product was dried. The hard uniform coated catalyst was
obtained that consisted of the Alundum support with the
continuous, strongly adhering coating of the active cat-
alyst. T~e catalyst was then calcined for 2 hours at 371C
in 40 ml./min. air.
Examples 9 to 23
Preparation o~ Maleic Anhydride from 1,3-butadlene
A portion of the catalyst particles prepared
in accordance with Examples 6 to 8 were charged to a 20 cc. -~
~ixed-bed reactor equipped with a 1.02 cm. inside diameter
stainless steel tube.
~ ~he reactor was heated to reaction tempera-
ture under a flow of air and a feed of 1,3-butadiene/air as
indicated below was fed over the catalyst at an apparent
contact time of 3 to 4 seconds and the performance evaluated
by collecting and analyzing the products.
The results of these experiments appear in
~A~LE II. ~
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~ 3 ~ l~i
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H ~I Q
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u~~u ~ ~ ~ L~ ~ In ~1 n o ~ ~ o o~
1 4 ~ In ~ r ~ ~ In In ~ ~i In In ~ ~
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S~ o~ o~d o~ oX
J,J o~i oX o~ o~ ~ ~ ~ ~ N ~ ~
g~ In In In n ~ o~i3 o~ o o o o
Ig O O O O O O O O O Yn ~ C~n~ ~n n C)n Cn
~n ~n In In In In In ~ N ~N
U~ U~ U~ j U, 1~
N t~l N ~ 1 N N ~1 N r l ~d '1~ r-i r l r l r-i
~l r~7 ~i ~ ~ ~) ~ p~ q jl~ Ij i N ~
~I N ~ o~
r-i ~i r-i r-~ r l r l r l r l r l ~i d d~ o~
~ 9 In~ n~ In
t~.
~ ~) O r l ~i ~ r m ~ o
~i r l r l r-l r l r-i r l r l r l ~1 --1 ~ ~1 ~1
1~
(I~q6!.)
(!Iq6 ~
( I, n6 i, )
10~33~t;S ( ! a65 )
Examples ~4 to 50: Pre~aration of Malelc ~nhydride ~Jsing
C~talvsts nescribed Within Formula III
_
~xamples 24 to 27
Various catalysts described within formula III
were prepared as follows:
~xample 24
Rbo 5Mo3P0 33x
An a~ueous slurry was prepared by adding 55.3
grams of molybdenum trioxide to one liter of boiling dis-
tilled water with stirring; the slurry was boiled for about
2 hours. To this aqueous slurry, 4.9 grams of 85~ solution
phosphoric acld was added; the color of the slurry changed
to yelIow. About 200 mls. of distilled water was added to ,
maintain an approximately 800 mls. solution level. To this
aqueous mixture, 7.5 grams of rubidium carbonate were added;
the color of the slurry became bright yellow; after about 30 -~
minutes 25 mls. of distilled water were added. The catalyst
was heated with stirring; boiled to dryness; and dried to
air at about 110C. The catalyst was ground and screened to
give a 10 by 30 mesh fraction.
''~ ,
Rxamples 25 to 27
Various catalysts of the present invention were
prepared. These catalysts have the general formula X0 5- ~;
Mo3P0 33x The catalysts were prepared according to the
procedure of Example 1, except 86.2 grams of MoO3, and 7.7
grams of 85~ H3P04 were employed. The element delineated by
X was added following the addition of phosphoric acid. To
prepare the catalysts, the following compounds and amounts
were used:
-15-
- .... ;. ,
... . . . . . . . .
6 1 )
~1~96~)
'9611 )
~L0~331~ 965 )
Example ~lement, ~ = Compound Amount~_~.
25 Cs cesium acetate 19.2
26 Tl thallous acetate 26.3
27 In indium acetate 29.2
~ollowing the addi~ion of the element, X, the catalysts were
boiled to dryness, dried in air, ground and screened in the
same manner described in Example 1.
Examples 28 to 46
Preparation of Maleic Anhydride from Butene-2
A portion of the catalyst particles prepared in
accordance with .xamples 25 to 27 were charged to a 20 cc.
fixed-bed reactor equipped with a 1.02 cm. inside diameter
stainless steel tube.
~he reactor was heated to reaction temperature
under a flow of and a feed of air/butene-2/H2O, as indicated
below, was fed over the catalyst at an apparent contact time
of 1.0 to 1.5 seoonds and the performance evaluated by
collecting and analyzing the products. The results of these
experiments appear in TABLE III.
'
Examples 47 to 50
Preparation of Maleic Anhydride From
Butene-2 Using Supported Catalysts
Various catalysts were prepare~ using the catalyst
of ExamPle 2 having the formwla Cso~5~o3P0~330x d
30% by weight of low surface area supports (i.e. ~ 20m2/gram).
These catalysts were reacted with butene-2 and air in the
same manner described above. The results of these experi-
ments appear in ~ABLE IV.
-16-
/
. . .
~: .
.
~33~
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Examples 51 to 60: Preparation of Ma]eic Anhydride Using
Catalysts Described ~ithin ~ormula IV
A catalyst of the formula Nio 2CuO 25~12Pl 32-
Rb20X was prepared as follows:
A slurry was prepared of 86.4 grams (o.6 mole) of
molybdenum trioxide and 7.7 grams (o.o67 mole) of 85% phos- -
phoric acid in 800 mls. of distilled water; boiled with
stirring for two hours which was yellew greenish in color.
0.74 grams (0.01 mole) of nickel oxide were added to the
slurry; no change in color, followed by the addition of 2.49
grams (0.0125 mole) of copper acetate hydrate and no change
in color was observed. Boiling was continued for an addi-
tional l.S hours, heating was discontinued, distilled water
was added to the mixture to bring the volume up to 800 mls.,
and the slurry was allowed to stir overnight. The next day
14.4 grams (0.1 mole) of rubidium acetate were added and a
heavy yellow precipitate immediately formed. This mixture
was boiled to a thick paste and dried in an oven at 110-
120C overnight. The catalyst was ground and screened to20/30 mesh size.
The reactor was constructed of a 1.02 c~. inside
diameter stainless steel tube. A portion of the aatalyst
fraction was charged to the 20 cc. reactlon zone of the
reactor.
The reactor was heated to reaction temperature and
a ~eed of air/butene-2, as indicated ~elow, was fed over the
catalyst at an apparent contact time Ol 1.0 to 1.5 seconds
and the performance was evaluated by collecting and analyz-
lng the products.
The results of the experiments appear in the Table
V in Examples 53 to 60.
--19--
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Example 52
,,
Preparation of ~aleic Anh _ride from 1~3-Butadi_ne
In the same manner described above, the catalyst
0.2C 0.25~o12Pl.32Rb2~x was reacted with air and 1,3-
butadiene. An air/1,3-butadiene feed of 84/1 was passed
over the catalyst at a reaction temperature of 285C at an
apparent contact time of 1.5 seconds. The results of this
experiment showed a 17.8% single pass yield of total acid.
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