Note: Descriptions are shown in the official language in which they were submitted.
- ` :
BACKGROUND OF THE INVE~TION
A number Or catalysts are known to be effective
for the oxidation of acrolein or methacrolein to acrylic
acid or methacrylic acid, respectively. However, the
y~elds obta~ned using the ca~alysts for the preparation o~
metahcrylic acid are low. West German Provisional Patent
No. 2,048,620 discloses catalysts containing the oxides of
molybdenum, phosphorus, and arsenic for the oxidation of
methacrolein and acrolein to methacrylic acid and acrylic
acid, respectively. U. S. Patent Mo. 3,761,516 discloses
catalysts containing oxides of molybdenum, arsenic and
phosphorus on a support, especially A12O3, having external
macropores and a surface not greate~ than 2 m2/g.
.
,. ,
.,
.
. . .
- (4957)
(~g58)
(4959)
~ 2~ ~
The present invention is a result of a se~rch for
more efficient and desirable catalysts for the production of
acrylic acid and methacrylic acid. Unexpectedly higher
yields of and selectivities to acrylic acid and methacrylic
acid are obtained by the vapor phase oxidation of acrolein
and methacrolein, respectively, with molecular oxygen in the
presence of the new and useful catalysts of the present
invention.
SUMMARY OF THE INVENTION
It has been disclovered according to the present
invention in the process for the preparation of acrylic acid
or methacrylic acid by the oxidation of acrolein or meth-
acrolein, respectively, with molecular oxygen in the vapor
phase at a reaction temperature of about 200C to about
500C in the presence of an oxide catalyst, and optionally in
the presence of steam, the improvement comprising
using as a catalyst a catalyst described by the
formula
xayb~lTol2pcAsdox
wherein X is a rare earth element or a mixture
thereof;
Y is at least one of Ag, Tl, Rh, Pd, RU, Pt,
Cd, Al, Au, Cu, al~aline earth metal~ Cl and
NH4;
wherein a is 0.001 to 10;
b is O to 10;
c is 0.~1 ~o 5;
d is 0.01 to 5;
x is the number of oxygens required to
satisfy the valence states of the okher
elements present; or
(4958)
(4959)
~ ing as a catalyst a catalyst described by the
formula
~aYbMl2PcAsdox
; wherein X is at least one element selected from the
group consisting of U, ~rl, Nb, Re, Pb, Zn
and Ga;
Y is Cu, a rare earth element, Ag, Ta, In,
Th, Cd, Tl, an alkaline earth metal, NH4,
Cl~ Ni, Al and Ge~
and wherein a is 0.001 to 10;
b is O to 10;
c is 0.01 to 5;
d is 0.01 to 5-
x is the number of oxygens required tosatisfy the valence states of the other
elements present; or
uslng as a cakalyst a catalyst describe~ by the
;~ formula
xaYbMI2PcASdOx
wherein X is at least one element selected from the
group consisting of Ag, Rh~ Ru and Au;
Y is at least one of Cd, Tl, Pd7 Al, Ge,
Cu, Pt, Ni, alkaline earth metal, NH4, and
Cl;
and wherein a is 0.001 to 10;
b is O to 10;
c is 0.01 to 5
d is 0.01 to 5;
x is the number of oxygens required to
satisfy the valence states of the other
elements present.
The surprisingly advarltageous catalysts of this
invention give im~roved yields of acrylic acid and methacrylic
acid from acrolein and methacrolein, res~ectively, in an
efficient, convenient, and economical manner at a relatively
low temperature. ~he exotherm of the reaction is low,
thereby allowing easy reaction control.
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~ (4958)
The most si~nificant aspect of the present inven
tion is the catalyst employed. The catalyst may be any of
the catalysts delineated by ~ormulae I to III. The cat-
alysts can be prepared by a number of different techniques
described in the art, such as coprecipitation of soluble
salts and calcination of the resulting product. The cat-
alysts of the invention have preferred limitations on their
composition.
When catalysts within formula I are employed, pre-
ferred are catalysts wherein a is 0.001 to 3, catalysts
wherein b is OoOOl to 3, and catalysts wherein b is zero.
Especially preferred are catalysts wherein X represents
cerium, erbium, or a mixture of rare earth elements con-
sisting essentially of Ce, La, Nd and Pr. Catalysts of
particular interest are described wherein Y is silver,
thallium or copper.
When catalysts within formula II are employed,
preferred are catalysts wherein a is 0.001 to 3, catalysts
wherein b is 0.001 to 3j and catalysts wherein b is zero.
Especially preferred are cata].ysts wherein each of the
elements described by X is separately incorporated into the
catalyst. This is conveniently accomplished by setting X
independently equal to the various elements. Catalysts of
particular ~.nterest are described wherein Y is at least one
element selected from the group consisting Or a rare earth
element, Al, Ag and Cu.
When catalysts within formula III are employed,
preferred are catalysts wherein a is 0.001 to 3, catalysts
wherein b is 0.001 to 3, and catalysts wherein b is zero.
Especially preferred are catalysts wherein each of the
elements described by X is separately incorporated into the
2~ ~ (4958)
(4959)
catalyst. Thls is conveniently accomplished by settln~ X
independently equal to the various elements. Also preferred
are catalysts wherein Y is at least one of Cd, Tl, Cu, NH
and Cl.
In the catalyst preparations, the various elements
oP the catalyst are combined, and the ~inal product is
calcined to obtain the catalyst. A number of methods of
combining the elements of the catalyst and calcining the
resultant product are known to those of sklll in the art.
In the ~road concept of the invention, the particular method
of preparing the catalysts is not critical.
There are, however, methods of preparing the
catalysts that have been found to be preferred. One preferred
preparation involves the preparation of the catalysts in an
aqueous slurry or solution of molybdenum, arsenic, and/or
phosphorus containing components, and adding the remaining
components; evaporation of this aqueous mix~ure; and calcination
o~ the resulting catalysts. Suitable molybdenum compounds
that may be employed in the preparation of the catalysts
delineated by the above formula include molybdenum
trioxide, phosphomolybdic acid, molybdic acld, ammonium
heptamolybdate and the like. Suitable phosphorus compounds
that may be employed in ~he preparation of the catalysts
include ortho-phosphoric acidg metaphosphoric acid, tri-
phosphoric acid, and phosphorus halides or oxyhalides.
The remaining components of the catalysts may be added as
oxlde, acetate, formate, sulfate, nitrate, carbonate, oxyhalide,
or halide and the like.
g ~g$~i~
Excellent results are obtained by refluxing
phosphoric acld, an arsenic containing compound, and molyb-
denum trioxide, or ammonium heptamolybdate in water for
about one-half hour to 3 hours, howe~er, commercial phospho
molybdic acid may be effectively utilized; adding the remain-
ing components to the aqueous slurry and boiling to a thick
paste; drying at 110C to 120C in air; and calclning the
resulting catalysts.
The calcination of the catalyst usually is accom-
plished by heating the dry catalytic components at a tempera- -
ture of about 200C to about 700C. The preferred procedure
of the invention is wherein the catalyst is calcined at a
temperature of 325C to 425C.
The reactants of the reaction of the invention are
methacrolein or acrolein and oxygen. Molecular oxygen is
normally supplied to the reaction in the form of air, but
oxygen gas could also be employed. About 0.5 to about 4
moles of oxygen are normally added per mole of methacrolein.
The reaction temperature may vary as different
catalysts are employed. Normally, temperature of about
~00C to about 500C are employed with temperature of 250C
to 370C being preferred.
The catalyst may be used alone or a support could
be employed. Suitable supports include silica, alumina,
Alundum~, silicon carbide, boron phosphate, zirconia 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 ha~ing a particle size of less than
about 300 microns. When a fluid-bed reactor is employed,
preferred catalysts are in the form of microspheroidal particles.
',!i.~
`:
(4957)
5 ~ (~958)
The contact time may be as low as a fraction of a second or
as high as 20 seconds or more. The reaction may be conducted
at atmospheric, superatmospheric or subatmospheric pressure,
wlth absolute pressures of about 0.5 to about 4 atmospheres
being preferred.
Excellent results are obtained using a coated
catalyst consisting essentially of an inert support material
having a diameter of at leas~ 20 microns and an outer surface
and a continuous coating of said active ca~alyst on said
inert support strongly adhering to the outer surface of said
support. The special coated ca~alyst cons~sts of an inner
support material having an outside surface and a coating of
the 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 and may have substantially any particle size although
a diameter of greater than 20 microns is preferred. Especially
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 o~ essentially inert support materials lnclude:
Alundum, silica, alumina, alumina-silica, slIicon carbide,
titania and zirconia. Especially preferred among these
supports are Alundum~ sllica, alumina and alumlna silica.
(4957)
~ 2~ ~ (4~958)
The catalysts may contaln essentially any proportions
of support and catalytically active material. The limits of
this relationship are only set by the relative abillty of
the catalyst and support material to accommodate each other.
Preferred catalysts contain about 10 to about 100 percent by
wei~ht o~ catalytically active material based on the weight
of the support.
The preparation of these coated catalysts can be
accomplished by various techniques. The baslc method of
preparing these catalysts is by partially wetting the
support material with a liquid and then contacting the
support material w~ith a powder of the catalytically active
material and gently agitating the mixture until the catalyst
is formed. The gentle agltation is most conveniently
accomplished by placing the partially wet support in a
rotating drum or ~ar and adding the powdered active catalytic
material.
Using the catalysts of the invention in the
preparation of methacrylic acid or acrylic acid, excellent
yields are obtained in a convenient reactlon with low
amounts of byproducts.
s~r~ I~OD~ S
Compara ive Exam~les A to D and Examples_l to 80:
Comparison of catalysts containing promoters of invention
with base catlyst in the preparation of methacrylic acid.
A 20 cc. fixed-bed reactor was constructed of a
1.3 cm. stainless steel tubing. Catalysts prepared as
described below were charged to the reactor and heated to
the reaction temperature under a flow of air and a feed of
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(4959)
methacrolein/air/nitrogen/steam of 1/5.7/4.6/8.7 w~s ~ed
over the catalyst at an a~parent contact time of 2 to 4
seconds. The reactor was run under the reaction conditions
for 1 to 6 hours and the product was collected and analyzed.
Comparative Example A
5% l2PlAso.sox + 75% Alundum
A solution was prepared consisting o~ 211.88 grams
of ammonium heptamolybdate, (NH4)6Mo7024.4H20, (1.2 mole
Mo), 500 mls. distilled water at 60C and 7.94 grams of
ammonium arsenate NH4H2AsO4, (0.05 mole As) as solution in
25 mls. distilled water. A white precipitate formed which
was heate~ to about 100C for two hours. To this mixture
was added 11.53 grams of 85% solution phosphoric acid (0.10
mole P). One-half hour later 5.0 grams of hydrazine hydra-te
was added. The slurry was evaporated to a thick paste,
dried overnight in an oven at 110 to 120C, and ground and
screened to less than 80 mesh. This powder was coated on
Norton 1/8" SA 5223 Alundum balls by taking 50 grams of
Alundum, partially wetting the Alundum wlth 1.8 grams of
water and adding 16.7 grams of active catalyst prepared
above in five equal portions. During and after each addition,
the Alundum was rolled in a glass ~ar. The powder was
evenly coated onto the surface of the Alundum and the flnal
product was dried. A hard unl~orm material was obtained
that consisted of an inner core of the Alundum support with
the continuous, strongly adhering coat of the powder on the
outside surface of the support. The material was then
calcined ~or 1 hour at 370C in 40 ml/min. air to form the
active catalyst.
(4957)
~ (4959)
Examples 1 to 9
Various c~talysts within formula I were prepared
as follows:
25% (Rare earth mlx~ure)o.25Mol2plAso-5ox 75% Al
. . .. . _ . .
A solution was prepared consisting of 105.9 grams
of ammonium heptamolybdate, (NH4)6Mo7O24.4H2O~ (0-6 mole
Mo), 700 mls. o~ distilled water at 60C and 4.~ grams of
ammonium arsenate NH4H2As04, (O~025 mole As) as solution in
25 mls. of water. A white precipitate formed which was
heated at 100C about one-half hour. To this mixture was
added 4.4 grams of Moly Corp. rare earth chloride mlxture
(Product Code No. 4700) consisting of 48% CeO2, 33% La2O3,
13% Nd2O3, 4.5% Pr6Ol and 1.5% other rare earth elements
calculated as oxides. ~o this solution was added 5.8 grams
of 85% solution phosphoric acid, H3PO4 (0.05 mole P). One-
half hour later 2.5 grams of hydrazine hydrate were added.
The slurry was evaporated to a thick paste, dried overnight
in an oven at 110 to 120C, and ground and screened to less
than 80 mesh size. The catalyst was then coated to a 25%
active level on 1/8't SA 5223 Alundum balls. Calci~ation was
the same as in Comparative Example A.
Examples 2 to 7
Preparation of the Catalysts
5% XaybMol2plAso~sGx + 75% Alundum
Various catalysts of the invention were prepared.
The catalysts were prepared according to the procedure of
~10~
(4957)
( 4958 )
a~ ( 4 9 5 9 )
Example 1, using 105. 9 grams of ammon~um molybdate, 700 mls.
of 60C. distilled water and 4 . O grams of ammonium arsenate
in so~ution o~ 25 mls. of water. The catalytic components
~delineated by X and/or Y were added immediately preceding
the addition o~ 5.8 grams of 85% phosphoric acid and 2.5
grams of hydrazlne hydrate. To prepare the catalystsg the
........
following compounds and amounts were used:
Example Element Compound Amount ? g.
2 CeO.25 cerium acetate 4.31
- 3 CeO 1 cerium acetate 1.72
4 ErO.25 erblum acetate 5.21
Rare Rare earth chloride 1.77
earth mixture (Moly Corp.
mixtu~el No. 4700)
' CU0.25 copper ~cetate 2.48
6 Rare Rare earth chloride 4.43
earth mixture
mixture
0.25
T10.05 thallium acetate o.66
7 CeO.15 cerium acetate 2.59
Ago.l silver acetate o.85
E_ample 8
25% Rare earth miXtUreO 25cuo~o5Mol2plAso.5ox 75
__ _ __
This catalyst was prepared ln the same manner
described in Example 1~ except 34.25 grams of ammonium
heptamolybdate, 1.28 grams of ammonium arsenate~ 1.43 grams
of rare earth chloride mixture, 0.161 grams of copper acetate,
1.88 grams of 85% phosphoric acid and 0.8 grams of hydrazine
hydrate were employed.
(~1957)
(4958)
~ ~ ~ 9 25 ~ (4959)
F,xample 9
25% Rare earth mixtureO 25Ago.lMl2PlAS0.50x + 75~ Al
_
This catalyst was prepared in the same manner
described in Example 8, except that 0.269 grams of silver
acetate were employed.
Comparative Examples B, C, and Examples lO to 20
The results of the experiments using catalysts
within formula I in the oxidation of methacrolein to produce
methacrylic acid are shown in TABLE I. The following
definitions are used in measuring the carbon atoms in the
feed and the products.
Moles of Methacrylic Acid Recovered lO0
% Single Pass Yield Moles of Methacrolein in the Feed x
Moles of Methacrolein Reacted
Total ~onversion Moles of Methacrolein in the ~eed x lO0
Sin~le Pass Yield
SelectiVitY = To-tal COnversion x lO0
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- 14 -
(49~7)
(4958)
~ (4959)
Examples 21 to 43
Various catalysts wlthin formula II were pre-
pared as follows:
Example 21
5%Uo.25Mol2plAso.sox + 75% Alundum
A solution was prepared consisting o~ 105.9 grams
of ammonium heptamolybdate, (NH4)6Mo7024.4H20, (o.6 mole
Mo), 700 mls. of distilled water at 60C and 4.0 grams of
ammonium arsenate, NH4H2AsO4, (O.025 mole As) as solution in
25 mls. of water. A white precipitate formed which was
heated at 100C about one-half hour. To this mixture was
added 5.3 grams of uranyl acetate (0.0125 mole U)~ followed
by the addition of 5.8 grams of 85% solution phosphoric ac~d
(0.05 mole P). One-half hour later 2O5 grams of hydrazine
hydrate were added. The slurry was evaporated to a thick
paste, dried overnight in an oven at 110 to 120C, and
ground and screened to less than 80 mesh size. The catalyst
was then coated to 25% active level on 1/8t' SA 5223 Alundum
balls. Calcination was the same as in Comparative Example A.
Example 22
5~ Tio.2Mo12PlAso.sox ~ 75% Alundum
This catalyst was prepared in the same manner
described in Example 21, except 7.72 grams of 20% titanium
trichloride solution were employed and hydrazine hydrate
was deleted in the catalyst preparation.
-15-
(4957)
(4958)
(4959)
Example 23
25~ (Rare earth miX~ure)O 2T1o.lM12PlAs0.50x + 75%
-
This catalyst was prepared in the same manner
described in Examplq 2l~except 3.54 grams of rare earth
chlorlde mixture, 0.5 grams o~ hydrazine hydrate were employed
and 3.85 grams of 20% titanium trichloride solution were
added.
, ,
Examples, ?4 to 39
Preparation of the Catalysts 25% XaYbMol2PlAsO.50x 75~
Various catalysts of the invention were prepared.
The catalysts were prepared according to ~he procedure OI'
Example 21, using 105.9 grams of ammonium molybdate~ 700 mls.
of 60C distilled water and 4.0 grams of ammonium arsenate
in solution of' 25 mls. of water. The catalytic components
delineated by X and/or Y were added immediately preced1ng
the addition of 5.8 grams of 85% solution phosphoric acid.
2.5 grams o~ hydrazine hydrate were added in all prepara~ions,
e~cept no hydrazine was added in Examples 2-~, 30, 32 and 3~;
1.0 gram of hydrazine was added in Example 14. To prepare
the catalysts, the following compounds and amounts were
used:
Example Element Com~ound Amount a ~.
24 NbO.25 niobium chloride 3.37
PbO.25 lead acetate 4.75
26 ZnO.25 zinc acetate 2.75
27 ReQ.25 rhenium sesquioxide 3.03
2 8 AgO.l~iO.2 20% titanium trichloride 7.72
silver acetate o.8
29 Ago lZnO 2 zinc acetate 2.19
' silver acetate o.8
-16
(4957)
(4958)
~ (4959)
Example Element Compound ~ E~
,
Nb Tl 2 niobium chloride O.67
0.05 . 20% titanium trichloride
solution 7.72
31 ReO 1CuO 25 rhenium sesquioxide 1.21
copper acetate 2.48
32 Ti znO 20% titanium chloride 5.78
0.15 .l zinc acetate l.l
33 ZnO 1 zinc acetate 1~09
(rare earth rare earth chloride mixture 3.54
mixture)~ 2 (Moly Corp. Product No.4700)
34 Tio o5CU0.05 20% titanium chloride 1.92
(rare earth copper acetate 3.54
mixture)O 2 rare earth chloride mixture
Zno.05CU0.05 zinc acetate 0.55
(rare earth copper acetate 0.50
mixture)O 2 rare earth chloride mixture 3.54
: 36 GaO.25 gallium oxide l.l
7 ~0 2A~o 05CuO 05 zinc acetate 2.19
aluminum chloride o.6
: copper acetate 0.50
38 Tio 2Rare earthO 05 20% titanium chloride 7.7
Cu Moly Corp. rare earth
5 mixture (4700) 0.90
copper acetate 0.50
39 Rare earth Pb lead acetate 3.8
0-1 0-2 rare earth mixture 1.77
Exam~le 4
5% l2PlAso.5Nbo.25Ago 05x + 75~o Alundum
This catalyst was prepared in the same manner
described in Example 21~except that 34.25 grams of ammonium
molybdate, 150 mls. water, 1.28 grams o~ ammonium arsenate,
: 0.537 grams niobium chloride, 0.134 grams of silver acetate,
1~86 grams of 85% phosphoric acid~ and 0.8 grams of ~ydrazine
hydrate were employed.
(4957)
~ Q ~ (4958)
Example 41
5% 12PlASo sNbo 2sCuO l~x + 75% Alundum
This catalyst was prepared in the same manner
as described in Example 24, except 0.322 ~rams of copper
acetate were added in addition to the niobium chloride.
Example 42
5% nO.2AlO.08CU0.05~l2P1 32Aso 5x ~ 75% Alundum
This catalyst was prepared in the same manner
described in Example 37, except that o.96 grams of aluminum
chloride hydrate and 7.6 grams of 85~ phosphoric acid were
employed.
Example 43
25~ ReO.lA10.091~U0~05Ml?Pl.32ASO 5~x ~ 75% Alundum
This catalyst was prepared in the same manner
described in Example 42, except that 1.1 grams of aluminum
chloride hydrate and 1.21 grams of Re207 were employed.
Comparative Examples B to D and Examples 44 to 67
The results of the experiments using catalysts
within formula II in the oxidation of methacrolein to
produce methacrylic acid are shown in TABLE II below. The
same definitions described above are used in measuring
the carbon atoms in the feed and the products.
In the same manner described above, catalysts
of the invention may be efrectively utilized in the prep-
aration of acrylic acid from acrolein.
-18-
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e u~In u~ u). u~ u~.,, u~ ~
X
- 20 -
;~
~ o~ u~ ~ ~ 0~ OD
u~
o ~ o ~ ~
C~ ~ _I o~ cr, cJ~ o ~
~ oo o~
E~
c ~ ~
~ ~ to
~ ~ ~ ~J ~r ~ U~ ~ ~ ~ `J
o ~l ¢
~ u
oo o ~J
~ ~ ,~ co ~ a~ ~ O
~ c) ~;
~ ~d ~ r~ O t~
e ~ u e
e
~ tO ~ U~
~ ~ ~ OX o ,~
i~ "~ ¢ oE X O
r~ 1 C ~ ~ :4
~ ~ ~0~ ~
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O~J 1~ ~ O o
o ~ ¢~ C,,~ ''~ ¢
a~ ~ ~ u~
O E X . O O ~:
~ P. ~ . ~:1 o o o
!~ E3 O o ~ ~ u~ ~ ~ ~ E O _I o
~ C~ ~u~ ¢ ~ L'`~
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?` O O O ~ 0 ~1 ~1 0 r~ O O
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P~ t~ C~ U'l oC ~ + ~
~ ~ ~ ~ ~ I~ ~ æ ~ ~ O
u~ Le~ + u~ ~ ~ 0~ ~ ¢
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(4g57)
~ (495g)
Examples 68 to 73
Various catalysts within formula III were prepared as follows:
Example 68
5% Ago.25Mo12PlAso~sox ~ 75% Alundum
A solution was prepared consisting of 105.9 grams
of ammonium heptamolybdate, (NH4)6Mo7O24.4H2O, (o.6 mole
Mo), 700 mls. of distilled water at 60C and 4.0 grams o~
ammonium arsenate, NH4H2AsO4, (0.025 mole As), as solution
in 25 mls. of water. A white precipitate formed which was
heated at 100C about one-half hour. To this mixture was
added 2.08 grams of silver acetate (0.0125 mole Ag), followed
by the addition of 5.8 grams of 85% solution phosphoric acid
(0.05 mole P). One-half hour later 2.5 grams of hydrazine
hydrate were added. The slurry was evaporated to a thick
paste, dried overnight in an oven at 110 to 120C, and
ground and screened to less than 80 mesh size. The catalyst
was then coated to 25% actlve level on 1/8" SA 5223 Alundum
balls. Calcination was the same as in Comparative Example A.
Example 69
0.05cdo.2Mol2Pl.o~so~5ox + 75~ Alundum
Thls catalyst was prepared in the same manner
described in Example 68, except that 150 mls. of water,
34.25 grams of ammonium molybdate, 1.28 grams of ammonium
arsenate, 0.862 grams of cadmium acetate, 0.318 grams of
gold chloride, 1.86 grams of 85~ phosphoric acid and o.8
grams of hydrazine hydrate were employed.
Example 70
5% RUo.2Mol2PlA~so.5~x ~ 75~ Alundum
This catalyst was prepared in the same manner
described in Example 68~ except that 500 mls. of water,
5 ~ (4958)
(4959)
70.6 grams of ammon~um molyhdate~ 2~64 grams of ammonium
arsenate, 1.74 grams of ruthenium chloride, RuC13 3H2O,
(0.006 mole Ru~, 3.84 grams of phosphoric acid, and 1.6
grams of hydrazine hydrate were employed.
Exam~es 71 to 73
Preparation of the Catalysts 25% XaYbMol2PlAsO.5Ox 75%
. . _ ,, . _ . _ . . , _ _ .
Various catalysts of the invention were prepared.
The catalysts were prepared according to the procedure of
Example 68, using 105.9 grams of ammonium molybdate, 700
mls. of 60C distilled water and 4.0 grams of ammonium
arsenate in solution of 25 mls. of water. The catalytic
components delineated by X and/or Y were added immediately
preceding the addition o~ 5.& ~rams o~ 85~ solution phos-
phoric acid, and 2.5 grams of hydrazine hydrate. To prepare
the catalysts, the following compounds and amounts were
used:
Exam~Ie Element Compound Amount~ ~.
. .
71 Ago.l silver acetate o.8
72 RhO.25 rhodium acetate 2.15
73 Auo 25 gold chloride 4.92
Comparati_e Examples B to_D and Examples 74 to 80
The results of the experiments using catalysts
within formula III in the oxidation of methacrolein to
produce methacrylic acid are shown in TABLE III. The same
definitions described above are used in measuring the
carbon atoms in the f'eed and the products.
In the same manner described above, catalysts of
the invention may be effectively utilized in the preparation
of acrylic acid from acroleln.
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