CATALYST WITH MO, V, TI AND PROCESS FOR PREPARING UNSATURATED ACIDS

CATALYSEUR AU MO, V ET TI, ET PROCEDE POUR LA PREPARATION D'ACIDES INSATURES

English Abstract

ABSTRACT OF THE DISCLOSURE
A novol catalyst comprising the elements
Mo, V and Ti, and an oxidation process, is provided
for oxidizing alpha beta unsaturated aliphatic
aldehydes in the vapor phase with molecular oxygen
to produce the corresponding alpha-beta unsaturated
carboxylic acid.
1.

Claims

WHAT IS CLAIMED IS:
1. A process for the production of unsaturated
aliphatic carboxylic acid by vapor phase catalytic
oxidation of the corresponding unsaturated alphatic
aldehyde with molecular oxygen in the presence of steam
said aldehyde having the structure
<IMG>
wherein R1 is H or a C1 to C6 alkyl radical and R2 and R3
are the same or different and are H or CH3
which comprises contacting the reaction mixture
with a calcined oxidation catalyst which is devoid, for
said catalytic oxidation purposes, of catalytically active
forms of W, Sb and Al and which contains the elements Mo,
V, Ti, and X in the ratio
Moa Vb Tic Xd
wherein X is selected from the group consisting
of Fe, Cu, Co, Cr, and/or Mn
a is 12,
b is 1 to 14,
c is 0.1 to 12, and
d is 0 to 3Ø
2. A process as in claim 1 in which said
unsaturated alphatic acid is acrylic acid and said
unsaturated alphatic aldehy?e is acrolein.
33.

3. A process as in claim 2 in which said
oxidation catalyst is supported on an inert support.
4. A process as in claim 3 in which said
support is silica, alumina or silica-alumina.
5. A process as in claim 3 in which a is 12,
b is 2 to 8, c is 1 to 2 and d is 0.01 to 1Ø
6. A process as in claim 5 in which X
comprises Fe.
7. A process as in claim 5 in which X
comprises Cu.
8. A process as in claim 5 in which X
comprises Co.
9. A process as in claim 5 in which X
comprises Cr.
10. A process as in claim 5 in which X
comprises Mn.
11. A calcined oxidation catalyst which is devoid
of catalytically active forms of W, Sb and Al and which
contains the elements Mo, V, Ti and X in the ratio
Moa Vb Tic Xd
wherein X is selected from the group consisting
of Fe, Cu, Co, Cr, and/or Mn
34.

a is 12,
b is 1 to 14,
c is 0.1 to 12, and
d is 0 to 3Ø
12. A catalyst as in claim 11 which is
supported on an inert support.
13. A catalyst as in claim 12 in which said
support is silica, alumina, or silica-alumina.
14. A catalyst as in claim 11 in which a
is 12, b is 2 to 8, c is 1 to 2 and d is 0.01 to 1Ø
15. A catalyst as in claim 12 in which X
comprises Fe.
16. A catalyst as in claim 12 in which X
comprises Cu.
17. A catalyst as in claim 12 in which X
comprises Co.
18. A catalyst as in claim 12 in which X
comprises Cr.
19. A catalyst as in claim 12 in which X
comprises Mn.
35.

20. A process for preparing a catalyst com-
position which is devoid of catalytically active forms of
W, Sb and Al and which contains the elements Mo, V, Ti
and X in the ratio.
Moa Vb Tic Xd
wherein X is selected from the group consisting
of Fe, Cu, Cr, Co and Mn and
a is 12,
b is 1 to 14,
c is 0.1 to 12, and
d is 0 to 3.0
which comprises dissolving water soluble compounds of each
of the elements Mo, V, Ti and X in an aqueous solution
thereof having a pH of 1 to 12, said compounds being used
in such quantities as to provide the desired a:b:c:d ratios,
removing the water from said solution, and
heating the resulting mixture of said compounds
in air or oxygen for 2 to 24 hours at 250 and 450°C.
21. A process for the production of unsaturated
aliphatic carboxylic acid by vapor phase catalytic oxidation
of the corresponding unsaturated aliphatic aldehyde with
molecular oxygen in the presence of steam
said aldehyde having the structure
<IMG>
36.

wherein R1 is H or a C1 to C6 alkyl radical and R2 and R3
are the same or different and are H or CH3
which comprises contacting the reaction mixture
with a calcined oxidation catalyst which is devoid, for said
catalytic oxidation purposes, of catalytically active forms
of W and Al and which contains the elements Mo, V, Ti and
X is in the ratio
Moa Vb and Tic Xd
wherein X is selected from the group consisting
of Fe, Cu, Co, Cr, and/or Mn
a is 12,
b is 2 to 8,
c is 0.5 to 2, and
d is 0.1 to 1Ø
22. A process as in claim 21 in which said
unsaturated aliphatic acid is acrylic acid and said
unsaturated aliphatic aldehyde is acrolein.
23. A process as in claim 22 in which said
oxidation catalyst is supported on an inert support.
24. A process as in claim 23 in which said
support is silica, alumina or silica-alumina.
25. A process as in claim 21 in which X
comprises Fe.
37.

26. A process as in claim 21 in which X
comprises Cu.
27. A process as in claim 21 in which X
comprises Co.
28. A process as in claim 21 in which X
comprises Cr.
29. A process as in claim 21 in which X
comprises Mn.
30. A process for the production of unsaturated
aliphatic carboxylic acid by vapor phase catalytic
oxidation of the corresponding unsaturated aliphatic
aldehyde with molecular oxygen in the presence of steam
said aldehyde having the structure
<IMG>
wherein R1 is H or C1 to C6 alkyl radical and R2 and R3
are the same or different and are H or CH3
which comprises contacting the reaction mixture
with a calcined oxidation catalyst containing the elements
Mo, V, Ti, and X in the ration
Moa Vb Tic Xd
wherein X is selected from the group consisting
of Fe, Cr and/or Mn
a is 12,
38.

b is 2 to 8,
c is 0.5 to 2, and
d is 0.1 to 1Ø
31. A process as in claim 30 in which said
unsaturated aliphatic acid is acrylic acid and said
unsaturated aliphatic is aldehyde is acrolein.
32. A process as in claim 31 in which said
oxidation catalyst is supported on an inert support.
33. A process as in claim 32 in which said
support is silica, alumina or silica-alumina.
34. A process as in claim 30 in which X
comprises Fe.
35. A process as in claim 30 in which X
comprises Cr.
36. A process as in claim 30 in which X
comprises Mn.
37. A process for the production of unsaturated
aliphatic carboxylic acid by vapor phase catalytic
oxidation of the corresponding unsaturated aliphatic
aldehyde with molecular oxygen in the presence of steam
said aldehyde having the structure
<IMG>
39.

wherein R1 is H or a C1 to C6 alkyl radical and R2 and R3
are the same or different and are H or CH3
which comprises contacting the reaction mixture
with a calcined oxidation catalyst consisting essentially
of the elements Mo, V, Ti, and X in the ratio
Moa Vb Tic Xd
wherein X is selected from the group consisting
of Fe, Cu, Co, Cr, and/or Mn
a is 12,
b is 1 to 14,
c is 0.1 to 12, and
d is 0 to 3Ø
38. A process as in claim 37 in which said
unsaturated aliphatic acid is acrylic acid and said
unsaturated aliphatic aldehyde is acrolein.
39. A process as in claim 38 in which said
oxidation catalyst is supported on an inert support.
40. A process as in claim 39 in which said
support is silica, alumina or silica-alumina.
41. A process as in claim 37 in which a is 12,
b is 2 to 8, c is 0.5 to 2 and d is 0.01 to 1Ø
42. A process as in claim 41 in which X
comprises Fe.
40.

43. A process as in claim 41 in which X
comprises Cu.
44. A process as in claim 41 in which X
comprises Co.
45. A process as in claim 41 in which X
comprises Cr.
46. A process as in claim 41 in which X
comprises Mn.
47. A process for the production of an
unsaturated aliphatic carboxylic acid by the vapor phase
catalytic oxidation with molecular oxygen of the correspond-
ing unsaturated aliphatic aldehyde having the structure:
<IMG>
wherein R1 is hydrogen or a C1 to C6 alkyl radical and R2
and R3 are the same or different and are H or CH3, which
comprises contacting said molecular oxygen and unsaturated
aldehyde in the presence of steam with an oxidation
catalyst consisting essentially of the elements Mo, V, Ti,
Fe and Y in combination with oxygen and having the
empirical formula:
Moa Vb Tic Fed Ye
wherein Y is selected from the group consisting
of Co, Cr, and/or Mn,
41.

a is 12
b is 1 to 14
C is 0. 1 to 12
d is a number greater than 0 and up to 3
e is 0 to 3 with the proviso that d+e is 3 or less;
said catalyst having been prepared by drying an aqueous
slurry or solution of salts of said elements followed by
calcination.
48. A process as is claim 47 in which said
unsaturated aliphatic acid is acrylic acid and said
unsaturated aliphatic aldehyde is acrolein.
49. A process as in claim 48 in which said
oxidation catalyst is supported on an inert support.
50. A process as in claim 49 in which said
support is silica, alumina or silica-alumina.
51. A process as in claim 49 in which a is 12,
b is 2 to 8, c is 0.5 to 2, d is 0.01 to 1.0 and e is 0 to
3 with the proviso that d+e is 3 or less.
52. A process as in claim 47 in which Y
comprises Co.
53. A process as in claim 48 in which Y
comprises Cr.
42.

54. A process as in claim 47 in which Y
comprises Mn.
55. An oxidation catalyst consisting essentially
of the elements Mo, V, Ti, Fe and Y in combination with
oxygen and having the empirical formula:
Moa Vb Tic Fed Ye
wherein Y is selected from the group consisting
of Co, Cr, and/or Mn,
a is 12
b is 1 to 14
c is 0. 1 to 12
d is a number greater than 0 and up to 3
e is 0 to 3 with the proviso that d+e is 3 or less;
said catalyst having been prepared by drying an aqueous slurry
or solution of salts of said elements followed by calcination.
56. An oxidation catalyst as in claim 55 which
is supported on an inert support.
57. An oxidation catalyst as in claim 56 in which
said support is silica, alumina or silica-alumina.
58. An oxidation catalyst as in claim 55 in which
a is 12, b is 2 to 8, c is 0.5 to 2, d is 0.01 to 1.0, and
e is 0 to 3 with the proviso that d+e is 3 or less.
59. An oxidation catalyst as in claim 55 in
which Y comprises Co.
43.

60. An oxidation catalyst as in claim 55 in which
Y comprises Cr.
61. An oxidation catalyst as in claim 55 in
which Y comprises Mn.
62. A process for preparing a catalyst consisting
essentially of the elements Mo, V, Ti, Fe and Y in
combination with oxygen and having the empirical formula:
Moa Vb Tic Fed Ye
wherein Y is selected from the group consisting
of Co, Cr, and/or Mn,
a is 12
b is 1 to 14
c is 0.1 to 12
d is a number greater than 0 and up to 3
e is 0 to 3 with the proviso that d+e is 3 or less;
which comprises drying an aqueous slurry or solution
of salts of said elements followed by calcination.
63. A process as in claim 62 in which said
oxidation catalyst is deposited on an inert support
prior to said calcination.
64. A process as in claim 63 in which said
support silica, alumina or silica-alumina.
65. A process as in claim 62 in which a is 12,
b is 2 to 8, c is 0.5 to 2, d is 0.01 to 1.0 and e is 0 to 3
with the proviso that d+e is 3 or less.
44.

66. A process as in claim 62 in which Y
comprises Co.
67. A process as in claim 62 in which Y
comprises Cr.
68. A process as in claim 62 in which Y
comprises Mn.
69. A process for the preparation of an un-
saturated aliphatic carboxylic acid by vapor phase catalytic
oxidation of the corresponding unsaturated aldehyde having
the structure
<IMG>
wherein R1 is H or a C1 to C6 alkyl radical and R2 and R3
are the same or different and are H or CH3, with molecular
oxygen in the presence of steam and a solid catalyst at a
temperature between about 200 to 400°C. with a contact time
of about 0.1 to 10 seconds, wherein said catalyst consists
essentially of the elements Mo, V, Ti and Cr in combination
with oxygen and having the empirical formula:
Mo12 Vb Tic Crd
wherein
b is 1 to 14
c is 0.1 to 12
d is 0 to 3.
45.

Description

9~62
10451~
BACKGROUND OF THE INVENTIOM
FIELD OF THE INVENTI~N
The invention relates to the vapor phase
catalytic oxida~ion of unsa~urated alipha~ic alde-
hydes to the corresp~nd~ng unsaturated aliphatic
carboxylic acid.
DESCRIPTION OF THE PRIOR ART
The use of molybdenum and vanadium containing ~-
catalyst sy~tem~ or the gas phase oxidation of ~
alpha-beta unsaturated aliphatic aldehydes, such as ; ~ .
acrol~in, to ~he corresponding alpha beta-unsaturated
.: ' '
carbo~ylic acids, such as acxylic acid9 has been known. : .
In these reactions a gaseou~ reac~ion mixture :
~ . . ..
which us~ally conta~ns the aldehyde, molecular oxygen
. and water, as steam, i6 brought into contnct with the
.
catalyst, by continuously passing a ~tream ~f the ~
rea tion mixture through a bed of the catalyst. Such
kn~v~n catalyst systems ;woald include those disclosed
in :the follow~ng U~ited~States patents: 3,087,964; ~ ::
,
: :20 . 3,35~,020 j~ 3,408,392; 3,~35,069; 39439,028, 3,S30,175;
33567,772; 3,567,773; 3,574,729; 3,644,509; 3~655?749;
~; 3~670aO17 and 39703:9548. ~ Not all of the~2 catalys~
ystem~, :however" are currently useful ~o~ commercial ;
;~ purpo~es. Some of these catalyst ~ystem ~ for ~exampl~
::do no~ prov~de the relatively high 1~7el8 o:l~ % c:on-:
version, ~ productivity and % selectiv~ty, which are all
2~
.

~0~5~06
9462
required, presiently, of a commercially useful catalyst
system. :
The terms % conversion, productivity, and %
selectivity which are employecl herein with re~pect to ; .
the present invention are defi.ned as follows:
% conversion = 100 X
moles of aldehyde in the re~
action mixture which i8 fed
to the catalyst bed per hour
of reaction time -
Ia wherein A ~ the molar aldehyde-equivalent sum
(carbon ba~is) of all c~rbon-containing
products, excluding the aldehyde in the
effluent, which are produced per hour
of re~ction time ~ .
II productivity - pounds of alpha~beta un~aturated
aliphatic carboxylic acid product
produced per cubic foot o cataly~t
(in the catalyst bed) per hour of . .
() ~ . reaction time
: moles o alpha-beta-un~aturated
aliphatic carboxylic acid pro~
/0 selectivity ~ 100 X~
whereln A is as defined above ln equation Ia.~ . .
.
~: ~ : , ..
A lpha-beta-unsaturated aliphatie carboxylic
aclds are produced with a relatively high % convérsion, : . -
produot~i~y and ~% selec ivi~y by oxidizing the corres- .
~ponding alpha-beta-unsaturated aldehyde in the vapor.
pha#e by con~tacting the aldehyde, in ~ha ~presenciie~o~
molecular oxygen and steam, with certaln catalyst
:: :
.
:
: ~ :
3 :,
~, ~
.. . . . .. ~.. .. . . . .. . . ., ,.. "., ,. .,....... .,, . : . . .

g462
~ 0~Slq:)6
compositions containing molybdenum, vanadium and
titanium. ::~
An object of the present invention is to
provide novel catalyst compositions for the vapor
phase oxidatlon of alpha~be~a-unsaturated aliphat-lc
aldehydes to the corresponding alpha~beta-unsaturated
aliphatic carboxylic acid.
A further object of the pre~ent in~en~ion ~ :
is to provide a process whereby alpha-beta-unsaturated
aliphatic aldehydes can be oxidized in the gas phase ~ ;
so to produce the co~responding alpha~be~a unsaturated
aliphatic carboxylic acid with a relat~vely high level :
of % conversion, productivity and % s~lectivity.
These and other ob~ects of the present ..
in~ention are a¢hieved by using as such a catalys~
in Quch a process a compo8ition comprising~thc elements
Mo, V, Ti and X in the rati~ .
a Vb~Tic Xd : - :
: wherein X is Fe~ Cu, Coj Cr, andlor M~
~ : a is 12,
b i~ I to 14~ and pre~erably 2 ~o 8,
c is 0.1 to 12, and preferably 0.5 to 2, and
d is 0 ~o 3.0, ~nd preferably O.Ol~to 1Ø
. . . .
The numerical values of a, b, c and d -.
:
represent ~he relative atom-mole ratios of ~he
- , . ': ' .

10~5~(J6
9462
e1ements Mo, V, Ti~ and X, respectively~ which are present
in the catalyst composition.
THE C TALYST
The elements Mo, V, Ti, and X are present ~n
the catalyst composition in combinatlon with oxygen in the
form; it is believed, of various metal oxid~s.
The catalyst is preferably prepared from a
solution of so1ub1e sa1ts and/or comp12xe~ and/or com- -
pounds of each of the metals Mo, V, T1 and X. The solu-
tion is preferably an aqueous system having a pH of 1-12,
and praferably 5 + 3, at a temperature of about 20 to ~ :
100C. Th2 solut~on of t4e metal containing compounds
is prepared by dissolving ~ufficient qu~ntities of soluble
compounds of each of the metals? BO as to provide:thé
desired a:b:c:d atom-mo1c ratios o ~he elem~nts Mo, V,
: Ti and X, respectively. The se1ected s~lts,~complexes
or compound6 of the meta1s Mo, V and Ti should be
mutually~soluble. If the se1ected salts, complexe8 or
compounds of the meta1 X are not mutually soluble with :~
20 : the other compounds they can be added la~t to the ~olution -~
6yst~em. -The catalyst composition is then prepsred
by removing the water or other solvent from the mixture of
the metal compounds in the solution system. Any portion,
and preferably i.e. about ~ S0 weight %, of the titanium may
: be repl~ced by tantalum and/or niobium in the ca a1yst
compo~ition. . .
5. . .
-

9462
~.~)45~L~6
The water or other solvent can be removed
~rom the mixture o:E the clissolved metal cc,mpounds by
evaporation,
Where the cata:Lyst is to be used on a
support, the metal compounds are depo~ited on a
porous support usually having a surfaoe area of
about 0~01 to 2 square meters per gram. The support
. .
has an apparent porosity of 30-60%; a~ leas~ 90% of
- the pores have a pore diameter in the range o~
20-1300 microns, The support is usually used in
the form o~ particles or pellets which are abou~
1/8 ~o 5/16 inch in diameter. The deposi~ion is
accomplished by immersing the support in the solu
, :
tion and then evaporating off the m~jor portion o~ ; .
;: . .....
~he solverlt~ and then dry~ng the system at about 80
to 140C. for 2 to 60 hours. The dried c~talyse is
then calc~ned by being heated at 250 to 450C., and
.. .
pref0rably 325-425C~ Eor 2 to 2~ hours in air ~o :;
: :
; produce the desired :;
: : 20 ~ Ma Vb Tic Xd
compo~iition.
When used on the support, the suppor~ed
oxides usually compriise about 10 to 50 weight %
o~ the total catalyst composition; of the total
, ~ . ~ .. .
. .
catalyst composition about 50 to 90 waight % is .
support .
' .
~ : : : 6~
: :.
, .
: . .

g462
lO~SlQ6 ~ ~
The molybdenum is preferably introduced
into solution in the form of ammoni~m salts thereof
such as ammonium paramoly~date, and organic acid salts
of mol~denum such as acet:ates, oxalates, mandelates
and glycolates. Other wat:er soluble molybdenum com-
pounds which may be used alre partially water soluble
molybdenum oxides, molybdic acid, and the nitrate~
and chlorides of molybdenum.
The vanadium is~preferably in~roduced l~o
solution in the form o~ ammonium sal ~ thereof such
as ammonium meta-vanadate and ammonium de~avanadate~
~nd organic acid salts of vanadium such as ace~atee,
oxalates and tartrates. ~Other water soluble van~dium
compounds which may be u9ed are par~ially water
soluble vanadium oxides, and the sul~ates and nitrates ~-
of vanadium~
: : The titanium is preferably i~troduced ~nto
solution in the form o~ a water soluble chelate~
: ¢oordfnated with ammonium lactate. Other ~oIuble
20~ titanium compound~ which may be used ars those in :
which titan~um i~ coordinated9 bonded, or c~mplexed
: ~ to a beta-diketonate, a carboxylic ac~id, n amin~,
~ an alcohol o~ an:alkanolamine.
. . . . .
, .
Where tantalum and/o~ niobi~m ar~ u5ed for
a portiorl of~the~tikanlum~ they are pr~ferab~y~ intro
duced:into solution in ~he ~orm o~ oxalate~, Other .
~ .
: 7.
' :
:~ ' : ' ,
:
. :.
:, ~ , , . . . . .: .

~04S10~ 9462
sources of soluble tantalum and niobium which may be used
are tantalum and nioblum compounds in which the t~ntalum
or niobium is coordinated, bonded~ or complexed to a beta-
diketonate, a carboxylic acid, an amine, an alcohol or an
alkanolamine.
The iron, copper, cobalt, chromium and manganese
are preferably introduced into solution in the form o~
nitrate~. Other water soluble compounds of theee ~lement~ .
which may be used are the water soluble chlorides ~nd ~ ~.
organic ~cid salts such as the acetates, oxalates, tartrates,
lac~ates, salicylates, formates and carbonates of such metals,
It is believed that, for the catalyst~ to be most
effective, the Mo, V, Ti, X metal components should be
reduced below their highest possible oxidation ~tates.
This may be aceomplished during the thermal treatment of the
~,. .. . .
catalyst in the presence of reducing agents such as NH3 or
organic reducing agents, such as the organic comple~ing
agents, which are introduced into the solution ~ystems from
which the catalysts are prepared. The catalyst may also be
:reduced in the reactors in which the oxidation reaction is to
be conducted by the passage of hydrocarbon reducing agents
such as propylene through the cata~yst bed.
TNE ALDEHYD~S
~ The alpha-bet~-unsaturated aldehydes which are
oxidizad in the process of the present invention have the
structure :
1 1 13
R2 - C - C - CH
::

wherein R1 is H or a C1 - C6 alkyl radical and
R2 and R3 are the same or different and are H or CH3.
These aldehydes thus include acrolein and meth-
acrolein. Where acroleing and/or methacrolein are oxidized,
the corresponding alpha-beta-unsaturated carboxylic acid
would be acrylic acid and/or methacrylic acid, respectively.
The aldehydes may be oxidized individually or
in combinations thereof.
THE REACTION MIXTURE
The components of the reaction mixtures which are
employed in the process of the present invention, and the
relative ratios of the components in such mixtures, are
the following
1 mole of aldehyde,
0.2 to 5 moles of molecular oxygen (as
pure oxygen or in the form of air),
1 to 25 moles of water (in the form of
steam), and
optionally, 0.1 to 5 moles of alpha-beta-
unsaturated oefin having the same nujmber of carbon
atoms as the aldehyde being oxidized. Propylene, for
example, can be used in the reaction mixture when
acrolein is being oxidized to acrylic acid.
The water, or steam, can be used as a reaction
diluent and as a heat moderator for the reaction. Other
diluents which may be used are inert gases such as nitrogen,
CO2 and gaseous saturated hydrocarbons.
The olefin may be present due to the fact
that the aldehyde feed may be emanating as the
9.

9462
1~ ~5 ~ 6
effluent from an olefin ~ aldehyde oxidation .
reaction process, and such effluent usually contains
unreacted olefin.
The components of the reac~ion mixture are
uniformly admixed prior to being introduced into the ..
reaction zone. The components are preheated, ;~
individually or after being admixed, prior to their
being introduced into the reaction zone, to a
temperature of about 200 to 300C. -
REACTION CONDITIONS
.
The preheated reaction mixture is brought
into contact with the catalyst composition, in the
reaction zone, under the following conditions~
pressure of about 1 to 10, and preferably .
of about 1 to 3 atmospheres, : :
. :
temperature of about 200 to 400C., and :
preferably of about 250 to 350C., ... ;
contact time (reaction mixture on catalyst)
of about 0.1 to 10, and preferably of about .~ .
1 to 3, seconds, and a space ~elocity of . .-
about 1000 to6000h~l, preferably 4000 to ~- .
5000 h-l. . ~
.. . .. . .. .
The contact time may also be defined as the ..
ratio between the apparent volume of the catalyst bed ,~.,.~.. ~
and the volume of the gaseous reaction mixture fed to :- :
the catalyst bed under the given reaction conditions
,,,, 10., ~ '.`.'
,

9462
~1)451Q6
in a unit of tim~.
The reaction pressure ls initially provided
by the feed of gaseous reactants and dil~ents, and
after the xeacti~n is comm~nced, the pressure is
maintained, pre~erably, by the use of suitable back-
pressure controllers placed on the gaseous effluent
side of the catalyst bed.
The reac~ion temperature i8 preferably
pro~ided by placing the catalyst bed within a
tubular converter who6e walls are imm~rs~d in a
suitable hea~ transer medium, sach as tetralin,
molten salt mixtures, or other suitable heat transfer ;-
agent, which i5 heated to the desired reaction t~mperature.~ ~ ~
The following examples are merely :
illuatrative of the present invention and are not
intended as a limitation upon the 8cope thereof.
The examples provided below disclose the
:~ preparation o~ various catalyst compositions, an~
;
: : the~ use of such composi~ions in the oxidation o~ .
- ~ ~ .. . .
~ 20 ~ acrolein to acrylic acid.
:; . ~ . .
~ . The acti~ity o each experimental ca~alyæt : K~ '
,.
was aetermined in a jacketed one-inch stainless
: steel reactor or converter tube 78 inohe6 long~ The
: jacket con~ained tetralin wh~ch served a~ a he~t
,
trans~er:m~dium.
~;
- 11, .
: :
, :

9~62
~ 45~)6
The center portion (55 inches) o the
reactor tube was charged with 800 ml of catalyst .
with a one-eighth inch movable thermocouple in the
catalyst bed,
The catalysts were tested at 30 pslg~ with
a space velocity of 4600 hr~l or contac~ time of 1,2
seconds, and an inlet eed composed of 3 mole % : ~ :
acroleing 6 mole % oxygen, 15 mole % steam, and 76
mole % nitrogen. .
The activity of the catalysts was tested
by adjusting ~he temperature of the reactor tube ~ :
jacket to produce a maximum temperature (hot spot) :
of 304-306C. in the catalyst bed, while the oxida-
tion reaction was occurring~
~ Space veloci~y is ca~culated by de~erminin~
the total reactor outlet: gas equi~alents (in liters)
of the totaI ef~luent evolved over a period of one . ~ -
hour, ~This rnom temperature~ volume is converted to
: : : the volume at 0C a~ 760 mm Hg. ~ - ;
IV Space Velocity = li~ers~of outlet ~as
quivalentslhour ..
ers:o catalyst in r~actor .~ .
. . ..
pressure
~:, : : .. ,:
: , :
~: , : : -
, -
.
~ ,., ~ ': ,, '
, : .;. . . - , , ~, . .. :. ,... . .. . . , .. . - ... . . . . - .

g~62
51(~i
EXAMPLE 1
M2 4V,6Ti,3Fe.15
Seventy grams of ammonium meta-vanadate (0.6
grams atoms of V) and 424 grams of ammon;um para- -
molybdate (2.4 gram atoms of Mo) were dissolved in two
liters of water while stirring at 60-80C. in a `
stainless steel beaker.
To the resulting solution were added 175 ~ -
grams of titanium ammonium lactate (chelate) solution
(containing 0.3 gram atoms Ti) and 60 grams of ferric
nitrate [Fe(NO3)3-9H2O] (0.15 gram atoms Fe) dissolved
in lO0-ml water.
The resulting mixture was heated while
st~rring and approximately 60 per cent of the water
was evaporated off.
The resulting concentrated slurry was trans~
ferred to a stainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumina (No. SA-5218)
1/4" spheres were added. This was followed by drying
by evaporation with stirring on a steam batch. Further
drying was carried out at a temperature of 120C. for
a period of 16 hours.
The dried material was then transferred to
a ~ray fabricated from 10-mesh stainless steel wire
screen and ealcined in a mu~fle furnace for 5 hours at ~ -
.~ . .
13
.,
.. '" '' .
` '' ':
,, , . ` ~ , ' ' ' '
,. . : .:, .
. ... .

9~62
4 5 1 Q 6
... . .
400C. in an ambien~ atmosphere o air. The amount
o~ catalyst deposited on the support calculated from
the weight increase o the ca~alyst obtained is 27,2
weigh~ %. Catal~tic test results for this material
are given in Table I.
EXAMP~E' 2
2,4V,6Ti,3Cu 15
.
Seventy grams of ammonium meta-vanadate -
(0.6 grams atoms o~ V)and 424 grams of ammonium
. . .
paramolybdate (2.4 grams atoms of Mo) were dissolved
in two liters of water while stirring at 60-80C in
.
a stalnless steel beaker.
To the resulting solution were added 175
, ! ' ` ".., ~, . .'", ~ ~.
grams of titanium ammonium lactate (chelate) solution
~contaLning 0.3 gram atoms Ti) and 36 grams of copper
nitrate [Cu(N03)3.3H20~ (0~15 gram atoms Cu) dissolved
in lOO~ml water.
:~.
The resulting mixture was heated while
~ stirring and approximately 60 per cent of the watsr
; 20 was evaporated o~f J , ' '
The resulting concentrated slurry wss
transferred to a stainless s~eel evapora~ing dish
and iO40 gram~ tlO00 ml) Norton silica-alumina
. . .
~No. SA-5218) 1/4" spheres were added. This was
~ol~o~ed by drying by è~aporation with ~tirring on ~-
' ' ;1 '.
14.
`,
- '..................... ..

9~62
10451~i
a steam bath, Fur~her drying was carried out at a
temperature of 120C ~or a period o~ 16 hours.
The dried materia~ was then transferred to
a tray fabricated from 10-mesh sta~nless 8teel wire
screen and calcined in a mu~fle furnace ~or S hours at
400C in an ambient atmosphere o~ airO Th~ amount o
catalys~,deposited on the support calculated from the
weight increase o~ the ca~alyst obtained, is 28.6
weight %. Catalytic test ~esults for thls material
. are given in Table I.
EXAMPLE:3 ~.
M~2 . 4V. 6Ti 3Mn 15 ~ '
Seventy grams o~ ammonium meta vanadate ~ ,,
(0.6 gram atoms of V)and 424 grams:of ammonium para ',
.
: molybdate (2~4 gram atoms of~Mo) were dissolved in ~ ,
: :,
'two:liters of water while s~irring at 60-80C, in a
stainless ~teel beaker, . ~ ~ ;
' To the resulting ~salution was added 175
grams~of titanium ammonium lact~ate (chelate) solu ~
::20 ~:tion ~(contaLning 0,3 gram atoms Ti) and 54 grams of
50.3%~manganese nitrate ,solution (0,15 gram,atom~ Mn) ~,~', ' ,
~ :~dissolv~d~in 100-ml water. ~ ~ ' ',.
: : ~ The resulting mixture wa~ heated whil~ '''
~ ~ .
stirrlng and approxima~ely 60~per cent of the water ' '.
` was evaporat~d o~. ' ~ " ',
:~ : : The resulting concentrate~ slurry~wa~ ,".;: -'
. .
- : 1SJ . : ~:
:..'

9~62
~ 45 ~
trans~erred to a stainless steel evaporating dish and
1040 grams (1000 ml) Norton silica-alumina (No. SA-5218)
1/4" spheres were added. This was followed by drying by
evaporation with stirring on a steam bath. Further dry-
ing was carried out at a temperature of 120C. ~or a
period of 16 hours.
The dried material was then transferred to a
tray fabricated from 10-mesh stainless steel wire screen -
and calcined in a muffle furnace for 5 hours at 400C. in
an ambient atmosphere of air. The amount of catalyst - v
deposited on the support calculated from the weight in-
crease of the ca~alyst obtained is 27.8 weight %.
Catalytic test results or this material are giuen in ~
Table I. ',~'~! , ,
EXAMPLE 4
M2 4V,6Ti, 3Cr, 15
Seventy grams of ammonium meta-vanadate (006
gram atoms of V) and 424 grams of ammonium para- ;
molybdate (2.4 gram atoms of Mo) were dissolved in
two liters of water while stirring at 60-80C. in a
stainless steel beaker~ ~ ;
To the resulting solution were added 175 `
grams of tita~ium ammonium lactate (chelate) solution ~ ;~
(containing 0.~3 gram atoms Ti) and 60 grams of chromium ;~
nitrate [Cr(N03) 9H20] (0.15 gram atoms Cr) dissolved
in 100-ml water.
';' . ' ' '
16. ~
~ ~. - .. . . .
" `, . '

D-9462-c
~451~6
The resulting mixture was heated while
stirring and approximately 60 per cent of the water
was evaporated off.
The resulting concentrated slurry was trans-
ferred to a stainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumina (No. SA-5218)
~" spheres were added. This was followed by drying
by evaporation with stirring on a steam bath. Further
drying was carried out at a temperature of 120C for
a period of:l6 hours.
The dried material was then transferred to a
tray f;bricated from 10-mesh stainless steel wire
screen and calcined in a muffle furnace for 5 hours
at 400C in-an ambient atmoephere of air. The
amount of catalyst deposited on the supported calculated
,.
from the welght increase of the catalyst obtained is
26.1 weight per cent. Catalytic test results for
~thi: material are given In Table I.
EXAMPLE 5
: . .
~ 20 M2 gV 7Ti 35
: .: .- , .
Eighty-two grams of ammoniom meta-vanadate (o.7)
.
,.
17- ~ ~
: ~0, :

9~62
~L~45~6 ; ~
gram atoms of V) and 494 grams of ammonium para-
molybdate (2~8 gram atoms of Mo) were dissolved in two
liters of water while stirring at 60-80C in a stain-
less steel beaker.
To the resulting solution were added 204
grams of titanium ammonium lactate (chelate) solution
(containing 0.35 gram atoms Ti) and 28 grams of ammonium
nitrate (NH4N03) (.35 gram moles N~14N03) dissolved in
100-ml water.
The resulting mixture was heated while stir-
ring and approximately 60 per cent of the water was
evaporated off.
The resulting concentrated slurry was trans-
ferred to a stainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumina (No. SA-5218)
1/4" spheres were added. This was followed by drying
by evaporation with stirring on a steam bath. Further
drying was carried out at a temperature of 120C. for
a period of 16 hours. `
The dried material was then transferred to `
a tray fabricated from 10-mesh stainless steel wire
screen and calcined in a muffle furnace for 5 hours
at 400C in an ambient atmosphere of air. The amount
, ,,:
of catalyst deposited on the support calculated from
the weight increase of the~ca~alyst obtalned is 30.4 ~;
weight %, Catalytic test results or this material
are given in Table I.
18.
.:

~462
~O~LS:1~6
EXAMPLE 6
M2.4V.6Ti.3CU,15made with (NH40H) 5 ~;
Seventy grams of ammonium meta-vanadate
(0.6 gram atoms of V) and 424 grams of ammonium
paramolybdate (2.4 gram atoms of Mo) were dissolved
in two liters of water while stirring at 60-80C. in
a stainless steel beaker.
To the resulting solution were added 175
grams of titanium ammonium lactate (chelate) solu-
tion containing 0.3 gram atoms of Ti and 18 grams of `~
ammonium hydroxide containing 28.6% NH3 (0.15 gram
moles NH3) plus 36 grams of copper nitrate
[Cu(NO3)2 3H2O] (0.15 gram atoms Cu) dissolved in
100-ml water. ` ; -
The resulting mixture was heated while
stirring and approx~mately 60 per cent of the water
was evaporated off.
The resulting concentrated slurry was
transferred to a stainless steel evaporating dish
and 1040 grams (1000 ml) Norton silica-alumina -
(No. SA-5218) 1/4" spheres were added. This was
followed by drying by evaporation with stirring -
on a steam bath. Further drying was carried out ~-
at a temperature of 120C for a period of 16 hours.
. ' ' ' . '
19. '' ~ ' .
' ~
','' . ,
.,~

1~51~6 946~
The dried material was then transferred to a
tray fabricated from 10-mesh stainless ~teel wire
screen and calcined in a muffle ~urnace for 5 hours at
400C. in an ambient atmosphere of air. The amoun~ of
catalyst depo~ited on the support calcula~ed from the
weight increase of the catalyst ob~ained is 27.8 weigh~
%. Ca~alytic test results for ~his ma~erial are given ~ : :
in Table I,
E~YAMPLE 7
., _ . . .
2,4v0.6Tlo~3coo 15
. Seven~y grams of ammonium met~-vanadate(0.6
gram atoms of V) and 424 gram~ of ammonium para-
molybdate (2~.4 gram stoms of Mo) were di9solved in two~
liters of water while stirring at 60-80C. in a~stain-
le8s steel beaker.
: To the resulting solu~ion were added 175 ~:
-
- grams of titan-.ium ammonium lactate (chelate) solution :.:
~ ~ I , . .
: ~20 ~(containing 0.3~gram a~oms Ti) and 44 grams o cobalt .`. ~
,. ~.:
nitrate LCO~N03)2~6H20](0.l5 gram atoms Co) dissolved ~: :
in 100-ml wa1:er.
~ .
The resulting mixture was heated whil~ ætir-
: ring and approximately~60 per cent of the water was
evaporated o~
. - : :
~ The resulting concentra~ed slurry was
..
~ .
~ 20,

104S1~ 9~62 - :
transferred to a stainless ste!el evaporating dish and
1040 grams (lO00 ml) Norton si.lica-alumina (No. SA-5218) .
1/4" spheres were added. Thi~ was foll~wed by dry~ng
by evaporation with stirring on a steam bath. Further
drying was cArried out at a ~emperature of 120C. for
a period of 16 hours.
The dried materLal wa~ then transferred to a ~-
tray fabricated from lO-mesh stainless steel wire screen
and calcin~d in a muffle furnace for 5 hours at 400C.
in an ambient atmosphere of air. The ~mount of catalyst
.
deposited on the support calculated from the weight
increase of the catalyst obtained is 27:.1 weight %.
M2 8V0. 7Tlo .175CUO.175
Eighty-two grams of ammonium meta-vanadate :
(0.7 gram atoms of V) and 495 grams of ammoaium para- :
molybdate (2.8 gram atom~ of M~) were dissolved Ln two ~ ~
liters of water while stirring at 60-80C in s~ain- ~;
less steel beaker. . :~.
;~
: 20 To the resulting solution were add~d 102
. :. .
grams of titanLum ammonium:lactate (chela~e) solution
: ~(cont~inlng 0.175 ~ram atoms Ti~ and 42 gram8 of
copper nltFate /Cu(N03)2 3H2 ~ ~(0~175 gram atoms Cu)
21. .;
:: ~ - :
~ , .
: , '', ~

~04S~6 9462
d~ssolved in 100-ml water. ~:
The resulting mixture was heated while
stirring and approximately 60 per cent of the water
was evaporated off. ~:
The resulting concentrated slurr~ was trans-
erred to a stainless steel evaporating dish and 1040
gram~ (1000 ml) Norton silica-alumina (No. SA~5218)
1/4" spheres were added. This was followed by drying -~
by evaporation with stirring on a steam bath. Further
drying was carried out a~ a temperature of 120C. for
a period o 16 hours.
The dried material was then transferred to
a tray fabricated from 10-mesh stainless steel wire
screen and calcined in a muffle furnace ~or 5 hours at
400C. in an ambient atmosphere of air. The amount of
catalyst deposited on the support calculated from the
weight increase of the catalyst obtained is 29.2 weight
per cent, Catalytic test results for this material
are~given in Table I.
; : 20 ~ : ~ EXA~ELE 9 . ~.
~ Mo2 4Vo~6Tio~3cuo~l5
:: :
Seventy grams of ammonium m~ta-vanadate(0.6
gram atoms o~ y) and~42~ grams of ammonium paramolyb~
date (2.~4 g.ram atoms o Mo) were dissolved in two lite~s
,
o water.while stirring at 60-80C. in a ~tainle~s ~teel
beal~er. : ~: -
:. 22.
.: ' ~ ' .

~0~5~6 946~
To ~he resulting solution was added a
solution containing ~4 grams of titanium hydrate pulp
(0,3 gram a~oms Ti), 54 grams o~ ammonium lactate
(0,6 moles ammonium lactate) and 40 grams 28,6% aqueous
ammonium hydroxide (0.67 moles ammonium ion). 36 grams
cupric nitrate (0.15 gram atoms Cu) in 100 ml water was
then added.
The resul~ing mixture was heated while stlr-
rin~ and approximately 60 per cent of the water was
evaporated off.
The resul~ing concentrated slurry was trans- ~
ferred ~o a stainless steel evaporating dish and 1040 ~-
grams (1000 ml) ~orton silica-alumina (~SA-5218) 1/4"
spheres were added. This was followed by drying by
evaporation with stirring on a steam bath. Further
~drying was carried out àt a temperature of 120C, for
a period of 16 hours. ~
The dried material~was then transferred to
a tray fabricated from 10-mesh stainless steel wire
20 ~ screen and calcLned in a mu~Ele furnace for 5 hours at
400C. ln an ambient a~mosphere of air. The amount of
catalyst deposited on the support calculated from the ,
wel~ht increase of the catalys~ obtained is 25.8
weight %. Catalytic test results for this material
are ~iven in Table I~
-
.. . .
~ ~ 23
.. .
, ~...
::

:: g462
S106
EXAMPLE 10 -
MO2 4Vo.6Feo~l5
Seventy grams of ammonium meta-vanadate (0.6
grams atoms of V) and 424 grams of ammonium paramolyb-
date (2.4 gram atoms of Mo) were dissolved in two
liters of water while stirring at 60-80C. in a
stainless steel beaker. ~ '
To the resulting solution were added 60 grams
ferric nitrate [Fe(NO3)3-9H2O] ~0.15 gram atoms Fe) dis-
solved in lO0-ml water. ,~
The resulting mixture was heated while stir- ~;
ring and approximately 60 per cent of the water was
e~aporated off.
The resulting concentra~ed slurry was trans-
ferred to a stainless s~eel evaporating dish and 1040
grams (lO00 ml) Norton silica-alumina (No. SA-5218) ,~
l/4" spheres were~added. This was followed by drying i;
by evaporation with stirring on a steam bath. Further ~ `~
~ drying was carried out at a temperature of 120C for a
period of 16 hours.
The dried material was then transferred to a
tray fabricated from 10-mesh stainless steel wire screen
and calcined in a muffle furnace for 5 hours at ~00C.
in an ambient~atmosphere of air. The amount of catalyst
deposited on the support calculated from the weight ~ -
i~crease of t~e catalyst obtained is 27.5 weight per
, , ,
'.:, ':
2~-
.

9462
,:
111 ~511:~6
cent. Catalytic test results for this material are
given in Table I.
EXAMPLE 11
Moz,4Vo,6Feo,ls made with 0.75 (mole) parts (NH~)2
oxalate
Seventy grams of ammonium meta-vanadate
(0.6 gram atQms of V) and 424 grams of ammonium ~ -
paramolybdate (2.4 gram atoms of Mo) were dissolved in ~ -
two liters of water while stirring at 60-80C. in a
stainless steel beaker. ' ;
To the resulting solution were added 107 ';~
grams of ammonium oxaIate 1(NH4)2C24 H20] (0-75 gram `;
moles (NH4)2C204) and 60 grams of ferric nitrate ~ ;
'; ;.:
[Fe(N03~3 9H20] (0.15 gram atoms Fe) dissolved in
100-ml water. ~-
The resulting mixture was heated while
... . . .. .
stirring and approximately 60~per cent of the water~-" ;~
was evaporated off.
The resulting concentrated slurry was trans~
~20 ~ f~rred to a s~ainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumina (#SA-5218) 1/4" ;~
, ~
spheres were-added. This was followed by drying by
evaporation with stirring on a steam bath. Fur~her
: . :
drying was carried out at a temperature of 120C, for
a period of 16 hours. i ;
The dried material ws5 then transferred to
~, -,,
. ' .:
. .. .
... . .
,: .:
-. . ~ , . . . . . . ,~,~ . ".. . . . . . . . .

9~62 ~
~.o~s~a6
a tray fabricated from 10-mesh stainless steel wire
screen and calcined in a muffle furnace for 5 hours at
400C. in an ambient atmosphere of air. The amount of
catalyst deposited on the support calculated from the
weight increase of the catalyst obtained is 26.3 weigh~
per cent. Catalytic test results for this material are
given in Table I.
EXAMPLE 12
Mo~.8V0.7
Eighty-two grams of ammonium meta-vanadate
(0.7 gram atoms of V and 256 grams of oxalic acid (2.1
moles) were dissolved in two liters of water while stir-
ring at 60-80C. in a stainless steel beaker.
To the resulting solution were added 495 grams ,~
of ammonium paramolybdate (2.8 gram atoms Mo) dissolved
in 1 liter of water.
The resulting mixture was heated while stirring
and approximately 60 per cent of the water was evaporated
off.
The resulting concentrated slurry was trans-
ferred to a stainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumina (#SA-5218) l/4'
spheres were added. This was followed by drying by
evaporation wi~h stirring on a steam bath. Further
drying was carried ou~ at a temperature of 1~0C. for
a period of 16 hours.
'
~ 26. !j
, ,~
'

" 9462
~ Q ~
The dired material was then transferred to
a tray fabricated from lO-mesh stainless steel wire
screen and calcined in a muffle furnace for 5 hours at
400C. in an ambient atmosphere of air. The amount of
catalyst deposited on the support calculated from the
weight increase of the catalyst obtained is 26.5 weight
%. Catalytic test results for this material are given ~:
in Table I.
EXAMPLE 13 .
10M2 4Vo,6TiO~3cuo~l5
Seventy grams of ammonium meta-vanadate :
(O.6 gram atoms of V) and 424 grams of ammonium para-
molybdate (2.4 gram atoms of Mo) were dissolved in two
liters of water while stirring at 60-80C. in a stain-
less steel beaker. -`:
To the resulting solution were added 84 grams -
of titanium hydrate pulp (0.3 gram atoms Ti~ 39 g~ams
~: .
of 28.6% ammonium hydroxide solution (0.67 moles ~:
. .
ammonium ion) and 36 grams of cupric nitrate (0.15 :~
gram atoms Cu).
The resulting mixture was heated while ~ :
stirring and approximately 60 per cent of the water
was evaporated of~
The resulting concentrated slurry was trans~
. :-,. .. .
ferred to a stainless steel evaporating dish and 1040
grams (1000 ml) Norton silica-alumlna (~SA-5218) 1/4"
,
27. :.
.
,; ~, ~ ', '

9462
~4S~
spheres were added. This was followed by drying by
evaporation with stirring on a steam bath. Further
drying was carried ou~ at a temperature of 120C.
for a period of 16 hours.
The dried material was then transferred to
a tray fabricated from lO-mesh stainless steel wire ~-
screen and calcined in a muffle furnace for 5 hours
at 400Co in an ambient atmosphere of air. The amount
of catalyst deposited on the support calculated from
the weight increase of the catalyst obtained is 26.0
weight per cent. Catalytic test results for this
material are given in Table I. ~ '
EXAMPLE 14
Mo2.4V.6Cu.15
Seventy grams of ammonium meta-vanadate
(0.6 gram atoms of V) and 424 grams o~ ammonium
paramolybdate (2.4 gram atoms o~ Mo) were dissolved '
in two liters of water while stirring at 60-80C.
in a stainLess steel beaker.
T the resulti~g solution were added 90
:,
grams of ammonium lactate solution (containing 0.6 :
gram mole NH4 lactate) and 36 grams of copper nitrate
[Cu(NO3)2 3H2O] (0.15 gram atoms Cu) dissolved in
100-ml water.
The resulting mixture was heated while ;;
stirringi;and approximately 60 per cent o the water
28.
~',,
,. .~- ,

9~62
1~L51~6
was evaporated off.
The resulting concentrated slurry was trans-
ferred ~o a stainless steel e~aporating dish and 1040
grams tlO00 ml) Norton silica-alumina (~o. SA-5218)
1/4" spheres were added. This was followed by drying
by evaporation with stirri.n~ on a steam bath, Further
drying was carried out at a temperature of 120C. for
a period o~ 16 hours.
The dried material was then tr~ns~erred to !',;" ;''"'
a trày fabricated from 10-mesh stainle s steel wire
screen and calcined ln a muffle furnace for 5 hours at
- -:
400C. in an am~ient atmosphere of air, The amount of
catalyst deposlted on the support calculated from the
weight increase of the eatalys~ obtai~ed is 26.0
~ . :
weight %, CataIytic test results for this material :~-
are given in Table I.
The 8upport u8ed in ~e examp~e~ wa~ ess'en-
tiaily an ~v86/14) Al203jS1~2 material having an
apparent porosity of 36-4~7~and a ~urface are~- of
20 ~lm~/gram, About lO~o of the pores in the support : :
had a pore diam~ter of about 20-180.
~ ~ The pH of;the ~olutions u~ed in each o~ the -
. "........
examples for the preparation o~ the catalysts was in
the range o~ 5 * 3. ~::
The resu~ts o~ Examples 1 to 8 reported below in
...
Table I demon~trate tha~t when the catalyst composltlon~ are
.
:~ - 29. ;
'
.' ~ . ' ' ' 1 . : . '.

4 5 ~ 6
9462
prepared in accordance with the teachings of the present,~
lnvention, as described above, the resulting catalysts
provide a combination of relatlvely hlgh levels of %
conversion, productivity and % selectivity ln the
oxidation of alpha~beta-unsaturated aldehydes such as
acroleln to the corresponding alpha-beta-unsaturated
acid.
The results of Examples 9 to 14 reported below
in Table I de~onstrate that not all compositions contain- -
ing the elements Mo, V and X, as defined above, provide -
catalysts which-can be used ln the oxldation o alpha-beta -
unsaturated aldehydes such as acrolein to produce the
corresponding alpha-beta unsaturated acld at relatively
high levels of % conversion, productivity and %
selectivity., ' ; , '
^' ' ,. .~' -.
,. ~ .
-
: : : '
- : :
: ' '
.
~: ~
: : 30,
: ~: : : , .,
,

lV45~L0~ii
9462
.
o o ~ ~
. :
~ ~ . y : ~
H~ 3 ~ C~l; ~ 0 ~ ~ 0
~ 0 ~ ~
PO æ ~ ~o ~0 ~0 ~ ô4
u ~U ~ U~ ~ tdo ~
,0 0 q- ~
N ,~ ~ ~ jc ~ o O
: . :
, ~ ~
. , . .. ~ ~ ~ . ; .
... , ~ . " .,.,.. . .. :. .

9462
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:.,
o~ o a~
' ~Z~ ~ ~ C~ ,
~ :
~ ~3 g ~ ~ o o , o o ~ - :
~ o
- .: . . . :
~ ~ ' ~ ~ ~ ; ' ~ ` ~
~ ~ ~ U~ o; o
~ ~~ C~ U ;3~ xo ~
~ ~ ~ ~ - o ~ ,~
h : '~ :: ,1 ~ o ~
,,y ~ ~ 0 0 ~
PO ~ æ æ~ ;P PO ~PO,
t~
U O O q t
:
:
`