Catalyst for oxidation of olefin or tertiary alcohol and process for production thereof

A catalyst used for producing, by catalytic gas phase oxidation of a C.sub.3 -C.sub.5 oelfin or tertiary alcohol, the corresponding unsaturated aldehyde and unsaturated carboxylic acid, said catalyst characterized by comprising molybdenum, iron and bismuth and having a specific surface area in the range from 1 to 20 m.sup.2 /gr, a pore volume in the range from 0.1 to 1.0 cc/gr and a pore diameter distribution in which the pore diameters are collectively distributed in the range of each of from 1 to 10 microns and from 0.1 to less than 1 micron; and a process for preparing said catalyst by charging an unfired material power into a centrifugal flow coating device to form particles having the average particle diameter of 2 to 10 mm and then firing the particles.

This invention relates to an oxide catalyst comprising molybdenum, iron and 
bismuth and being suitable for producing, from an olefin or tertiary 
alcohol, the corresponding unsaturated aldehyde and unsaturated carboxylic 
acid and a process for the production thereof. More specifically, this 
invention relates to a catalyst which exhibits high activity and excellent 
durability owing to its specific properties and which is used for the 
oxidation of an olefin or tertiary alcohol and a process for the 
production of said catalyst with good reproducibility. 
There are proposals for various catalysts for producing, from an olefin or 
tertiary alcohol (especially tertiary butanol), the corresponding 
unsaturated aldehyde (and unsaturated carboxylic acid) at high yields by a 
catalytic gas phase oxidation reaction. These proposals are mainly 
concerned with selection of components for catalysts and ratios thereof, 
and some of them are also concerned with selection of catalyst properties 
and production processes with reproducibility. For example, there are many 
proposals concerning catalyst properties such as specific surface area, 
pore volume, pore diameter, etc., with regard to catalysts used for the 
oxidation and ammoxydation reactions of an olefin and comprising 
molybdenum, bismuth and iron. However, none of these proposed catalysts 
are on a satisfactory level, as will be mentioned hereinbelow. 
With regard to the specific surface area, catalysts having specific surface 
areas in the range from 0.01 to 50 m.sup.2 /g are described in Japanese 
Patent Publications Nos. 21081/1972, 10434/1977, 13488/1969, 5632/1978, 
36384/1980, 24658/1981, 28180/1981 and 29139/1983 and Japanese Laid-Open 
Patent Publication No. 26690/1973. However, these catalysts are not 
satisfactory as industrial catalysts, since they have low activity in 
spite of defined high reaction temperatures or they have low selectivity 
to a corresponding unsaturated aldehyde. With regard to the pore volume, 
Japanese Laid-Open Patent Publication No. 119837/1982 describes that the 
pore volume of 0.2 to 0.4 cc/g is preferable. However, Examples thereof 
merely disclose the use mainly in ammoxydation. With regard to the pore 
diameter, the same Japanese Laid-Open Patent Publication No. 119837/1982 
describes that the average pore radius of not less than 2,000 .ANG. is 
preferable. The pore radii therein are controlled by addition of organic 
substance such as cellulose, etc., to material for catalyst. Japanese 
Patent Publication No. 113141/1983 describes, with regard to the pore 
diameter, that the pores having a diameter smaller than 100 .ANG. should 
be less than 3%. However, the catalysts disclosed therein all have low 
activity, and none of them can be used as an industrial catalyst for 
producing acrolein and acrylic acid or methacrolein and methacrylic acid 
at high yields by oxidation of propylene, isobutylene or tertiary butanol. 
In the case of producing acrolein and acrylic acid or methacrolein and 
methacrylic acid by an oxidation reaction of propylene, isobutylene or 
tertiary butanol by the use of a reaction apparatus having a fixed bed or 
moving bed, catalysts are used, in general, in the form of pellets having 
a suitable size. Such pellets are formed by using a tablet-forming 
machine, extruder, pill-forming machine, rolling particle-forming machine, 
etc. However, there are many cases where it is difficult to form pellets 
without degradation of catalyst performance, and most cases show poor 
reproducibility of catalyst performance. 
Therefore, the present inventors made an assiduous study of those causes of 
variations of catalyst performance which take place at the time of 
preparing catalyst pellets. As a result, they have found that, in 
catalysts containing Mo, Fe and Bi as essential components, the catalyst 
performance decreases to a great extent and the performance and physical 
property values vary depending upon the methods of formation thereof. The 
main cause thereof is that the forming procedure has influence on the 
pores of a catalyst and has consequent influence on the specific surface 
area, pore volume and average pore diameter of the catalyst. 
As a result of the present inventor's further study, they have found that a 
catalyst containing Mo, Fe and Bi as essential components has to meet 
three conditions, in order to exhibit excellent properties, that it has a 
specific surface area in the range from 1 to 20 m.sup.2 /gr, preferably 
from 5 to 20 m.sup.2 /gr, that it has a pore volume in the range from 0.1 
to 1.0 cc/gr, preferably from 0.3 to 0.9 cc/gr, and that it has a pore 
diameter distribution in which its pore diameters are collectively 
distributed in the range of each of from 1 to 10 .mu.m and from 0.1 to 
less than 1 .mu.m. 
Accordingly, the present invention provides a catalyst which comprises 
containing Mo, Fe and Bi and having the above three properties in 
combination and which is used for producing, by catalytic gas phase 
oxidation of a C.sub.3 -C.sub.5 olefin or tertiary alcohol, the 
corresponding unsaturated aldehyde and unsaturated carboxylic acid. 
In the present invention, the well-balanced presence of pores having pore 
diameters of 1 to 10 .mu.m and pores having pore diameters of 0.1 to less 
than 1 .mu.m is one of the important conditions. Catalysts for an 
oxidation reaction of propylene exhibit performance enhanced in both 
catalyst activity and selectivity when the catalysts have a pore diameter 
distribution in which the pore volume consisting of pores having pore 
diameters in the range from 0.1 to less than 1 .mu.m is not less than 30%, 
preferably in the range from 45 to 80%, based on the entire pore volume 
and the pore volume consisting of pores having pore diameters in the range 
from 1 to 10 .mu.m is not less than 20%, preferably in the range from 25 
to 60%, based on the entire pore volume. On the other hand, it is one of 
the important conditions for the performance of catalysts used for an 
oxidation reaction of isobutylene or tertiary butanol that the ratio of 
the pore volume consisting of pores having pore diameters in the range 
from 1 to 10 .mu.m should be greater than the ratio of the pore volume 
consisting of pores having pore diameters in the range from 0.1 to less 
than 1 .mu.m. 
In general, a pore having a smaller pore diameter has a larger contribution 
toward the surface area and pore volume. However, in the catalyst 
comprising Mo, Fe and Bi for oxidation of an olefin or tertiary alcohol in 
the present invention, the mere larger ratio of the smaller pores [i.e., 
pores having pore diameters in the range of 0.1 to less than 1 .mu.m] is 
not sufficient to obtain the aforementioned activity and selectivity, and 
the fairly larger ratio of the larger pores (i.e., pores having pore 
diameters in the range of 1 to 10 .mu.m) is necessary as well. 
By forming an unfired catalyst material powder into pellets having the 
average diameter of 2 to 10 mm by the use of a centrifugal flow coating 
device, the catalyst having the above physical properties in the present 
invention can be obtained with very good reproducibility as compared with 
usual formation methods. In usual formation methods of catalysts, a 
rolling particle-forming method, marmerizer forming method, fluidized bed 
particle-forming method, etc., are used for the preparation of spherical 
shapes, and an extrusion method, tablet-forming method, etc., are used for 
cylindrical shapes. However, in the case of using these formation methods, 
it is difficult in many cases to form catalysts without degrading the 
catalyst performance, the performance varies widely and the 
reproducibility is often poor. In contrast thereto, in the present 
invention, the use of a centrifugal flow coating device, which is simple 
and good in producibility, makes it possible to prepare spherical or 
particulate catalysts having the aforespecified specific surface area, 
pore volume and pore diameter distribution, with good reproducibility. 
Further, the formation by a centrifugal flow coating device has advantages 
that catalysts having a narrow distribution of particle size can be 
obtained and that, since said catalysts are particulate or spherical, the 
catalysts have high mechanical strength, little pressure loss and high 
resistance to wear and are easy to fill in or take out from a reaction 
apparatus. 
A centrifugal flow coating device and the use thereof are known as one 
method of forming powder material into particles. For example, Japanese 
Patent Publication No. 10878/1971 discloses them as a method of forming 
sugar coatings of medicaments, and Japanese Patent Publication No. 
17292/1977 discloses the coating of particulate cores with a catalyst or 
carrier by a centrifugal flow coating device. 
The present invention applies this method to the preparation of an oxide 
catalyst comprising Mo, Fe and Bi elements as essential components, and 
easily makes it possible to obtain a spherical or particulate catalyst 
having the aforespecified specific surface area, pore volume and pore 
diameter distribution and having high physical strength, by only using, as 
a binder, a liquid such as water, or by optionally using, in combination 
therewith, a substance which gives pores into a catalyst by combustion or 
volatility at the time of firing. 
As a preparation example by a centrifugal flow coating device, there can be 
cited a method which comprises charging a powder of an unfired oxide 
composition not shaped or pre-stage catalyst particle material composition 
not converted to oxide into a centrifugal flow coating device, forming the 
powder into particles with blowing heated air thereinto and spraying a 
binder such as water, taking out the particles grown to the desired size 
in batch-type operation or in successive operation, then drying the 
particles as necessary and thereafter firing them. 
The catalyst of the present invention can be used by diluting it with an 
inert carrier or by holding it on an inert carrier according to a case 
where it is necessary. In the formation of particles, it is preferable to 
use, as a core, granules obtained by preforming a powder of catalyst per 
se to a size about 10 times as large as that of the material powder. 
Naturally, an inert carrier can be also used as this core. Examples of the 
inert carrier include silicon carbide, silica, alpha-alumina and others 
known as a refractory material. With regard to a catalyst powder for 
coating to grow a particle diameter, it is preferable to preadjust it to 
not more than 100 mesh. 
In order to produce a catalyst having the specific surface area, pore 
volume and pore diameter distribution specificed by the present invention 
with good reproducibility, it is possible to add, for example, a polyvinyl 
alcohol, stearic acid, etc., to a material particles at the time of 
preparation of a catalyst powder or add it to a catalyst powder at the 
time of shaping. In the case, for example, when it is necessary to make 
the degree of powdering smaller, it is possible to use a whisker or glass 
fiber. As a binder of the powder, it is also possible to use water, 
cellulose, ammonium nitrate, graphite, starch, etc. Organic solvents such 
as alcohol, acetone, etc., can be used as well. 
The catalyst of the present invention comprises Mo, Fe and Bi as essential 
components. Most preferably, it has a composition represented by the 
following formula, 
EQU Mo.sub.a W.sub.b Bi.sub.c Fe.sub.d A.sub.e B.sub.f C.sub.g D.sub.h O.sub.x 
wherein Mo denotes molybdenum, W denotes tungsten, Bi denotes bismuth, Fe 
denotes iron, A denotes at least one element selected from the group 
consisting of nickel and cobalt, B denotes at least one element selected 
from the group consisting of alkali metal, alkaline earth metal and 
thallium, C denotes at least one element selected from the group 
consisting of phosphorus, tellurium, antimony, tin, cerium, lead, niobium, 
boron, arsenic, manganese and zinc, D denotes at least one element 
selected from the group consisting of silicon, aluminum, titanium and 
zirconium, and O denotes oxygen; and further, a, b, c, d, e, f, g, h and x 
denote atomic ratios respectively, when the olefin is propylene and when 
a=2 to 12, b=0 to 10 and a+b=12, then c=0.1 to 10, d=0.1 to 10.0, e=2 to 
20, f=0.005 to 3.0, g=0 to 4.0, h=0.5 to 15 and x is a numerical value 
determined depending upon the atomic values of the other elements than 
oxygen, and when the olefin is isobutylene or when the tertiary alcohol is 
tertiary butanol and when a=12, then b=0 to 10, c=0.1 to 10, d=0.1 to 20, 
e=2 to 20, f=0 to 10, g=0 to 4, h=0 to 30 and x is a numerical value 
determined depending upon the atomic values of the other elements than 
oxygen. 
A catalytic gas phase oxidation using a catalyst of the present invention 
is carried out by introducing a mixture gas consisting of 1.0 to 10% by 
volume of an olefin or tertiary butanol, 3 to 20% by volume of molecular 
oxygen, 0 to 60% by volume of water vapor and 20 to 80% by volume of an 
inert gas such as nitrogen, carbon dioxide gas, etc., onto the catalyst at 
a temperature in the range from 250.degree. to 450.degree. C., at a 
pressure of an atmospheric pressure to 10 atm and at a space velocity of 
300 to 7,000 hr.sup.-1 (STP).

The following Examples and Comparative Examples will illustrate the present 
invention more in detail, however, the present invention is not limited 
thereto. In the present specification, the conversion, selectivity and 
total yield in a single flow are respectively defined as follows. 
##EQU1## 
[EXAMPLE I] 
Preparation of suspension of catalyst material 
While 4,500 ml of distilled water was heated with stirring, 3,186 g of 
ammonium molybdate and 972 g of ammonium paratungstate were added and 
dissolved therein. Separately, a solution of 2,100 g of cobalt nitrate in 
400 ml of distilled water, a solution of 729 g of ferric nitrate in 600 ml 
of distilled water and a solution of 876 g of bismuth nitrate in 900 ml of 
distilled water acidified by addition of 180 ml of conentrated nitric acid 
were prepared respectively, and a mixture of these three nitrate solutions 
was added to the above water solution containing ammonium molybdate and 
ammonium paratungstate. Then, a liquid obtained by dissolving 732 g of 
silica sol containing 20% by weight of silica and 6.06 g of potassium 
hydroxide in 450 ml of distilled water was added and stirred to prepare 
the suspension. (This suspension is referred to as suspension-A.) 
EXAMPLE I-1 
(Centrifugal flow coating method) 
The suspension-A was heated, stirred, evaporated and dried to solidify it, 
and then the resulting solid was milled to about 100 mesh to obtain a 
powder. This powder was charged into a centrifugal flow coating device 
blowing heated air at 90.degree. C. with using distilled water as a 
binder, and formed into spherical particles having the average diameter of 
5 mm. These particles were dried in a drier at 120.degree. C. for 12 hours 
and then fired under an air current at 450.degree. C. for 6 hours to 
prepare a catalyst (I-1). The ratio of elements other than oxygen in this 
catalyst oxide was Co.sub.4 Bi.sub.1 Fe.sub.1 W.sub.2 Mo.sub.10 
Si.sub.1.35 K.sub.0.06. 
EXAMPLES I-2-1 AND I-2-2 
(Tablet forming method) 
A suspension-A was prepared in the same way as in the above, and the 
suspension-A was evaporated with stirring under heat to solidify it. Then 
the resulting solid in block state was dried in a drier under air current 
at 200.degree. C. for 12 hours. The dried block was milled to not more 
than 100 mesh. 2% by weight of a carbon powder was added to this milled 
powder and the resulting mixture was formed into tablets having a diameter 
of 5 mm and height of 5 mm. The tablets were fired under air current at 
450.degree. C. for 6 hours to prepare a catalyst (I-2-1). Then, the same 
procedure was repeated to prepare a catalyst (I-2-2). 
EXAMPLES I-3-1 AND I-3-2 
(Extrusion method) 
A suspension-A was prepared in the same way as in the above, and the 
suspension-A was condensed until it was extrudable, and extruded to form 
extrudates having a diameter of 5 mm and height of 5 mm. The extrudates 
were dried at 120.degree. C. for 12 hours and fired under air current at 
450.degree. C. for 6 hours to prepare a catalyst (I-3-1). Then, the same 
procedure was repeated to prepare a catalyst (I-3-2). 
EXAMPLE I-4 
(Marmerizer-forming method) 
A suspension-A was prepared in the same way as in the above, and the 
suspension-A was treated with externally applied heat for condensation 
thereof to obtain a soil-like product, 40% by weight of which was 
dissipated when it was fired at 500.degree. C. (i.e., its solid content 
was 60% by weight). This product was extruded to form extrudates having a 
diameter of 6 mm and lengths of 4 to 7 mm, and then the extrudates were 
subjected to a marmerizer to form elliptic spheres having a breadth of 3 
mm and length of 5 mm. The elliptic spheres were dried at 120.degree. C. 
for 12 hours and fired under air current at 450.degree. C. for 6 hours to 
prepare a catalyst (I-4-1). 
EXAMPLE I-5 
(Rolling particle-forming method) 
A suspension-A was prepared in the same way as in the above, and the 
suspension-A was evaporated and dried with stirring under heat to solidify 
it. The resulting solid was milled to about 100 mesh to obtain a powder. 
This powder was formed into spherical particles having the average 
diameter of use of a rolling particle-forming machine and heated air at 
80.degree. C. and distilled water as a binder. The particles were dried at 
120.degree. C. for 12 hours and then fired under air current at 
450.degree. C. for 6 hours to prepare a catalyst (I-5). 
EXAMPLE I-6 
(Pill-forming method) 
A suspension-A was prepared in the same way as in the above, and the 
suspension-A was treated with externally applied heat for condensation 
thereof to obtain a soil-like product, 45% by weight of which was 
dissipated when it was fired at 500.degree. C. (i.e., its solid content 
was 55% by weight). This product was formed into shapes having the average 
diamter of 5 mm by the use of a usual pill-forming machine. This resulting 
spherical product was dried at 120.degree. C. for 12 hours and then fired 
under air current at 450.degree. C. for 6 hours to obtain a catalyst 
(I-6). 
REACTION TEST 
Catalysts I-1 to I-6 obtained in the above EXAMPLES (1,500 ml each) were 
charged respectively to steel reaction tubes having an internal diameter 
of 25.4 mm, and a mixture gas composed of 7% by volume of propylene, 12.6% 
by volume of oxygen, 10% by volume of water vapor and 70.4% by volume of 
nitrogen was introduced thereinto to carry out catalytic gas phase 
oxidation reactions of propylene at a reaction temperature of 310.degree. 
C. for a contact time of 2.25 seconds. The results are shown in Table 1. 
[EXAMPLE II] 
(Preparation of catalyst and its reproducibility) 
Catalyst material suspensions-A were prepared on a scale four times as 
large as that of EXAMPLES I-1 to I-6 series, and catalysts (EXAMPLES II-1 
to II-4) were prepared by using the suspensions-A, by using forming 
methods shown in Table 2 and according to EXAMPLE I. In each of EXAMPLES 
II-1 to II-4, four catalysts were prepared under the same conditions 
(batch Nos. 1 to 4) in order to test the presence or absence of the 
reproducibility of catalyst preparation. Tests of performance were carried 
out according to the method of EXAMPLES I-1 to I-6. The results are shown 
in Table 2. 
As is clear in Table 2, it is seen that the formation of a centrifugal flow 
coating method can give catalysts having smaller variation of physical 
values and high activity. The fact that the variation of physical values 
is small means that catalysts were prepared with good reproducibility. On 
the other hand, it is further seen that catalysts prepared by the other 
forming methods include those that have not the specific surface area, 
pore volume and pore diameter specified by the present invention although 
they were prepared in batches under entirely the same conditions, and that 
the catalyst performance thereof is inferior to that of the catalysts 
obtained by a centrifugal flow coating method. 
[EXAMPLE III] 
Preparation of catalyst material suspension 
The preparation of the catalyst material suspension for EXAMPLES I-1 to I-6 
series was repeated except that thallium nitrate and barium nitrate were 
used in place of potassium hydroxide. The resulting suspension is referred 
to as suspension-B. 
EXAMPLE III-1 
(Centrifugal flow coating method) 
The suspension-B was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.4 Bi.sub.1 Fe.sub.1 W.sub.2 Mo.sub.10 Si.sub.1.35 Tl.sub.0.04 
Ba.sub.0.05. 
EXAMPLES III-2-1 AND II-2-2 
(Tablet-forming method) 
The suspension-B was treated according to the process described in EXAMPLE 
I-2 to prepare catalysts. 
[EXAMPLE IV] 
Preparation of catalyst material suspension 
The preparation of the catalyst material suspension for EXAMPLES I-1 to I-6 
series was repeated except that cesium nitrate was used in place of 
potassium hydroxide, and further, titanium dioxide was also used together 
with silica sol containing 20% by weight of silica. The resulting 
suspension is referred to as suspension-C. 
EXAMPLE IV-1 
The suspension-C was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.4 Bi.sub.1 Fe.sub.1 W.sub.2 Mo.sub.10 Si.sub.1.35 Cs.sub.0.02 
Ti.sub.1.0. 
EXAMPLES IV-2-1 AND IV-2-2 
(Extrusion method) 
The suspension-C was treated according to EXAMPLE I-3 to prepare catalysts. 
[EXAMPLE V] 
Preparation of catalyst material suspension 
The preparation of the catalyst material suspension for EXAMPLES I-1 to I-6 
series was repeated except that strontium nitrate was used in place of 
potassium hydroxide. The resulting suspension is referred to as 
suspension-D. 
EXAMPLE V-1 
(Centrifugal flow coating method) 
The suspension-D was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.4 Bi.sub.1 Fe.sub.1 W.sub.2 Mo.sub.10 Si.sub.1.35 Sr.sub.0.06. 
EXAMPLES V-2-1 AND V-2-2 
(Marmerizer-forming method) 
The suspension-D was treated according to EXAMPLE I-4 to prepare catalysts. 
[EXAMPLE VI] 
Preparation of catalyst material suspension 
The preparation of the catalyst material suspension for EXAMPLES I-1 to I-6 
series was repeated except that calcium nitrate was used in place of 
potassium hydroxide, and further, silica sol and calcium nitrate were 
added and then niobium pentoxide was added. The resulting suspension is 
referred to as suspension-E. 
EXAMPLE VI-1 
(Centrifugal flow coating method) 
The suspension-E was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.4 Bi.sub.1 Fe.sub.1 W.sub.2 Mo.sub.10 Si.sub.1.35 Ca.sub.0.06 
Nb.sub.0.5. 
EXAMPLES VI-2-1 AND VI-2-2 
(Rolling particle-forming method) 
The suspension-E was treated according to EXAMPLE I-5 to prepare catalysts. 
[EXAMPLE VII] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in the 
preparation of the catalyst suspension for EXAMPLES I-1 to I-6 series, 
nickel nitrate was added together with cobalt nitrate, rubidium nitrate 
was used in place of potassium hydroxide and phosphoric acid was used in 
place of ammonium paratungstate. The resulting suspension is referred to 
as suspension-F. 
EXAMPLE VII-1 
(Centrifugal flow coating method) 
The suspension-F was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.3 Ni.sub.1 Bi.sub.1 Fe.sub.2 Mo.sub.12 Si.sub.4.7 P.sub.1.0 
Rb.sub.0.1. 
EXAMPLES VII-2-1 and VII-2-2 
(Pill-forming method) 
The suspension-F was treated according to EXAMPLE I-6 to prepare catalysts. 
[EXAMPLE VIII] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in the 
preparatiin of the catalyst suspension for EXAMPLES I-1 to I-6 series, 
nickel nitrate and aluminum nitrate were added together with cobalt 
nitrate and boric acid was used in place of ammonium paratungstate. The 
resulting suspension is referred to as suspension-G. 
EXAMPLE VIII-1 
(Centrifugal flow coating method) 
The suspension-G was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.3 Ni.sub.1 Bi.sub.1 Fe.sub.2 Mo.sub.12 Si.sub.4.7 B.sub.2.0 
K.sub.0.2 Al.sub.1.0. 
EXAMPLES VIII-2-1 and VIII-2-2 
(Tablet-forming method) 
The suspension-G was treated according to EXAMPLE I-2 to prepare catalysts. 
EXAMPLES VIII-3-1 and VIII-3-2 
(Extrusion method) 
The suspension-G was treated according to EXAMPLE I-3 to prepare catalysts. 
[EXAMPLE IX] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in the 
preparation of the catalyst suspension for EXAMPLES I-1 to I-6 series, 
nickel nitrate was added together with cobalt nitrate, potassium nitrate 
was used in place of potassium hydroxide and arsenious acid was used in 
place of ammonium paratungstate. The resulting suspension is referred to 
as suspension-H. 
EXAMPLE IX-1 
(Centrifugal flow coating method) 
The suspension-H was treated in the same way as in EXAMPLE I-1 to prepare a 
catalyst. The ratio of elements other than oxygen in this catalyst oxide 
was Co.sub.3 Ni.sub.1 Bi.sub.1 Fe.sub.2 Mo.sub.12 Si.sub.4.7 As.sub.0.5 
Tl.sub.0.05. 
EXAMPLES IX-2-1 and IX-2-2 
(Tablet-forming method) 
The suspension-H was treated according to EXAMPLE I-2 to prepare catalysts. 
EXAMPLES IX-3-1 and IX-3-2 
(Extrusion method) 
The suspension-H was treated according to EXAMPLE I-3 to prepare catalysts. 
EXAMPLES IX-4-1 and IX-4-2 
(Marmerizer-forming method) 
The suspension-H was treated according to EXAMPLE I-4 to prepare catalysts. 
EXAMPLES IX-5-1 and IX-5-2 
(Rolling particle-forming method) 
The suspension-H was treated according to EXAMPLE I-5 to prepare catalysts. 
EXAMPLES IX-6-1 and IX-6-2 
(Pill-forming method) 
The suspension-H was treated according to EXAMPLE I-6 to prepare catalysts. 
[EXAMPLE X] 
The preparation of the suspension for EXAMPLES I-1 to I-6 series was 
repeated to prepare a suspension. This suspension is referred to as 
suspension I. The suspension-I was shaped, dried and fired in the same way 
as in EXAMPLE I-1 to prepare a catalyst. However, this EXAMPLE used 40% by 
weight aqueous solution of ammonium nitrate as a binder. Reaction test was 
carried out according to the method of EXAMPLES I-1 to I-6. The resulting 
catalyst had a specific surface area of 12.3 m.sup.2 /g, a pore volume of 
0.51 cc/g and a pore volume distribution in which the pore volume 
consisting of pores having pore diameter in the range from 1 to 10 m was 
55% and the pore volume consisting of pores having pore diameter in the 
range from 0.1 to less than 1 .mu.m pores was 45%. This catalyst exhibited 
performance that the conversion of propylene was 99.2 mol%, the yield of 
acrolein in a single flow was 85.7 mol% and that the yield of acrylic acid 
in a single flow was 9.1 mol%. 
TABLE 1 
__________________________________________________________________________ 
Specific Reaction 
Conversion 
Yield in single 
surface 
Pore 
Pore diameter 
tempera- 
of flow (mol %) 
area volume 
distribution 
ture propylene Acrylic 
EXAMPLE Forming method 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
Acrolein 
acid 
__________________________________________________________________________ 
Example I-1 
Centrifugal flow 
10.6 0.460 
35 62 310 98.7 85.4 9.5 
coating method 
Example I-2-1 
Tablet-forming 
8.2 0.350 
5 90 310 90.3 75.9 8.1 
method 
Example I-2-2 
Tablet-forming 
4.2 0.250 
0 92 310 86.5 69.2 10.1 
method 
Example I-3-1 
Extrusion method 
8.7 0.380 
10 85 310 92.3 78.5 9.0 
Example I-3-2 
Extrusion method 
3.5 0.230 
0 97 310 90.0 75.1 9.8 
Example I-4 
Marmerizer-forming 
10.1 0.500 
30 64 310 91.8 78.9 9.3 
method 
Example I-5 
Rolling particle- 
12.5 0.400 
35 60 310 93.0 77.1 10.9 
forming method 
Example I-6 
Pill-forming method 
9.5 0.380 
35 59 310 93.4 77.6 10.0 
__________________________________________________________________________ 
*.sup.1 Ratio (%) of pore volume consisting of pores having diameters in 
the range from 1 to 10 .mu.m to the entire pore volume 
*.sup.2 Ratio (%) of pore volume consisting of pores having diameters in 
the range from 0.1 to 1 (exclusive) .mu.m to the entire pore volume 
TABLE 2 
__________________________________________________________________________ 
Re- Conver- 
Specific action 
sion of 
Yield in single 
surface 
Pore 
Pore diameter 
temper- 
propyl- 
flow (mol %) 
Batch 
area volume 
distribution 
ature 
ene Acrylic 
EXAMPLE 
Forming method 
No. 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
Acrolein 
acid 
__________________________________________________________________________ 
Example II-1 
Centrifugal flow 
1 10.5 0.460 
33 65 310 98.9 85.5 9.7 
coating method 
" 2 10.1 0.480 
35 61 310 98.1 85.7 9.3 
" 3 10.3 0.450 
33 64 310 98.5 85.2 9.4 
" 4 10.7 0.460 
32 65 310 99.2 85.0 10.5 
Example II-2 
Tablet-forming 
1 9.5 0.330 
40 56 310 93.2 75.5 9.1 
method 
" 2 4.0 0.250 
15 75 310 88.7 73.7 8.4 
" 3 10.2 0.370 
35 62 310 92.0 75.3 8.1 
" 4 7.4 0.350 
43 53 310 90.6 76.0 9.1 
Example II-3 
Extrusion method 
1 7.5 0.350 
35 60 310 91.9 78.7 9.5 
" 2 5.0 0.270 
45 47 310 87.1 76.2 7.0 
" 3 8.1 0.360 
37 62 310 92.1 79.1 8.9 
" 4 6.7 0.320 
41 43 310 89.6 78.5 8.1 
Example II-4 
Rolling particle- 
1 11.7 0.420 
27 68 310 93.5 78.6 9.2 
forming method 
" 2 10.1 0.450 
18 72 310 90.5 77.9 8.5 
" 3 13.5 0.480 
21 71 310 93.0 79.3 8.6 
" 4 8.6 0.360 
35 57 310 89.1 77.4 8.6 
__________________________________________________________________________ 
*.sup.1 & *.sup.2 Same as the remarks to Table 1. 
TABLE 3 
__________________________________________________________________________ 
Specific Reaction 
Conversion 
Yield in single 
surface 
Pore 
Pore diameter 
tempera- 
of flow (mol %) 
area volume 
distribution 
ture propylene Acrylic 
EXAMPLE Forming method 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
Acrolein 
acid 
__________________________________________________________________________ 
III 
III-1 
Centrifugal flow 
12.5 0.410 
32 60 310 99.5 87.8 7.2 
coating method 
III-2-1 
Tablet-forming 
10.2 0.320 
31 61 310 93.1 77.3 10.2 
method 
III-2-2 
Tablet-forming 
7.8 0.230 
45 46 310 87.9 74.2 9.3 
method 
IV IV-1 Centrifugal flow 
9.2 0.430 
45 50 310 91.0 82.3 6.0 
coating method 
IV-2-1 
Extrusion method 
8.5 0.350 
29 63 310 88.5 75.2 6.3 
IV-2-2 
Extrusion method 
6.9 0.180 
0 92 310 85.1 68.9 7.3 
V V-1 Centrifugal flow 
10.5 0.430 
35 59 310 98.3 88.9 6.1 
coating method 
V-2-1 
Marmerizer-forming 
9.2 0.350 
30 65 310 92.7 78.8 9.5 
method 
V-2-2 
Marmerizer-forming 
8.7 0.270 
32 61 310 90.3 77.1 8.9 
method 
VI VI-1 Centrifugal flow 
11.2 0.420 
38 60 310 98.7 87.8 6.0 
coating method 
VI-2-1 
Rolling particle- 
10.2 0.350 
33 61 310 94.3 81.0 7.0 
forming method 
VI-2-2 
Rolling particle- 
7.8 0.280 
27 65 310 90.2 79.0 7.3 
forming method 
VII 
VII-1 
Centrifugal flow 
10.7 0.380 
34 58 310 95.6 81.0 9.6 
coating method 
VII-2-1 
Pill-forming method 
10.2 0.300 
37 57 310 91.3 75.8 8.4 
VII-2-2 
Pill-forming method 
7.9 0.260 
41 50 310 88.5 73.5 8.7 
VIII 
VIII-1 
Centrifugal flow 
9.5 0.350 
30 65 310 93.0 74.1 9.6 
coating method 
VIII-2-1 
Tablet-forming 
9.0 0.310 
10 82 310 89.3 71.4 8.3 
method 
VIII-2-2 
Tablet-forming 
8.5 0.250 
0 90 310 86.1 69.2 7.1 
method 
IX IX-1 Centrifugal flow 
10.3 0.420 
34 60 310 97.2 81.6 6.3 
coating method 
IX-2-1 
Tablet-forming 
9.7 0.320 
30 59 310 90.1 75.7 6.1 
method 
IX-2-2 
Tablet-forming 
8.5 0.250 
0 89 310 88.2 73.4 6.0 
method 
IX-3-2 
Extrusion method 
9.0 0.370 
27 68 310 93.1 76.1 7.1 
IX-3-2 
Extrusion method 
8.8 0.270 
0 93 310 90.3 74.7 6.7 
IX-4-1 
Marmerizer-forming 
9.2 0.360 
35 60 310 93.2 76.9 7.1 
method 
IX-4-2 
Marmerizer-forming 
8.7 0.210 
42 49 310 90.6 75.2 7.2 
method 
IX-5-1 
Rolling particle- 
11.2 0.420 
41 55 310 94.1 77.6 7.5 
forming method 
IX-5-2 
Rolling particle- 
9.1 0.350 
44 54 310 92.7 76.5 6.9 
forming method 
IX-6-1 
Pill-forming method 
10.1 0.400 
31 65 310 91.6 75.3 7.2 
IX-6-2 
Pill-forming method 
8.5 0.290 
42 50 310 89.7 73.2 7.0 
__________________________________________________________________________ 
*.sup.1 & *.sup.2 Same as the remarks to Table 1. 
[EXAMPLE XI] 
Preparation of catalyst material suspension 
Cobalt nitrate (14.56 kg) and 2.02 kg of ferric nitrate were dissolved in 
10 liters of distilled water. 2.43 kg of bismuth nitrate was also 
dissolved in a nitric acid/distilled water solution consisting of 300 ml 
of concentrated nitric acid and 1,200 ml of distilled water. Separately, 
while 30 liters of distilled water was heated with stirring, 10.59 kg of 
ammonium paramolybdate and 2.65 kg of ammonium paratungstate were 
respectively added and dissolved therein, and the above two aqueous 
solutions of nitrate were added dropwise to the solution. And then an 
aqueous solution of 390 g of cesium nitrate in 1 liter of distilled water 
and 2.03 kg of 20%-by-weight-concentrated silica sol were consecutively 
added thereto and dissolved to obtain a suspension. (The resulting 
suspension is referred to as suspension-J.) 
EXAMPLE XI-1-1 
(Centrifugal flow coating method) 
A part of the suspension-J was evaporated and dried to solidify it while it 
was heated with stirring, and then the resulting solid in the state of 
block was dried in a drier at 200.degree. C. for 5 hours and milled to not 
more than 100 mesh to obtain a powder. 
At first, alpha-alumina particles having the average diameter of 1 mm were 
charged into a centrifugal flow coating device. And then the above powder 
was charged into the device blowing heated air at 90.degree. C. with using 
distilled water as a binder and formed into spherical particles having the 
average diameter of 5 mm. The resulting spherical particles were fired 
under an air current at 500.degree. C. for 6 hours. The ratio of elements 
other than oxygen in this catalyst oxide was Mo.sub.12 W.sub.2 Co.sub.10 
Bi.sub.1 Fe.sub.1 Si.sub.1.35 Cs.sub.0.4. 
EXAMPLE XI-1-2 
(Centrifugal flow coating method) 
EXAMPLE XI-1-1 was repeated except that 40% by weight aqueous solution of 
ammonium nitrate was used as a binder in place of distilled water, to 
prepare a catalyst. 
EXAMPLES XI-2-1 and XI-2-2 
(Tablet-forming method) 
A part of the suspension-J was evaporated and dried with stirriing under 
heat to produce a block state. The blocked product was dried in a drier 
under an air current at 200.degree. C. for 5 hours. This dried block was 
milled to not more than 100 mesh. 2% by weight of a carbon powder was 
added to the milled powder and the resulting mixture was formed into 
tablets having a diameter of 5 mm and height of 5 mm. The tablets were 
fired under an air current at 500.degree. C. for 6 hours to prepare a 
catalyst (XI-2-1). And then the same procedure was repeated to prepare a 
catalyst (XI-2-2). 
EXAMPLES XI-3-1 and XI-3-2 
(Extrusion method) 
A part of the suspension-J was evaporated and condensed until it was 
extrudable, and extruded to form extrudates having a diameter of 5 mm and 
height of 5 mm. The extrudates were fired under air current at 500.degree. 
C. for 6 hours to prepare a catalyst (XI-3-1). Then, the same procedure 
was repeated to prepare a catalyst (XI-3-2). 
EXAMPLE XI-4 
(Marmerizer-forming method) 
A part of the suspension-J was treated with externally applied heat for 
condensation until it was extrudable. And the product was extruded to form 
extrudates having a diameter of 6 mm and lengths of 4 to 7 mm, and then 
the extrudates were subjected to a marmerizer to form elliptic spheres 
having a breadth of 3 mm and length of 5 mm. The elliptic spheres were 
fired under air current at 500.degree. C. for 6 hours to prepare a 
catalyst (XI-4). 
EXAMPLE XI-5 
(Rolling particle-forming method) 
A part of the suspension-J was evaporated and dried with stirring under 
heat to solidify it into a block state. The resulting solid was dried in a 
drier at 200.degree. C. for 5 hours and milled to about 100 mesh to obtain 
a powder. At first, alpha-alumina having the average diameter of 1 mm was 
charged into a rolling particle-forming machine and then the above powder 
was charged into the machine. By the use of heated air at 80.degree. C. 
and distilled water as a binder, the mixture was formed into spherical 
particles having the average diameter of 5 mm. The particles were fired 
under an air current at 500.degree. C. for 6 hours to prepare a catalyst 
(XI-5). 
EXAMPLE XI-6 
(Pill-forming method) 
A part of the suspension-J was treated with externally applied heat for 
condensation thereof to obtain a soil-like product, 50% by weight of which 
was dissipated when it was fired at 500.degree. C. This product was formed 
into shapes having the average diameter of 5 mm by the use of a usual 
pill-forming machine. The resulting spherical product was fired under an 
air current at 500.degree. C. for 6 hours to obtain a catalyst (XI-6). 
REACTION TEST 
Catalysts XI-1 to XI-6 obtained in the above EXAMPLES (1,500 ml each) were 
charged respectively to steel reaction tubes having an internal diameter 
of 25.4 mm, and a mixture gas composed of 6% by volume of isobutylene, 
13.2% by volume of oxygen, 15% by volume of water vapor and 65.8% by 
volume of nitrogen was introduced thereinto to carry out reactions at 
reaction temperatures of 330.degree. to 340.degree. C. and at a space 
velocity of 1,600 hr.sup.-1. The results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Conver- Total 
Pore Re- sion yield 
Specific diameter 
action 
of Selectivity 
in 
surface 
Pore 
distri- 
temper- 
iso- Meth- 
single 
Ex- area volume 
bution 
ature 
butylene 
Meth- 
acrolein 
flow 
ample 
Forming method 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
acrolein 
acid (mol %) 
__________________________________________________________________________ 
XI-1-1 
Centrifugal flow 
30 0.420 
58 39 330 99.3 85.1 3.4 87.9 
coating method 
XI-1-2 
" 2.9 0.415 
56 40 330 99.5 86.0 3.0 88.6 
XI-2-1 
Tablet-forming 
1.8 0.312 
23 75 340 98.0 83.7 3.7 85.7 
method 
XI-2-2 
" 2.1 0.300 
20 78 340 97.5 84.2 3.2 85.2 
XI-3-1 
Extrusion method 
2.2 0.350 
35 63 340 98.6 84.0 3.5 86.3 
XI-3-2 
" 2.0 0.372 
31 66 340 98.1 84.4 3.0 85.7 
XI-4 
Marmerizer-forming 
2.1 0.342 
37 61 340 98.7 84.1 3.4 86.4 
method 
XI-5 
Rolling particle- 
2.7 0.372 
42 55 340 98.2 84.7 2.2 85.3 
forming method 
XI-6 
Pill-forming method 
2.6 0.321 
35 63 340 97.8 84.1 2.7 84.9 
__________________________________________________________________________ 
*.sup.1 Ratio (%) of pore volume consisting of pores having diameters in 
the range from 1 to 10 .mu.m to the entire pore volume 
*.sup.2 Ratio (%) of pore volume consisting of pores having diameters in 
the range from 0.1 to 1 (exclusive) .mu.m to the entire pore volume 
[EXAMPLE XII] 
(Preparation of catalyst and its reproducibility) 
A suspension-J was prepared in the same way as in EXAMPLE XI, and catalysts 
(EXAMPLES XII-1 to XII-6) were prepared by the use of the suspension-J and 
six different forming methods shown in Table 5 according to EXAMPLE XI. In 
each of EXAMPLES XII-1 to XII-6, four catalysts were prepared under the 
same conditions (batch Nos. 1 to 4) in order to test the presence or 
absence of the reproducibility of catalyst preparation. Tests of 
performance were carried out according to the method of EXAMPLES XI-1 to 
XI-6 series. With regard to EXAMPLE XII-1, the method of EXAMPLE XI-1-1 
was applied. The results are shown in Table 5. 
As is clear in Table 5, it is seen that the formation by a centrifugal flow 
coating method can give catalysts having smaller variation of physical 
values and high activity. The fact that the variation of physical values 
is small means that catalysts were prepared with good reproducibility. On 
the other hand, it is further seen that catalysts prepared by the other 
forming methods include those that have not physical values specified by 
the present invention although they were prepared in batches under 
entirely the same conditions, and that the catalyst performance thereof is 
inferior to that of the catalysts obtained by a centrifugal flow coating 
method. 
TABLE 5 
__________________________________________________________________________ 
Conver- Total 
Pore Re- sion yield 
Specific diameter 
action 
of Selectivity 
in 
surface 
Pore 
distri- 
temper- 
iso- Meth- 
single 
Ex- Batch 
area volume 
bution 
ature 
butylene 
Meth- 
acrolein 
flow 
ample 
Forming method 
No. 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
acrolein 
acid (mol 
__________________________________________________________________________ 
%) 
XII-1 
Centrifugal flow 
1 2.9 0.417 
58 40 330 99.2 85.3 3.6 88.2 
coating method 
2 3.0 0.420 
59 40 330 99.0 85.2 3.5 87.8 
3 2.9 0.418 
60 38 330 99.4 85.6 3.2 88.2 
4 3.1 0.420 
59 40 330 99.3 85.3 3.5 88.2 
XII-2 
Tablet-forming 
1 1.7 0.312 
20 77 340 98.1 83.6 3.5 85.4 
method 2 1.5 0.297 
19 80 340 97.6 83.1 3.5 84.5 
3 1.1 0.253 
24 75 340 97.2 83.7 3.6 84.9 
4 2.0 0.330 
18 80 340 98.2 82.2 3.2 85.8 
XII-3 
Extrusion method 
1 2.4 0.380 
35 63 340 98.9 84.1 3.3 86.4 
2 2.1 0.292 
31 66 340 98.1 82.7 3.4 84.5 
3 1.8 0.270 
38 59 340 97.6 83.6 3.3 84.8 
4 2.2 0.350 
30 66 340 98.5 82.1 3.2 84.0 
XII-4 
Marmerizer-forming 
1 2.5 0.301 
35 64 340 98.1 82.7 3.4 84.5 
method 2 2.0 0.295 
28 71 340 97.2 82.5 3.4 83.5 
3 2.2 0.300 
30 68 340 97.8 83.5 3.2 84.8 
4 2.6 0.312 
37 61 340 98.3 82.1 3.4 84.0 
XII-5 
Rolling particle- 
1 2.5 0.365 
41 58 340 98.2 84.1 3.5 86.0 
forming method 
2 2.9 0.400 
34 64 340 98.7 83.5 3.4 85.8 
3 2.1 0.312 
31 68 340 97.5 83.2 3.3 84.3 
4 2.6 0.354 
40 57 340 98.1 83.6 3.4 85.3 
XII-6 
Pill-forming method 
1 2.1 0.312 
28 71 340 97.6 82.7 3.3 83.9 
2 2.4 0.341 
31 68 340 97.1 83.6 3.3 84.4 
3 2.9 0.378 
34 64 340 98.1 83.1 3.3 84.8 
4 2.7 0.350 
39 60 340 96.5 84.2 3.3 84.5 
__________________________________________________________________________ 
*.sup.1 & *.sup.2 Same as the remarks to Table 4 
[EXAMPLE XIII] 
Preparation of catalyst material suspension 
EXAMPLE XI was repeated except that 230.9 g of rubidium nitrate and 50.5 g 
of potassium nitrate were used in place of cesium nitrate to obtain a 
suspension (the resulting suspension is referred to as suspension-K). 
EXAMPLE XIII-1 
(Centrifugal flow coating method) 
A part of the suspension-K was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 W.sub.2 Co.sub.7 Bi.sub.3 Fe.sub.1 
Si.sub.1.35 Rb.sub.0.4 K.sub.0.1. 
EXAMPLES XIII-2-1 and XIII-2-2 
(Tablet-forming method) 
A part of the suspension-K was treated in the same way as in EXAMPLE XI-2 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XIII-1 and XIII-2, 
reactions were carried out in the same way as in EXAMPLE XI. The results 
are shown in Table 6. 
[EXAMPLE XIV] 
Preparation of catalyst material suspension 
EXAMPLE XIII was repeated except that 21.0 g of lithium hydroxide and 127.5 
g of sodium nitrate were used in place of cesium nitrate and potassium 
nitrate to obtain a suspension (which is referred to as suspension-L). 
EXAMPLE XIV-1 
(Centrifugal flow coating method) 
A part of the suspension-L was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 W.sub.2 Co.sub.7 Bi.sub.3 Fe.sub.1 
Si.sub.1.35 Li.sub.0.1 Na.sub.0.3. 
EXAMPLES XIV-2-1 and XIV-2-2 
(Extrusion method) 
A part of the suspension-K was treated in the same way as in EXAMPLE XI-3 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XIV-1 and XIV-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
[EXAMPLE XV] 
Preparation of catalyst material suspension 
EXAMPLE XI was repeated except that 115.3 g of 85% orthophosphoric acid was 
added after ammonium paratungstate and that 532.7 g of thallium nitrate 
was used in place of cesium nitrate, to obtain a suspension (which is 
referred to as suspension-M). 
EXAMPLE XV-1 
(Centrifugal flow coating method) 
A part of the suspension-M was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 W.sub.2 Co.sub.10 Bi.sub.1 Fe.sub.1 
Si.sub.1.35 Tl.sub.0.4 P.sub.0.2. 
EXAMPLES XV-2-1 and XV-2-2 
(Marmerizer-forming method) 
A part of the suspension-M was treated in the same way as in EXAMPLE XI-4 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XV-1 and XV-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
[EXAMPLE XVI] 
Preparation of catalyst material suspension 
EXAMPLE XI was repeated except that 11.6 kg of nickel nitrate was used in 
place of cobalt nitrate and that 1.282 g of magnesium nitrate and 1,180.7 
g of calcium nitrate were used together with 195 g of cesium nitrate, to 
obtain a suspension (which is referred to as suspension-N). 
EXAMPLE XVI-1 
(Centrifugal flow coating method) 
A part of the suspension-N was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 W.sub.2 Ni.sub.8 Bi.sub.1 Fe.sub.1 
Si.sub.1.35 Cs.sub.0.2 Mg.sub.1.0 Ca.sub.1.0. 
EXAMPLES XVI-2-1 and XVI-2-2 
(Rolling particle-forming method) 
A part of the suspension-N was treated in the ame way as in EXAMPLE XI-5 to 
prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XVI-1 and XVI-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
[EXAMPLE XVII] 
Preparation of catalyst material suspension 
EXAMPLE XI was repeated except that 1,306.7 g of barium nitrate and 1,058.1 
g of strontium nitrate were used in place of magnesium nitrate and calcium 
nitrate to obtain a suspension (which is referred to as suspension-O). 
EXAMPLE XVII-1 
(Centrifugal flow coating method) 
A part of the suspension-O was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 W.sub.2 Ni.sub.8 Bi.sub.1 Fe.sub.1 
Si.sub.1.35 Cs.sub.0.2 Ba.sub.1.0 Sr.sub.1.0. 
EXAMPLES XVII-2-1 and XVII-2-2 
(Pill-forming method) 
A part of the suspension-O was treated in the same way as in EXAMPLE XI-6 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XVII-1 and XVII-2, 
reactions were carried out in the same way as in EXAMPLE XI. The results 
are shown in Table 6. 
[EXAMPLE XVIII] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in EXAMPLE 
XI, ammonium paratungstate was not used, the amount of ferric nitrate used 
was changed to 6.06 kg, the amount of cobalt ntirate used was changed to 
10.2 kg, the amount of cesium nitrate used was changed to 97.5 g, the 
amount of 20%-by-weight-concentrated silica sol used was changed to 16.5 
kg and 1,656 g of lead nitrate was added before the above silica sol, 
which gave a suspension. (The suspension is referred to as suspension-P). 
EXAMPLE XVIII-1 
(Centrifugal flow coating method) 
A part of the suspension-P was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 Co.sub.7 Bi.sub.1 Fe.sub.3 Si.sub.11 
Cs.sub.0.1 Pb.sub.1.0. 
EXAMPLES XVIII-2-1 and XVIII-2-2 
(Tablet-forming method) 
A part of the suspension-P was treated in the same way as in EXAMPLE XI-2 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XVIII-1 and XVIII-2, 
reactions were carried out in the same way as in EXAMPLE XI. The results 
are shown in Table 6. 
[EXAMPLE XIX] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in EXAMPLE 
XI, ammonium paratungstate and cesium nitrate were not used, the amount of 
ferric nitrate used was changed to 6.06 kg, 8.7 kg of nickel nitrate and 
399 g of titanium dioxide were used respectively in place of cobalt nirate 
and silica sol, 2.9 kg of antimony trioxide was added together with 
ammonium paramolybdate, and 753.4 g of stannic oxide and 399.0 g of 
tellulium dioxide were added before titanium dioxide, which gave a 
suspension. (The suspension is referred to as suspension-Q). 
EXAMPLE XIX-1 
(Centrifugal flow coating method) 
A part of the suspension-Q was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 Ni.sub.6 Bi.sub.1 Fe.sub.3 Ti.sub.1 
Sb.sub.2.0 Sn.sub.1 Te.sub.0.5. 
EXAMPLES XIX-2-1 and XIX-2-2 
(Extrusion method) 
A part of the suspension-P was treated in the same way as in EXAMPLE XI-3 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XIX-1 and XIX-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
[EXAMPLE XX] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in EXAMPLE 
XI, ammonium paratungstate was not used, the amount of cobalt nitrate used 
was changed to 7.3 kg, the amount of ferric nitrate used was changed to 
24.2 kg, 252.7 g of potassium nitrate was used in place of cesium nitrate 
and 1,875.6 g of aluminum nitrate was used in place of silica sol, which 
gave a suspension. (The suspension is referred to as suspension-R). 
EXAMPLE XX-1 
(Centrifugal flow coating method) 
A part of the suspension-R was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 Co.sub.5 Bi.sub.1 Fe.sub.12 Al.sub.1.0 
K.sub.0.5. 
EXAMPLES XX-2-1 and XX-2-2 
(Marmerizer-forming method) 
A part of the suspension-R was treated in the same way as in EXAMPLE XI-4 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalyst obtained in EXAMPLES XX-1 and XX-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
[EXAMPLE XXI] 
Preparation of catalyst material suspension 
In preparing a catalyst material suspension in the same way as in EXAMPLE 
XI, ammonium paratungstate was not used, 1,336.3 g of zirconyl nitrate was 
used in place of silica sol, the amount of cobalt nitrate used was changed 
to 8.7 kg and 1,435.2 g of manganese nitrate, 1,487.4 g of zinc nitrate 
and 664.5 g of niobium pentaoxide were used at the last step, which gave a 
suspension. (The suspension is referred to as suspension-S.) 
EXAMPLE XXI-1 
(Centrifugal flow coating method) 
A part of the suspension-S was treated in the same way as in EXAMPLE XI-1-1 
to prepare a catalyst. The ratio of elements other than oxygen in this 
catalyst oxide was Mo.sub.12 Co.sub.6 Bi.sub.1 Fe.sub.1 Zr.sub.1 
Cs.sub.0.4 Ce.sub.1 Mn.sub.1 Zn.sub.1 Nb.sub.0.5. 
EXAMPLES XXI-2-1 and XXI-2-2 
(Rolling particle-forming method) 
A part of the suspension-S was treated in the same way as in EXAMPLE XI-5 
to prepare a catalyst. 
REACTION TEST 
By the use of the catalysts obtained in EXAMPLES XXI-1 and XXI-2, reactions 
were carried out in the same way as in EXAMPLE XI. The results are shown 
in Table 6. 
TABLE 6 
__________________________________________________________________________ 
Conver- Total 
Pore Re- sion Selectivity 
yield 
Specific diameter 
action 
of (mol %) in 
surface 
Pore 
distri- temper- 
iso- Meth- 
single 
area volume 
bution ature 
butylene 
Meth- 
acrolein 
flow 
Example Forming method 
(m.sup.2 /g) 
(cc/g) 
A*.sup.1 
B*.sup.2 
(.degree.C.) 
(mol %) 
acrolein 
acid (mol 
__________________________________________________________________________ 
%) 
XIII 
XIII-1 
Centrifugal flow 
3.5 0.453 
59 38 330 98.8 85.7 4.0 88.6 
coating method 
XIII-2-2 
Tablet-forming 
2.1 0.334 
28 71 340 95.1 83.1 4.4 83.2 
XIII-2-2 
method 2.6 0.342 
23 76 340 97.7 82.6 4.3 84.8 
XIV XIV-1 Centrifugal flow 
3.7 0.400 
57 42 330 97.9 80.6 3.5 82.3 
coating method 
XIV-2-1 
Extrusion method 
2.7 0.351 
36 62 340 97.1 78.0 4.5 80.1 
XIV-2-2 2.5 0.312 
31 68 340 96.3 76.2 4.1 77.3 
XV XV-1 Centrifugal flow 
2.6 0.376 
53 45 330 95.0 86.0 2.2 83.8 
coating method 
XV-2-1 
Marmerizer-forming 
2.6 0.312 
32 67 340 94.7 84.1 2.1 81.6 
XV-2-2 
method 2.5 0.307 
30 69 340 94.0 84.0 1.9 80.7 
XVI XVI-1 Centrifugal flow 
3.0 0.357 
56 42 330 98.9 81.2 3.5 83.8 
coating method 
XVI-2-1 
Rolling particle- 
3.0 0.314 
42 56 340 98.0 79.5 3.2 81.0 
XVI-2-2 
forming method 
2.6 0.287 
37 61 340 97.2 79.2 3.1 80.0 
XVII 
XVII-1 
Centrifugal flow 
3.4 0.326 
62 37 330 98.1 79.3 3.5 80.5 
coating method 
XVII-2-1 
Pill-forming 
2.5 0.302 
41 56 340 96.2 78.1 4.1 79.1 
XVII-2-2 
method 2.4 0.298 
32 66 340 97.0 77.5 4.2 79.2 
XVIII 
XVIII-1 
Centrifugal flow 
3.2 0.321 
63 35 330 93.5 78.9 3.0 76.6 
coating method 
XVIII-2-1 
Tablet-forming 
1.6 0.301 
21 78 340 91.0 77.1 2.5 72.4 
XVIII-2-2 
method 1.4 0.278 
28 71 340 89.2 78.2 2.4 71.9 
XIX XIX-1 Centrifugal flow 
3.3 0.376 
62 36 330 89.6 78.1 3.0 72.7 
coating method 
XIX-2-1 
Extrusion method 
2.6 0.342 
41 57 340 89.1 76.0 2.5 69.9 
XIX-2-2 2.5 0.310 
29 69 340 88.0 75.1 3.0 68.7 
XX XX-1 Centrifugal flow 
2.9 0.362 
57 42 330 94.8 76.0 4.0 75.8 
coating method 
XX-2-1 
Marmerizer-forming 
2.8 0.314 
35 62 340 94.1 71.9 5.0 72.4 
XX-2-2 
method 2.4 0.276 
27 70 340 93.6 70.3 5.5 70.9 
XXI XXI-1 Centrifugal flow 
3.8 0.396 
64 35 330 93.2 74.0 6.0 74.6 
coating method 
XXI-2-1 
Rolling particle- 
3.5 0.351 
42 56 340 92.7 71.2 6.2 71.7 
XXI-2-2 
forming method 
3.2 0.306 
36 61 340 92.0 69.5 6.1 69.6 
__________________________________________________________________________ 
*.sup.1 & *.sup.2 Same as the remarks to Table 4 
[EXAMPLE XXII] 
A reaction was carried out by the use of the catalyst obtained in batch No. 
1 of EXAMPLE XII-1 and tertiary butanol in place of isobutylene. In the 
reaction test, EXAMPLE XII was repeated except that 6% by volume of 
tertiary butanol was used in place of isobutylene. (Accordingly, the gas 
after a dehydration reaction of tertiary butanol was composed, on an 
average, of 5.66% by volume of isobutylene, 12.45% by volume of oxygen, 
19.81% by volume of water vapor and 62.08% by volume of nitrogen. And the 
space velocity was 1,700 hr.sup.-1.) The results of the reaction were that 
the conversion ratio of tertiary butanol was 100 mole%, the selectivity to 
methacrolein was 84.9%, the selectivity to methacrylic acid was 3.4% and 
unreacted isobutylene was 1.3%. Based on this reaction, it is seen that 
the same result is obtained even if isobutylene is changed to tertiary 
butanol. 
[EXAMPLE XXIII] 
By the use of the catalyst obtained in batch No. 2 of EXAMPLE XII-1, the 
reaction test for a long period of time of 8,000 hours was carried out. 
Said reaction test was carried out in the same way as in EXAMPLE XII. The 
temperature at the beginning of the reaction was 330.degree. C. and it was 
sufficient to raise the reaction temperature by only 10.degree. C. during 
the period of 8,000 hours. The results of the reaction at the time after 
8,000 hours were that the conversion of isobutylene was 98.7 mol%, the 
selectivity to methacrolein was 85.3 mol% and the selectivity to 
methacrylic acid was 3.2 mol%.