AU603224B2 - Catalyst for oxidation of olefin or tertiary alcohol and process for production thereof - Google Patents

Description

AUSTRALIA

Patents Act 60O2244 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: 'This doument contains the arne: dmnents made under Section 49 and is correct for printing.

APPLICANT'S REFERENCE: Name(s) of Applicant(s): .a 3 Nippon Shokubai Kagaku Kogyo Co. Ltd

C

Address(es) of Applicant(s): 1, Koraibashi, Higashi-ku, Osaka,

JAPAN.

Address for Service is: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: CATALYST FOR OXIDATION OF OLEFIN OR TERTIARY ALCOHOL AND PROCESS FOR PRODUCTION THEREOF Our Ref 97190 POF Code: 1349/46755 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/l 1 1 0 r.

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 o 10 process for the production of said catalyst with good 0 0 reproducibility.

0 0" There are proposals for various catalysts for 00 c oc producing, from an olefin or tertiary alcohol (especially oS°oo tertiary butanol), the corresponding unsaturated aldehyde G0o0Dc 15 (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 C Vconcerned with selection of catalyst properties and production processes with reproducibility. For example, there are not a few 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 j 25 comprising molybedenum, bismuth and iron. However, none of these proposed catalysts are on a satisfactory level, k4 ias 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 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 PubliA.tion No. 26690/1973.

However, these catalysts are not satiofactory as ;y I

I

2 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 2,0008 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 S- 15 to the pore diameter, that the pores having a diameter 1- smaller than 100 should be less than 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 o 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 partcile-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 inventors' 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 2 surface area in the range from 1 to 20 m that it has a pore volume in the range from 0.1 to 1.0 cc/g 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 microns and from 0.1 to 1 (exclusive) microns.

Accordingly, the present invention provides a catalyst for producing, by catalytic gas phase oxidation of propylene, isobutylene or tertiary butanol, a corresponding unsaturated aldehyde and unsaturated carboxylic acid, said catalyst comprising molybdenum, iron and bismuth and having a specific surface area in the range from 1 to 20 m 2 a pore volume in the range from 0.1 to 1.0 cc/g, 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 1 (exclusive) micron, wherein the catalyst for oxidation of propylene has a pore diameter distribution in which the pore volume consisting of pores having pore diameters in the range from 0.1 to 1 (exclusive) micron is not less than 30% based on the entire pore volume and the pore volume consisting of pores having pore diameters in the range from 1 to 10 microns is not less than 20% based on the entire pore volume, and wherein in the catalyst for oxidation of isobutylene or tertiary butanol, the ratio of the pore volume consisting of pores having pore diameters in the range from 1 to 10 microns is greater than the ratio of the pore volume consisting of pores having pore diameters in the range 39 from 0.1 to 1 (exclusive) micron.

3 The present invention also provides a process for the preparing the above catalyst, comprising charging an unfired material powder into a centrifugal flow coating device to form particles having the average diameter of 2 to 10mm and then firing the particles thereby to obtain, with good reproducibility, the catalyst.

In the present invention, the well-balanced presence of pores having pore diameters of 1 to 10 microns and pores having pore diameters of 0.1 to 1 (exclusive) microns 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 1 (exclusive) microns is not less than 30%, preferably in the range from 45 to 80%, based on the 4665j, 3A

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r p p

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ii 4 entire pore volume and the pore volume consisting of pores having pore diamters in the range from 1 to 10/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 performace 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 mn should be greater than the ratio of the pore volume consisting of pores having pore diameters in the range from 0.1 to 1 (exclusive)Lm.

In general, a pore having a smaller pore diame ter 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 pores having pore Aiameters in the range of 0.1 to 1 (exclusiveuLml is not sufficient to obtain the aforementioned activity and selectivity, and the fairly larger ratio of the larger pores pores having core diameters in the range of 1 to 10wn) is necessary as well.

By forming an unfired catalyst material powder into pellets having the average diameter of 2 to 10mm 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 particleforming method, etc., are used for the preparation of spherical shapes, and an extrusion method, tablet-forming method, etc., are used for cyrindrical 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

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II: 5 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 methcd 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 chauning a powder of an unfired oxide composition -6not 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 succesive 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 i necessary. In the formation of particles, it is preferable to use, as a core, granules obtained by preforming a powder of catalyst per ne 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 dia- meter, 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 jthe 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, -7it has a composition represented by the following formula, MoaWbBicFedAeBfCgDhO x 0 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, alkali earth metal and thallium, C denotes at least one element selected from the group consisting of phosphorus, 1 0 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 0 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 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 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 molecualr oxygen, 0 to 60% by volume of water vapor and 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 to 450 0 C, at a pressure of an atmospheric pressure to 10 atm and at a spece velocity of t 8- -l 300 to 7,000hr 1

(STP).

The following Examples and Comparative Exan will illustrate the present invention more in detal, however, the present invention is not limited theretc In the present specification, the conversion, selecti and total yield in a single flow are respectively def as follows.

Conversion ratio (mol%) Nnmhr of mnlAP nf rpacte- nrnnvlpne.

iples .vity fined isobutylene or tertiary butanol Number of moles of charged propylene, isobutylene or tertiary butanol x 100 Selectivity (mol%) Number of moles of produced acrolein and acrylic acid or methacrolein and methacrylic acid Number of moles of reacted propylene, isobutylene or tertiary butanol x 100 Total yield of a single flow (mol%) Number of moles of produced acrolein and acrylic acid or methacrolein and methacrylic acid Number of moles of charged propylene, isobutylene or tertiary butanol x 100 L~j [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 L -9.

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 0 C with using distilled water as a binder, and formed into spherical particles having the average diameter of 5mm. These particles were dried in a drier at 120 0 C for 12 hours and then fired under an air current at 450 0 C for 6 hours to prepare a catalyst The ratio of elements other than oxygen in this catalyst oxide was Co 4 Bi FelW 2 Mol0Sil.

3 5

K

0 0 6 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 0 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 5mm and height of 5mm. The tablets were fired under air current at 450 0 C for 6 hours to prepare a catalyst Then, the same procedure was repeated to prepare a catalyst 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 dimeter of 5mm and height of 5mm. The extrudates were dried at 120°C for 12 hours and fired under air current ii. I'I~I 10 at 450 0 C for 6 hours to prepare a catalyst Then, the same procedure was repeated to prepare a catalyst EXAMPLES 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 0 C its solid content was 60% by weight). This product was extruded to form extrudates having a diamter of 6mm and lengths of 4 to 7mm, and then the extrudates were subjected to a marmerizer to form elliptic spheres having a breadth of 0, 3mm and length of 5mm. The elliptic spheres were dried at 120 0 C for 12 hours and fired under air current at 450 0 C for 6 hours to prepare a catalyst EXAMPLES 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 particleforming machine and heated air at 80°C and distilled i 25 water as a binder. The particles were dried at 120 0 C for 12 hours and then fired under air current at 450 0 C for 6 i hours to prepare a catalyst EXAMPLES I-6 (Pill-forming method) i ^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°C its solid content was 55% by weight). This product was formed into shapes having the average diamter of 5mm by the use of a usual pill-forming machine. This resulting spherical 11 product was dried at 120 0 C for 12 hours and then fired under air current at 450 0 C for 6 hours to obtain a catalyst REACTION TEST Catalysts I-i to 1-6 obtained in the above EXAMPLES (1,500 ml each) were charged respectively to steel reaction tubes having an internal diameter of 25.4mm, and a mixture gas composed of 7% by volume of propylene, 12.6% by volume of oxygen, 10% by volume of i 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 0 C fcr 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-i to 1-6 series, and catalysts (EXAMPLES II-1 to II-4) were prepared by using the suspensions-,, by using forming methods shown in Table 2 and according to EXAMPLE I. In each of EXAMPLES II-i to 11-4, 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 1-6. The results are shown in Table 2.

As is clear in Table 2, it is seen that the A 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 the specific surface area, pore volume and pore diameter specified by the present 12 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 meterial 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.

EXAMPLES 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 4 BilFelW 2 MolSi.

35 TI 04 Ba 0 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.

SEXAMPLE 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 4 BilFelW 2 Mo 1 0 Si 1 35 Cs 0 .02Ti 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.

w a,* -13- [EXAMPLE VI Preparation of catalyst material suspension The preparation of the catalyst material suspension for EXAMPLES I-i 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-l (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 Co4BilFelW 2 Mo 10 Sil.

3 5 Sr0.

0 6 EXAMPLES V-2-1 and V-2-2 (Marmerizer-forming method) The suspension-D was treated according to EXAMPLE I-4 to prepare catalysts.

[EYAMPLE 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 4 BilFelW 2 Mo l0 Sil.

3 5 Ca0.

06 Nb 0 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 VIII Preparation of catalyst material suspension In preparing a catalyst material suspension in the same way as in the preparation of the catalyst .1 .iil 14 suspension for EXAMPLES I-i 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-i to prepare a catalyst. The ratio of elements other than oxygen in this catalyst oxide was Co3NilBiFe 2 Mo2Si4.7P.0Rb0.1 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 l the same way as in the preparation 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 ammoniuim paratungstate. The resulting suspension is referred to az suspension-G.

EXAMPLE VIII-1 (Centrifugal flow coating method) The suspension-G was treated in the same way 25 as in EXAMPLE I-1 to prepare a catalyst. The ratio of elements other than oxygen in this catalyst oxide was Co3NilBilFe2Mo2Si4.7B2.0K Al.

0 3 1 1 2 12 4.7 2.0 0.2 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 i 15 the same way as in the preparation of the catalyst suspension for EXAMPLES I-1 to 1-6 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 Co3NilBi Fe2Mo2Si 4As. T 3 1 1 e 2

M

2 4.7 0.5 0 0 5 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) SThe suspension-H was treated according to EXAMPLE I-6 to prepare catalysts.

[EXAMPLE X] SThe preparation of the suspension for EXAMPLES I-i 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 1-6. The ii -16resulting catalyst had a specific surface area of 12.3m 2 a pore volume of 0.51cc/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 and the pore volume consisting of pores having pore 0 diameter in the range from 0.1 to 1(exclusivem 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%.

j L Table 1 Specific Pore Pore diameter Reaction Conversion Yield in single surface volume distribution tempera- of flow (mol%) EXAMPLE Forming method area ture propylene 2 *1 B *2Acrylic (m 2 (cc/g) A7 B* 2 (mol%) Acrolein acid Example I- coating method 10.6 0.460 35 62 310 98.7 85.4 catgletod: Example 1-2-1 Tablet-form-g 8.2 0.350 5 90 310 90.3 75.9 8.1 method Example 1-2-2 Tablet-forming 4.2 0.250 0 92 310 86.5 69.2 10.1 method Example 1-3-1 Extrusion method 8.7 0.380 10 85 310 92.3 78.5 Example 1-3-2 Extrusion method 3.5 0.230 0 97 310 90.0 75.1 9.8 Example 1-4 Marmerizer-forming 10.1 0.500 30 64 310 91.8 78.9 9.3 method Example 1-5 Rolling particle- 12.5 0.400 35 60 310 93.0 77.1 10.9 forming method Example 1-6 Pill-forming method 9.5 0.380 35 59 310 93.4 77.6 10.0 *1 RatioC%) of pore volume consisting of pores in the range from 1 to 10 to the entire having diameters pore volume *2 Ratio(%) of pore volume consisting of pores having diameters in the range from 0.1 to 1 (exclusive),/&m to the entire pore volume

L

r Table 2 Specific Pore Pore diameter Re- Conver- Yield in single surface volume distribution action sion of flow (mol%) EXAMPLE Forming method Batch area temper- propyl- No. 2 *1 *2 ature ene Acryi (m (cc/g) A B (OC) (mol%) Acrolein Arylic acid~ Centrifugal flow 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 it 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 11-2 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 11-3 Extrusion method 1 7.5 0.350 35 60 310 91.9 78.7 2 5.0 0. 270 45 47 310 87.1 76.2 3 8.1 0.360 37 G2 310 92.1 79.1 8.9 4 6.7 0.320 41 43 310 89.6 78.5 8.1 Eyample 11-4 Rolling particle- 1 11.7 0.420 27 68 310 93.5 78.6 9.2 E__mpleII-4 forminq method I 2 10.1 0.450 18 72 310 90.5 77.9 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 *1 *2 Same as the remarks to Table 1.

_j k Table 3 Specific Pore Pore diameter Reaction Conversion Yield in single surface volume distribution tempera- of flow (mol%) EXAMPLE Forming method area ture propylene 2 *1 B*2 Acrylic (m (cc/g) A B (OC) (mol%) Acrolein Aci acid Centrifugal flow 12.5 0.410 32 60 310 99.5 87.8 7.2 III-i_ coating method 111 111-2-1 Tablet-forming 10.2 0.320 31 61 310 93.1 77.3 10.2 method 111-2-2 Tablet-forming 7.8 0.230 45 46 310 87.9 74.2 9.3 III-2-2 method IV-i Centrifugal flow 9.2 0.430 45 50 310 91.0 82.3 IV 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-1 Centrifugal flow 10.5 0.430 35 59 310 98.3 88.9 6.1 coating method V V-2-1 Marmerizer-forming 9.2 0.350 30 65 310 92.7 78.8 V _V-2_1 method V-2-2 Marmerizer-forming 8.7 0.270 32 61 310 90.3 77.1 8.9 method VI-I Centrifugal flow 11.2 0.420 38 60 310 98.7 87.8 coating method VI VI-2-1 Rolling particle- 10.2 0.350 33 61 310 94.3 81.0 forming method I I VI-2-2 Rolling particle- 7.8 0.280 27 65 310 90.2 79.0 7.3 forming method I-1 Centrifugal flow 10.7 0.380 34 58 310 95.6 81.0 9.6 VII VII-I coating method I I 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 to be continued *1 *2 Same as the remarks to Table 1.

r7

L

Table 3 (continued) Specific Pore Pore diameter Reaction Conversion Yield in single surface volume distribution tempera- of flow (mol%/ EXMIIPLE Forming method area __-ture propylene 2t g (cg A B 2 (OC) Acrolein Acrylic Cm /g ccgacid VIII- Centrifugal flow 9.5 0.350 30 65 310 93.0 74.1 9.6 method VIII VII21Tablet-forming 9.0 0.310 10 82 310 1 89.3 71.4 8.3 VIII2-lmethod VIII-2-2 Tablet-forming 8.5 0.250 0 90 310 86.1 69.2 7.1 IX-l Centrifugal flow 10.3 0.420 34 60 310 97.2 81.6 6.3 method IX-2-1 Tablet-forming 9.7 0.320 30 59 310 90.1 75.7 6.1 IX-2-2 Tablet-forming 8.5 0.250 0 89 310 88.2 73.4 method IX-3-2 Extrusion method 9.0 0.370 27 68 310 93.1 76.1 7.1 Ix 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 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 _______forming method IX52Rolling particle- 9.1 0.350 44 54 310 92.7 76.5 6.9 IX52forming method IX-6-1 Pill-forming method 10.1 0.400 j31 65 310 91.6 75.3 7.2 IX-6-2 Pill-forming method 8.5 0.290 142 50 310 89.7 73.2 1 7.01 *1 *2 Same as the remarks to Table 1.

G Fi Ct 21 [EXAMPLE XI] Preparation of catalyst material suspension Cobalt nitrate (14.56kg) and 2.02kg 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 300ml of concentrated nitric acid and 1,200ml of distilled wacer.

Separately, while 30 liters of distilled water was heated with stirring, 10.59kg of ammonium paramolybdate and 2.65kg 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 390g of cesium nitrate in 1 liter of distilled water and 2.03 kg of trated 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 0 C for 5 hours and milled to not more than 100 mesh to obtain a powder.

At first, alpah-alumina particles having the average diameter of Imm were charged into a centrifugal flow coating device. And then the above powder was charged into the device blowing heated air at with using distilled water as a binder and formed into spherical particles having the average diameter of 5mm. The resulting spherical particles were fired under an air current at 500 0 C for 6 hours. The ratio of elements other than oxygen in this catalyst oxide was Mol 2

W

2 Col 0 BilFelSil.

3 5 Cs .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 a 'aI 4, 22 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 stirring under heat to produce a block state.

The blocked product was dried in a drier under an air current at 200 0 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 5mm and height of 5mm. The tablets were fired under an air current at 500 0 C for 6 hours to prepare a catalyst 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 dimeter of 5mm and height of The extrudates were fired under air current at 500 0 C for 6 hours to prepare a catalyst Then, the same S 20 procedure was repeated to prepare a catalyst (XI-3-2).

EXAMPLES 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 diamter of 6mm and lengths of 4 to 7mm, and then the extrudates were subjected to a marmerizer to form elliptic spheres having a breadth of 3mm and length of 5mm, The elliptic spheres were fired under air current at 500°C for 6 hours to prepare a catalyst (XI-4).

EXAMPLES 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 2000C for 5 hours and milled to about 100 mesh to obtain a powder. At first, alpha-almina having the average T- i 1 -23diameter of 1mm was charged into a rolling particleforming machine and then the above powder was charged into the machine. By the use of heated air at 80 0 C and distilled water as a binder, the mixture was formed into spherical particles having the average diameter of The particles were fired under an air current at 500 0

C

for 6 hours to prepare a catalyst EXAMPLES 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°C. This product was formed into shapes having the average diamter of 5mm by the use of a usual pill-forming machine. The resulting spherical product was fired under an air current at 500 0

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 25.4mm, 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 to 340 0 C and at a space velocity of 1,600hr-1. The results are shown in Table 4.

_1 1 L

CS-

'i 3i ,j 3.

r :i L-.

Table 4 Specific Pore Pore Re- Conver- Total surface volume diameter action sion Selectivity yield Ex- Forming method area distri- temper- of in ample 2 bution ature iso- Meth- single (m (cc/g) butylene Meth- acrolein flow *1 *2 (mol%) acrolein aci (mol%) A B XI-1-1 Centrifugal flow 3.0 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 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 *1 Ratio(%) of pore volume consisting of pores having diameters in the range from 1 to 10/,zm to the entire pore volume *2 Ratio(%) of pore volume ccnsisting of pores having diameters in the range from 0.1 to 1 (exclusive) zm to the entire pore volume 25 [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-l 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-l 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-l 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 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 Sthe 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.

L

L

yo Table Specific Pore Pore Re- Conver- Total surface volume diameter action sion Selectivity yield Ex- Forming method Batch area distri- temper- of in ample No. 2 bution ature iso- Meth- single (m (cc/g) (OC) butylene Meth- a le flow 1 *2 (mol%) acrolein acid (mol%) A 1 2.9 0.417 58 40 330 99.2 85.3 3.6 88.2 XII-1 Centrifugal flow 2 3.0 0.420 59 40 330 99.0 85.2 3.5 87.8 coating method 3 2.9 0.418 60 38 330 99.4 85.6 3.2 88.2 3.1 0.420 59 40 330 99.3 85.3 3.5 88.2 1 1.7 0.312 20 77 340 98.1 83.6 3.5 85.4 XII-2 Tablet-forming 2 1.5 0.297 19 80 340 97.6 83.1 3.5 84.5 method method 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 1 2.4 0.380 35 63 340 98.9 84.1 3.3 86.4 XII-3 Extrusion method 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 2.2 0.350 30 66 340 98.5 82.1 3.2 84.0 1 2.5 0.301 35 64 340 98.1 82.7 3.4 84.5 XII-4 Marmerizer-forming 2 2.0 0.295 28 71 340 97.2 82.5 3.4 83.5 method ethod 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 to be continued *1 *2 Same as the remarks to Table 4 L_ i r i Table 5 (continued) Specific Pore Pore Re- Conver- Total surface volume diameter action sion Selectivity yield Ex- Forming method Batch area distri- temper- of ample No. 2 bution ature iso- Meth)-- single (M Ccc/g) (OC) butylene Meth- acrolein flow *2 (mol%) acrolein acid (M01l%) 1 2.5 0.365 41 58 340 98.2 84.1 3.5 86.0 Rolling particle- 2 2.9 0.400 34 64 340 98.7 83.5 3.4 85.8 formin metho fomn ehd3 2.1 0.312 31 68 340 97.5 83.2 3.3 84.3 4 2.6 0.354 40 157 1340 98.1 83.6 3.4 85.3_ 1 2.1 0.312 28 71 340 97.6 82.7 3.3 83.9 XII-6 Pill-forming method 2 2.4 0.341 31 68 340 97.1 83.6 3.3 84.4 3 1 2.9 0.378 34 64 340 98.1 83.1 3.3 84.8 4 2.7 0.350 39 160 340 96584.2 3.3 84.5 *1 *2 Same as the remarks to Table 4 28 [EXAMPLE XIII] Preparation of catalyst material suspension EXAMPLE XI was repeated except that 230.9g of rubidium nitrate and 50.5g 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 Mol 2

W

2 Co 7 Bi 3 FelSi .35Rb0.4KO.1 12 2 7 3 1 1.35 0.4 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 SEXAMPLE XIII was repeated except that 21.0g of lithium hydroxide and 127.5g 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 122Co7Bi3FelSil.35i0.1Na0.3 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 Lr- 29 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 115.3g of 85% orthophosphoric acid was added after ammonium paratungstate and that 532.7g 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 Sratio of elements other than oxygen in this catalyst oxide was Mol 2

W

2 ColBilFelSil 35

TI

0 .4P0.2 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 1,282g of magnesium nitrate and 1,180.7g of calcium nitrate were used together with 195g 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 l 2

W

2 Ni 8 BilFelSil.

3 5 Cs0.2Mgl.0Ca 1 .0.

i EXAMPLES XVI-2-1 and XVI-2-2 (Rolling particle-forming method) A part of the suspension-N 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 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

XVIII

Preparation of catalyst material suspension EXAMPLE XI was repeated except that 1,306.7g of barium nitrate and 1,058.1g 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-0 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 2

W

2 Ni 8 BiFelSi 3 5 Cs02Bal.

0 Srl.

EXAMPLES XVII-2-1 and XVII-2-2 (Pill-forming method) A part of the suspension-0 was treated in the same way as in EXAMPLE XI-6 to prepare a catalyst.

S 25 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 6.06kg, the amount of cobalt nitrate used was changed to 10.2kg, the amount of cesium nitrate used was changed 1 ~e 31 to 97.5g, the amount of silica sol used was changed to 16.5kg and 1,656g 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 Mol2Co 7 BilFe 3 SillCs0.1Pbl.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 6.06kg, 8.7kg of nickel nitrate and 399g of titanium dioxide were used respectively in place of cobalt nitrate and silica sol, 2.9kg of antimony trioxide was added together with ammonium paramolybdate, and 753.4g of stannic oxide and 399.Og 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 Mol2Ni6Bi Fe3TiSb2.0SnlTe0.5' 32 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 SIn 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 7.3kg, the amount of ferric nitrate used was changed to 24.2kg, 252.7g of potassium nitrate was used in place of cesium nitrate and 1,875.6g 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 1 2 Co 5 BilFel 2 Al..

0

K

0 EXAMPLES XX-2-1 and XX-2-2 (Marmerizer-forming method) ji 25 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 catalysts 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, 1,336.3g of zirconyl nitrate was used in place i i i 33 of silica sol, the amount of cobalt nitrate used was changed to 8.7kg and 1,435.2g of manganese nitrate, 1,487.4g of zinc nitrate and 664.5g 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 Mo2Co 6 Bi 1 FelZr Cs0.4CelMnZn Nb0.

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

S° 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.

2;71- 4' ~v.

Table 6 Specific Pore Pore Re- Conver- Total surface volume diameter action sion Selectivity yield Forming method area distri- temper- of 0/ in Example (2/g bution ature iso- Meth- single Cm/) (cc/g) (OC) butylene Meth- acrolein flow A*1 *2 acrolein acid (mol%) XII- Centrifugal flow 3.5 0.453 59 38 330 98.8 85.7 4.0 88.6 XIII XIII-2-2 Taltfrig2.1 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 4.2 84.8 XIV-l Centrifugal flow 3.7 0.400 57 42 330 97.9 80.6 3.5 82.3 coating methodII XrIV XIV-2-1 Exrso ehd2.7 0 .351 36t 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 XV1 Centrifugal flow 2.6 0.376 53 45 330 95.0 86.0 2.2 83.8 coating method amrzrfrig 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 80.7J to be continued- *1 *2 Sam as the remarks to Table 4 0 04.4 4.40 4.

4. S 0 4. 4.

4. 4.

Table 6 (continued) Specific Pore Pore Re- Conver- Total surface volume diameter action sion Selectivity yield Forming method area diti tme-of(o% in Example 2 bution ature .SO Methr- single (M (cc/g) (OC) butylene Meth- aoei lw *1 *2(mol%) acrolein acrid M0% IB acid__ XVIl1 Centrifugal flow 3.0 0.357 56 42 330 98.9 81.2 3.5 83.8 coating methodI

I

XVI 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-l Centrifugal flow 3.4 0.326 62 37 330 98.1 79.3 3.5 80.5 coating method XVII XVII-2-1 ilfomn 2.5 0.302 41 56 340 96.2 78.1 4.1 79.1 1 XVII-2-2 method 2.4 0.298 32 66 340 97.0 77.5 4.2 79.2 XVIII-1 Centrifugal flow 3.2 0.321 63 35 330 93.5 78.9 3.0 76.6 coating methodII XI XVIII-2-1l alt-omn 1.6 0.301 21 78 340 91.0 77.1 2.5 72.4 XVIII-2-2 method 1.4 T 0.278 28 71 340 89.2 78.2 2.4 71.9 to be continued *1 *2 Same as the remarks to Table 4

I

Table 6 (continued) specific Pore Pore Re- Conver- Total surface volume~ diameter action sion Selectivity, yield Forming method area distri- temper- of (MOM% in Example 2 bution ature iso- Mt- single (M (cc/g) 0 C) butylene Meth- acrolein flow *1T *2 (imol%)e acrolein acid (0% XIX-l Centrifugal flow 3.3 0.376 62 36 330 89.6 78.1 3.0 72.7 method XIX XIX-2-1 2.6 0.342 41 57 340 89.1 76.0 2.5 69.9 Extrusion method XIX-2-2 j 2.5 0.310 29 69 340 88.0 75.1 3.0 68.7 XX-l Centrifugal flow 2.9 0.362 57 42 330 94.8 76.0 4.0 75.8 coating method___ XX 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-1 Centrifugal flow 3.8 0.396 64 35 330 93.2 74.0 6.0 74.6 XXI XXI-2-1l. .5 2 5 4 27 7. 6.2 71.7 Rolling particle-3. 035 42 6 30 9.712 XXI-2-2 forming method 3.2 0.306 1 36 61 340 1 92.0 69.5 JT 6.1 1 69.61 *1 *2 Same as the remarks to Table 4 Ji I '1 37 [EXAMPLE XXIII 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 1,700hr1.) 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 metahcrylic acid was 3.4% and unreacted isobutylene was 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 0 C and it was sufficient to raisi the reaction temperature by only 10 0 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%.

I

IL

A:

Claims (4)

1. A catalyst for producing, by catalytic gas phase oxidation of propylene, isobutylene or tertiary butanol, a corresponding unsaturated aldehyde and unsaturated carboxylic acid, said catalyst comprising molybdenum, iron and bismuth and having a specific surface area in the range from 1 to 2 m a pore volume in the range from 0.1 to 1.0 cc/g, and a pore diameter distribution in which the pore diameters are collectively distributed in the range of each of from 1 to microns and from 0.1 to 1 (exclusive) micron, wherein the cataivst for oxidation of propylene has a pore diameter distribution in which the pore volume consisting of pores o 4. O. having pore diameters in the range from 0.1 to 1 (exclusive) micron is not less than 30% based on the entire pore volume and the pore volume consisting of pores having pore diameters in the range from 1 to 10 microns is not less than 20% based on the entire pore volume, and wherein in the catalyst for oxidation of isobutylene or tertiary butanol, the ratio of the pore volume consisting of pores having pore diameters in 0 the range from 1 to 10 microns is greater than the ratio of o0 the pore volume consisting of pores having pore diameters in the range from 0.1 to 1 (exclusive) micron. S4*A

2. A process for preparing the catalyst of claim 1 comprising charging an unfired material powder into a centrifugal flow coating device to form particles having the a average diameter of 2 to 10mm and then firing the particles thereby to obtain, with good reproducibility, the catalyst.

3. A catalyst according to claim 1 substantially as herein described in relation to any one of the Examples, but excluding the Comparative Examples.

4. A process according to claim 2 substantially as herein described in relation to any one of the Examples, but excluding the Comparative Examples. DATED: 7 August, 1990. PHILLIPS ORMONDE FITZPATRICb ATTORNEYS FOR:- _a^AC d -1 d NIPPON SHOKUBAI KAGAKU KOGYO CO., LTD. l .865i 38 ~1