JP2012045516A - Method of manufacturing catalyst for manufacturing unsaturated aldehyde and/or unsaturated carboxylic acid and the catalyst, and method of manufacturing acrolein and/or acrylic acid using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently and stably manufacturing a catalyst having excellent mechanical strength for manufacturing respectively corresponding unsaturated aldehyde and/or unsaturated carboxylic acid by performing catalytic gas phase oxidation on propylene, isobutylene or TBA under the presence of molecular oxygen.SOLUTION: In the method of manufacturing the catalyst carrying a catalytic active component containing molybdenum, bismuth and iron as essential components by an inert carrier, powder and granular product of the catalytic active component and/or its precursor and the inert carrier are continuously supplied to a carrying treatment device used in a carrying treatment process, and the supply amount (per volume) of the powder and granular product of the catalytic active component and/or its precursor is controlled to a range of 1 to 10 times per hour relative to the volume of the carrying treatment device.

Description

  The present invention relates to a method for producing a catalyst for producing an unsaturated aldehyde and / or unsaturated carboxylic acid, specifically, at least one selected from propylene, isobutylene or tertiary butyl alcohol (hereinafter sometimes referred to as “TBA”). A method for producing a catalyst suitable for producing a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by catalytic gas phase oxidation in the presence of molecular oxygen in the presence of molecular oxygen as a raw material, and using the obtained catalyst The present invention relates to a process for producing these unsaturated aldehydes and / or unsaturated carboxylic acids.

  Conventional catalysts used for producing acrolein and / or acrylic acid by vapor-phase catalytic oxidation of propylene, or catalysts used for producing methacrolein and / or methacrylic acid by vapor-phase catalytic oxidation of isobutylene or TBA As a production method, many proposals for supporting a catalytically active component on an inert carrier have been made.

For example, an unfired catalyst raw material powder containing molybdenum, iron, and bismuth is put into a centrifugal fluidized coating apparatus, granulated to an average diameter of 2 to 10 mm, and fired. 5 to ²⁰ m ² / g, the pore volume is in the range of 0.3 to 0.9 cc / g, and the pore diameter distribution is 1 to 10 μm and 0.1 to 0.9 μm. A method of obtaining a catalyst having a distribution concentrated in each range (Patent Document 1), a metal oxide in which five elements of molybdenum, bismuth, iron, cobalt and thallium have a specific atomic ratio, and the specific surface area of the metal oxide In which an inert carrier is coated with a powder of 10 to 20 m ² / g, containing molybdenum and bismuth as catalytic active components and having an average diameter of 2 to 200 μm A method of using a certain inorganic fiber as a supporting aid in the range of 0.5 to 50% by weight based on the catalytically active substance (Patent Document 3), a catalyst having a catalytically active component supported on a carrier, and an average of the catalyst A catalyst having a particle size of 4 to 16 mm, an average particle size of the support of 3 to 12 mm, a calcination temperature of 500 to 600 ° C., and a loading amount of the catalytic active component on the support of 5 to 80 wt% (Patent Document 4), molybdenum and A dry mixture is prepared from the starting compound of the elemental component of the catalytically active oxide containing bismuth, heat treated at a temperature of 150 to 350 ° C. to form a precursor, and the support is wetted with water and then contacted with the precursor A precursor layer deposited on the surface of a wet support, dried and finally calcined at a temperature of 400-600 ° C. to obtain a catalyst in which the support has a ring geometry (patent) Reference 5) It has been disclosed.

  Moreover, as a carrying | support processing apparatus to be used, a centrifugal fluid coating apparatus (patent document 1), a rolling granulator (patent document 4), a rocking mixer (patent document 5), etc. are known, for example.

Japanese Patent Laid-Open No. 63-200839 Japanese Patent Laid-Open No. 2-25443 Japanese Patent Laid-Open No. 6-381 JP-A-10-28877 JP-T-2004-515337

  However, although all of the catalysts obtained by the above prior art are estimated to have improved mechanical strength to some extent, the yield during the production of the catalyst, the particle size distribution of the obtained catalyst, and the stability of the catalyst performance Until is not considered at all. Further, in the conventional method as a loading method, a fixed amount of inert carrier and a fixed amount of catalytically active component powder are charged all at once into a loading treatment device, loaded and treated, and the catalyst obtained each time is loaded into the device. Since it is a so-called batch system, it is necessary to repeat a series of operations from preparation to removal several times in order to produce a quantity of several tons to several tens of tons like an industrial scale. There is a problem that is low. Therefore, a method for efficiently and stably producing a catalyst having higher mechanical strength is desired.

  The object of the present invention is to solve the above-mentioned problems of the prior art, and to produce at least one compound selected from propylene, isobutylene or TBA as a raw material, and subject the corresponding unsaturated aldehyde by catalytic gas phase oxidation in the presence of molecular oxygen. Another object of the present invention is to provide a method for producing a catalyst suitable for producing an unsaturated carboxylic acid, specifically, a method for efficiently and stably producing a catalyst having excellent mechanical strength.

  As a result of intensive studies to solve the above problems, the present inventors have responded by catalytic vapor phase oxidation using at least one compound selected from propylene, isobutylene or TBA as a raw material in the presence of molecular oxygen. In the process for producing a molybdenum-bismuth-iron-based supported catalyst for producing an unsaturated aldehyde and / or unsaturated carboxylic acid, the catalyst active component and / or The precursor particles (hereinafter sometimes simply referred to as “catalytically active component particles”) and the inert carrier are continuously supplied to the supporting treatment apparatus, and the catalytically active component particles at that time are supplied. It was found that a catalyst having high mechanical strength can be produced efficiently and stably by setting the supply amount of the product within a specific range. Furthermore, the catalytically active component granular material and the inert carrier are continuously supplied to a supporting treatment device such as a rolling granulator used in the supporting treatment step, and the resulting supported catalyst or its precursor ( Hereinafter, it may be simply referred to as “support”.) By continuously discharging the support from the support processing apparatus, the support is made from the charging of the catalytically active component granular material and the inert carrier as compared with the conventional batch type. As a result, the present inventors have found that a series of operations such as extraction can be greatly reduced.

  The unsaturated aldehyde and / or unsaturated carboxylic acid production catalyst according to the present invention is produced by the production method of the present invention.

  Furthermore, the method for producing an unsaturated aldehyde and / or unsaturated carboxylic acid according to the present invention comprises catalytic vapor phase oxidation using at least one compound selected from propylene, isobutylene or TBA as a raw material in the presence of molecular oxygen. In the production of the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid, it is achieved by using the catalyst of the present invention.

  According to the present invention, at least one compound selected from propylene, isobutylene or TBA is used as a raw material, and the corresponding unsaturated aldehyde and / or unsaturated carboxylic acid is produced by catalytic gas phase oxidation in the presence of molecular oxygen. Therefore, it is possible to efficiently and stably produce a catalyst having excellent mechanical strength.

  Hereinafter, although the manufacturing method of the catalyst concerning this invention and the manufacturing method of unsaturated aldehyde and / or unsaturated carboxylic acid using the catalyst obtained by this method are demonstrated in detail, the scope of the present invention is restrained by these explanations. The present invention is not limited to the following examples, and can be appropriately modified and implemented without departing from the spirit of the present invention.

  The method for producing an unsaturated aldehyde and / or unsaturated carboxylic acid production catalyst according to the present invention comprises the above-mentioned carrying treatment in a carrying treatment step of carrying a catalytically active component containing molybdenum, bismuth and iron as essential components on an inert carrier. The catalytically active component granular material and the inert carrier are continuously supplied to the supporting treatment device in the process, and the catalytically active component granular material is 1 hour relative to the capacity of the supporting processing device on a volume basis. It is important to supply in the range of 1 to 10 times, preferably 2 to 8 times. Here, the capacity of the loaded processing apparatus is the maximum allowable amount under the use conditions of the processing container. For example, when the processing container is used with a certain inclination angle (angle of the processing container central axis with respect to the horizontal plane). , Equal to the volume of water entering the inclined processing vessel. As a processing container of the said carrying | support processing apparatus, it is 10-70 degrees normally, Preferably it is used with the inclination angle of 20-60 degrees.

  By continuously supplying the catalytically active component particles and the inert carrier to the supporting treatment apparatus, the catalytically active component particles are sequentially supported on the inert carrier to form a carrier. As the loading amount increases, the particle size of the carrier increases, and the coefficient of friction with the processing vessel of the supporting processing device decreases, so that a new catalyst that gradually flows to the upper layer in the supporting processing device and is continuously supplied. Active ingredient powders, inert carriers, and those with a small loading amount flow to the lower layer because of their small particle size and large friction coefficient. The carrier having a desired carrying amount or a desired particle size is discharged beyond the weir (rim) of the processing vessel by the inclination of the carrying processing device, the depth of the processing vessel, the number of rotations, or a combination thereof, and is discharged. The carrier can be obtained continuously by collecting the carrier. That is, “continuously” in the present invention means that it is not a batch type.

  When the supply amount of the catalytically active component granular material per 1 hour of the above-described carrying processing apparatus capacity is less than 1 time, the yield is lowered, for example, a plurality of carriers are stuck together to form one lump. In addition, the mechanical strength is also lowered, which is not preferable. On the other hand, when the number is more than 10 times, the particle size distribution of the obtained support and thus the catalyst is expanded, or the catalyst in which the granular material is not supported on the carrier and is granulated only with the granular material (hereinafter referred to as “no core”). In addition, the yield decreases and the mechanical strength of the catalyst also decreases, which is not preferable.

  In the present invention, the catalytically active component granular material and the inert carrier are continuously supplied. In the initial stage of starting the supporting treatment process, the catalytically active component granular material and the inert carrier supporting treatment device It is not always necessary to start the supply to For example, only a part of the inert carrier is charged in advance in the supporting treatment apparatus, and then the supply of the catalytically active component powder and the remaining inert carrier is started, or the supply of the catalytically active component powder is started first. Then, the catalytically active component powder and the inert carrier may be continuously supplied in the majority of the supporting treatment process, such as starting the supply of the inert carrier later. Among them, in order to start the supporting treatment more smoothly, a method in which a part of the inert carrier is previously charged in the supporting treatment apparatus and then the catalytically active component powder and the remaining inert carrier are continuously supplied is preferable. . In that case, it is preferable that the amount of the inert carrier charged in the supporting treatment apparatus in advance is charged 0.1 to 0.9 times the capacity of the supporting processing apparatus.

Further, when the catalytically active component powder and the inert carrier are continuously supplied, the ratio of the supply amount (volume basis) (the supply amount of the catalytically active component granular material: the supply amount of the inert carrier) is 1. : 0.3 to 1: 1.5 is preferable.
The supply device for the catalytically active component granular material and the inert carrier is not particularly limited as long as the supply amount can be adjusted, such as a vibratory feeder or a belt feeder.

The supporting treatment apparatus is not particularly limited as long as the method of the present invention can be applied, but it is preferable to use a rolling granulator from the scale of the apparatus and the ease of handling. The capacity of the supported processing apparatus is set according to the required production amount and the processing capacity of the supported processing apparatus and cannot be specified unconditionally. However, on the industrial scale, it is usually several tens of dm ³ to several m ³ . A capacity carrying processor is used.

As the catalytically active component containing molybdenum, bismuth and iron as essential components used in the present invention, a composite oxide represented by the following general formula (1) is preferably used.
_{Mo 12 Bi a Fe b A c} B d C e D f O x (1)
(Where Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc The element, O is oxygen, a, b, c, d, e, f and x represent the atomic ratios of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 < b ≦ 20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a numerical value determined by the oxidation state of each element.
As a method for producing the catalyst according to the present invention, the catalytically active component granular material and the inert carrier are continuously supplied to the above-described supporting treatment apparatus, and the supply amount of the catalytically active component granular material is based on volume. It is generally used for the preparation of known unsaturated aldehyde and / or unsaturated carboxylic acid production catalysts except that it is controlled within the range of 0.1 to 1.0 times the capacity of the supported treatment apparatus per hour. It can be manufactured according to the method.

  Specifically, the raw materials for the catalytically active component represented by the general formula (1) include oxides, hydroxides, ammonium salts, nitrates, carbonates, sulfates, organic acid salts and the like of each component element. A salt, an aqueous solution thereof, a sol, or a compound containing a plurality of elements can be used.

  These raw materials are mixed with water to form an aqueous solution or an aqueous slurry (hereinafter sometimes referred to as “starting raw material mixed solution”).

  Next, if necessary, the obtained starting material mixture is dried by various methods such as heating and decompression to obtain a catalytically active component precursor. As a drying method by heating, for example, a powdery catalytically active component precursor can be obtained using a spray dryer, a drum dryer or the like, or air or nitrogen can be used using a box-type dryer, a tunnel-type dryer or the like. It is also possible to obtain a block-like or flake-like catalytically active component precursor by heating in an inert gas or other air stream such as nitrogen oxide. In addition, once the starting material mixture is concentrated and evaporated to dryness to obtain a cake-like solid, a method of further heat-treating the solid can be adopted, and the obtained catalytically active component precursor can be used. Furthermore, the method of baking and making it into a baked product is also employable. As a drying method by reduced pressure, for example, a block or powdery catalyst active component precursor can be obtained using a vacuum dryer.

  The obtained catalytically active component precursor or calcined product is made into a granular material having an appropriate particle size through a pulverization step and a classification step as necessary. The catalytically active component powder obtained in this way is sent to the subsequent supporting treatment step, where it is supported on an inert carrier to obtain a support. The particle size of the catalytically active component granular material is not particularly limited, but is preferably 500 μm or less in view of excellent handling properties such as ease of handling, uniformity of the supported material, and good yield.

  Examples of the inert carrier include alumina, silica, silica-alumina, titania, magnesia, steatite, cordierite, silica-magnesia, silicon carbide, silicon nitride, zeolite, and the like. There is no restriction | limiting in particular also about the shape, A thing of well-known shapes, such as spherical shape, cylindrical shape, and ring shape, can be used.

  In the supporting treatment step, a supporting aid or a binder for improving the supporting state can be used. Specific examples include organic compounds such as ethylene glycol, glycerin, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, butyl alcohol or phenols, water, nitric acid, ammonium nitrate, and ammonium carbonate. These supporting aids and binders may be sprayed or impregnated in an inert carrier before supporting in advance, or may be supplied by spraying or spraying into the apparatus during the supporting process, or a combination of both. May be.

  Further, for the purpose of forming appropriate pores in the catalyst, a pore-forming agent or inorganic fibers may be added for the purpose of improving the mechanical strength of the catalyst. The pore-forming agent is not particularly limited, and starch, cellulose, urea, polyvinyl alcohol, melamine cyanurate and the like can be used, and the inorganic fiber is not particularly limited and includes glass fiber, ceramic fiber, metal Fibers, mineral fibers, carbon fibers and the like can be used. As for the addition method, as long as it can be uniformly dispersed or contained in the catalytically active component, it can be added to the starting mixed solution, or the catalytically active component fine particles and the inorganic fibers can be mixed in the granular state. Any method can be used. Of course, as long as it can be dispersed or dissolved in the above-mentioned supporting aid or binder, it can be used together with the supporting aid or binder.

  The carrier obtained in the supporting treatment step is sent to the subsequent drying step and / or firing step.

  In the drying process, the carrier can be dried by heating in a stream of inert gas such as air or nitrogen or other nitrogen oxides using a commonly used box-type dryer, tunnel-type dryer or the like. The drying temperature is 80 to 300 ° C, preferably 130 to 250 ° C, and the drying time is preferably 1 to 20 hours.

  In the firing step, the firing temperature is 350 ° C. to 600 ° C., preferably 400 ° C. to 550 ° C., more preferably 420 ° C. to 500 ° C., and the firing time is preferably 1 to 20 hours. The firing atmosphere may be an oxidizing atmosphere, but a molecular oxygen-containing gas atmosphere is preferable, and it is particularly preferable to perform the firing step under the flow of the molecular oxygen-containing gas. Air is suitably used as the molecular oxygen-containing gas. In addition, calcining may be performed after the drying step, and in the case of using the previously calcined catalytically active component particles for supporting, the calcining step is not necessarily required, and only the drying step may be performed. In addition, there is no restriction | limiting in particular as a baking furnace used by a baking process, What is necessary is just to use the box-type baking furnace or tunnel type baking furnace etc. which are generally used.

  If necessary, a sieving step may be provided after the supporting treatment step or after the drying step or firing step, but it is preferably performed after the supporting step treatment from the viewpoint of recycling described later. In that case, the carrier that does not satisfy the desired loading rate or particle size that has been sieved may be recycled to the loading step or may be separately loaded so as to obtain the desired loading rate or particle size. There is no limitation in particular as a sieving apparatus, For example, a net sieve, a punching metal, a specific gravity sorter, a roller-type sorter etc. can be used, You may use combining two or more apparatuses.

  As for the reactor used for producing unsaturated aldehyde and / or unsaturated carboxylic acid by catalytic gas phase oxidation of propylene, isobutylene or TBA using molecular oxygen in the present invention, as long as it is a fixed bed reactor Although there is no particular limitation, a fixed bed multitubular reactor is particularly preferable. The inner diameter of the reaction tube is usually 15 to 50 mm, more preferably 20 to 40 mm, and still more preferably 22 to 38 mm.

  Each reaction tube of the fixed-bed multitubular reactor does not necessarily need to be filled with a single catalyst, and a plurality of conventionally known types of catalysts (each may be referred to as a “reaction zone”) are provided. It is also possible to fill as much as possible. For example, a method of filling a plurality of catalysts having different occupied volumes as disclosed in JP-A-4-217932 so that the occupied volume decreases from the raw material gas inlet side to the outlet side, or JP-A-10-168003 A method of filling a plurality of catalysts having different loading rates such as from the raw material gas inlet side to the outlet side so that the loading rate increases, or a part of the catalyst as disclosed in JP-A-2005-320315 is inactive. A method of diluting with a simple carrier or a combination of these may be employed. At this time, the number of reaction zones is appropriately determined depending on the reaction conditions and the scale of the reactor. However, if the number of reaction zones is too large, problems such as complicated packing of the catalyst may occur. About 2-6 is desirable.

The reaction conditions in the present invention are not particularly limited, and any conditions generally used for this type of reaction can be used. For example, the raw material gas is 1-15% by volume, preferably 4-12% by volume propylene, isobutylene or TBA, 0.5-25% by volume, preferably 2-20% by volume molecular oxygen, 0-30% by volume. Preferably, a mixed gas consisting of 0 to 25% by volume of water vapor and the balance of an inert gas such as nitrogen is 300 to 5,000 hr ⁻¹ under a pressure of 0.1 to 1.0 MPa at a temperature range of 250 to 450 ° C. What is necessary is just to contact a catalyst with the space velocity of (standard state).

  The grade as the reaction raw material gas is not particularly limited. For example, when propylene is used as the raw material, polymer grade or chemical grade propylene can be used. Also, a propylene-containing mixed gas obtained by propane oxidative dehydrogenation reaction can be used. If necessary, air or oxygen can be added to this mixed gas.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, for convenience, “parts by mass” may be simply referred to as “parts”. The conversion rates and yields in the examples and comparative examples were determined by the following equations.
Conversion rate [mol%]
= (Mole number of reacted starting material) / (Mole number of supplied raw material) × 100
Selectivity [mol%]
= (Total number of moles of unsaturated aldehyde formed and unsaturated carboxylic acid formed) / (Number of moles of reacted starting material) × 100
Yield [mol%]
= (Total number of moles of unsaturated aldehyde produced and unsaturated carboxylic acid produced) / (Number of moles of starting material fed) x 100
[Bulk specific gravity of active ingredient powder and inert carrier]
A 100 ml graduated cylinder is filled with a catalytically active component and / or a precursor thereof or an inert carrier, and tapped on a rubber cushion until there is no change in the volume. The volume and mass of the catalytically active component and / or its precursor or inert carrier filled in the graduated cylinder at that time were measured to determine the bulk density (g / ml).
[Measuring mechanical strength of catalyst]
A stainless steel reaction tube having an inner diameter of 25 mm and a length of 5000 mm is installed in the vertical direction, and the lower end of the reaction tube is closed with a stainless steel receiving plate having a thickness of 1 mm. About 50 g of the catalyst is dropped into the reaction tube from the upper end of the reaction tube, the stainless steel receiving plate at the lower end of the reaction tube is removed, and the catalyst is gently extracted from the reaction tube. The extracted catalyst was sieved with a sieve having an opening of 5 mm, and the mass of the catalyst remaining on the sieve was weighed.
Mechanical strength of catalyst [mass%]
= Mass of catalyst remaining on sieve / mass of catalyst dropped from top of reaction tube x 100
<Example 1>
(Catalyst preparation)
In 4000 parts of distilled water, 1000 parts of ammonium paramolybdate, 2.9 parts of potassium nitrate, and 340 parts of 20% by mass silica sol were dissolved (solution A). Separately, 50 parts of 65% by weight nitric acid was added to 600 parts of distilled water to dissolve 252 parts of bismuth nitrate, 879 parts of cobalt nitrate, 238 parts of iron nitrate and 275 parts of nickel nitrate (Liquid B). B liquid was added to the obtained A liquid, and stirring was continued for 30 minutes. Thereafter, 133 parts of alumina was added, and stirring was further continued for 1 hour to obtain a slurry. The obtained slurry was heated and stirred to obtain a cake-like solid, and the obtained solid was dried at 220 ° C. for about 3 hours in an air atmosphere to obtain a dried product. The obtained dried product was pulverized to 500 μm or less to obtain a powder of a catalytically active component precursor.

About 40 kg of a silica-alumina spherical carrier having an average particle size of 4.0 mm was charged into a rolling granulator (maximum allowable amount = 0.059 m ³ ) having a diameter of 1.3 m, a weir height of 500 mm, and an inclination angle of 55 °. While rotating at a rotation speed of 15 rpm, the powder of the catalytically active component precursor was continuously charged at a supply rate of 0.56 m ³ / hr using a belt-type feeder while spraying a 15% by mass ammonium nitrate aqueous solution as a binder. At the same time, the same carrier as that previously charged in the apparatus was continuously fed using a belt-type feeder at a supply rate of 0.21 m ³ / hr. Under this condition, the supporting treatment was continuously performed for about 8 hours. The carrier discharged beyond the weir (rim) of the rolling granulator was sorted using a specific gravity sorter, and then calcined at 470 ° C. for about 6 hours in an air atmosphere to obtain catalyst 1. The catalyst 1 was supported at a rate of about 145 mass%, the yield was 92 mass%, and the metal element composition excluding oxygen was as follows.
Catalyst 1: Mo ₁₂ Bi _1.1 Co _6.4 Fe _1.25 Ni ₂ Si _2.4 Al _5.5 K _0.06
The carrying rate and yield were obtained from the following formula.
Loading rate [mass%]
= (Mass of catalyst obtained-mass of carrier used) / mass of carrier used x 100
Yield [mass%]
= Mass of the obtained support / (mass of the catalytically active component used + mass of the carrier used) × 100
Table 1 shows the mechanical strength of each condition and the obtained catalyst 1.
[Reactor]
A reactor made of a stainless steel reaction tube having a total length of 3000 mm and an inner diameter of 25 mm and a shell for flowing a heat medium covering the same was prepared in the vertical direction. The catalyst 1 obtained from the upper part of the reaction tube was dropped and filled so that the layer length was 2800 mm.
[Oxidation reaction]
From the lower part of the reaction tube filled with the catalyst, a mixed gas consisting of 7.5% by volume of propylene, 14% by volume of oxygen, 6% by volume of water vapor and the balance of an inert gas such as nitrogen at a space velocity of 2000 hr ⁻¹ (standard state). The propylene oxidation reaction was carried out. At that time, the heat medium temperature (reaction temperature) was adjusted so that the propylene conversion was about 97 mol%. The results are shown in Table 2.
<Example 2>
In Example 1, the rotational speed of the rolling granulator was changed to 10 rpm, the supply amount of the powder of the catalytically active component was changed to 0.093 m ³ / hr, and the supply amount of the carrier was changed to 0.026 m ³ / hr. In the same manner, Catalyst 2 was obtained. The supported rate of the catalyst 2 was about 165% by mass, the yield was 89% by mass, and the metal element composition excluding oxygen was the same as that of the catalyst 1. Table 1 shows each condition and the mechanical strength of the obtained catalyst 2.

The obtained catalyst 2 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2.
<Comparative Example 1>
In Example 2, except for changing the supply amount of the powder of catalytically active component 0.80 m ³ / hr, the feed rate of the carrier to 0.22 m ³ / hr similarly to yield the catalyst 3. The supported rate of the catalyst 3 was about 145% by mass, the yield was 69% by mass, and the metal element composition excluding oxygen was the same as that of the catalyst 1. Table 1 shows the mechanical strength of each condition and the obtained catalyst 3. The powder of the catalytically active component was not supported on the carrier and many nuclei were granulated only with the powder, resulting in a significantly low yield. Further, the particle size variation was large and the mechanical strength was low.

The obtained catalyst 3 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2. Since the mechanical strength was low, the combustion activity was high and the yield was low.
<Example 3>
(Catalyst preparation)
1000 parts of ammonium paramolybdate, 3.8 parts of potassium nitrate, and 425 parts of 20% by mass silica sol were dissolved in 4000 parts of distilled water (A liquid). Separately, 65 parts by weight of 65% by weight nitric acid was added to 600 parts of distilled water to dissolve 275 parts of bismuth nitrate, 550 parts of cobalt nitrate, 267 parts of iron nitrate and 412 parts of nickel nitrate (Liquid B). B liquid was added to the obtained A liquid, and it stirred for 1 hour, and obtained the slurry. The obtained slurry is heated and stirred to obtain a cake-like solid. The obtained solid is dried at 200 ° C. for about 2 hours in an air atmosphere, and then fired at 470 ° C. for about 6 hours in an air atmosphere to obtain a fired product. Obtained. The obtained fired product was pulverized to 500 μm or less to obtain a powder of a catalytically active component. About 40 kg of a silica-alumina spherical carrier having an average particle size of 4.0 mm was charged into a rolling granulator (maximum allowable amount = 0.045 m ³ ) having a diameter of 1.3 m, a weir height of 500 mm, and an inclination angle of 60 °. While rotating at a rotation speed of 15 rpm, the powder of the catalytically active component was charged at a supply rate of 0.25 m ³ / hr using a belt-type feeder while spraying a 15% by mass aqueous ammonium nitrate solution as a binder. Ten minutes after the introduction of the catalytically active component, the same carrier as that previously charged in the apparatus was introduced using a belt feeder at a supply rate of 0.37 m ³ / hr. Under this condition, the supporting treatment was continuously performed for about 8 hours. The carrier discharged beyond the weir (rim) of the rolling granulator was sorted using a specific gravity sorter, and then dried at 220 ° C. for about 3 hours in an air atmosphere to obtain catalyst 4. The catalyst 4 loading was about 35% by mass, the yield was 95% by mass, and the composition of metal elements excluding oxygen was as follows.
Catalyst 4: Mo ₁₂ Bi _1.2 Co ₄ Fe _1.4 Ni ₃ Si ₃ K _0.08
Table 1 shows the mechanical strength of each condition and the catalyst 4 obtained.

The obtained catalyst 4 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2.
<Example 4>
In Example 3, except for changing the rotational speed of the tumbling granulator 12 rpm, the supply amount of the powder of catalytically active component 0.33 m ³ / hr, the feed rate of the carrier to 0.25 m ³ / hr, In the same manner, Catalyst 5 was obtained. The supported rate of the catalyst 5 was about 70% by mass, the yield was 94% by mass, and the metal element composition excluding oxygen was the same as that of the catalyst 4. Table 1 shows each condition and the mechanical strength of the obtained catalyst 5.

The obtained catalyst 5 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2.
<Comparative example 2>
In Example 3, except for changing the supply amount of the powder of catalytically active component 0.041m ³ / hr, the feed rate of the carrier to 0.026 ³ / hr similarly to yield the catalyst 6. The loading ratio of the catalyst 6 was about 70% by mass, the yield was 66% by mass, and the metal element composition excluding oxygen was the same as that of the catalyst 4. Table 1 shows each condition and the mechanical strength of the obtained catalyst 6. A large number of catalysts in which a plurality of carriers were stuck together to form one lump were generated, resulting in a low yield. Further, the particle size variation was large and the mechanical strength was low.

The obtained catalyst 6 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2. Since the mechanical strength was low, the combustion activity was high and the yield was low.
<Example 5>
(Catalyst preparation)
1000 parts of ammonium paramolybdate and 2.4 parts of potassium nitrate were dissolved in 5000 parts of distilled water (solution A). Separately, 65 parts by weight of 65% by weight nitric acid was added to 600 parts of distilled water to dissolve 366 parts of bismuth nitrate, 783 parts of cobalt nitrate and 191 parts of iron nitrate (Liquid B). B liquid was added to the obtained A liquid, and stirring was continued for 30 minutes. Thereafter, 164 parts of tungsten oxide and 120 parts of alumina were added, and the mixture was further stirred for 1 hour to obtain a slurry. The obtained slurry was heated and stirred to obtain a cake-like solid, and the obtained solid was dried at 160 ° C. for about 5 hours in an air atmosphere to obtain a dried product. The obtained dried product was pulverized to 500 μm or less to obtain a powder of a catalytically active component precursor. About 40 kg of a silica-alumina spherical carrier having an average particle size of 4.0 mm was charged into a rolling granulator having a diameter of 1.3 m, a weir height of 500 mm, and an inclination angle of 55 °. While rotating at a rotational speed of 10 rpm, the powder of the catalytically active component precursor was continuously charged at a supply rate of 0.17 m ³ / hr using a belt-type feeder while spraying a 15% by mass ammonium nitrate aqueous solution as a binder. At the same time, the same carrier as that previously charged in the apparatus was continuously fed using a belt feeder at a supply rate of 0.11 m ³ / hr. Under this condition, the supporting treatment was continuously performed for about 8 hours. The carrier discharged beyond the weir (rim) of the rolling granulator was sorted using a specific gravity sorter, and then calcined at 470 ° C. for about 6 hours in an air atmosphere to obtain catalyst 7. The catalyst 7 was supported at a rate of about 100% by mass, the yield was 93% by mass, and the metal element composition excluding oxygen was as follows.
Catalyst 7: Mo ₁₂ Bi _1.6 Co _5.7 Fe _1.0 W _1.5 Al _5.0 K _0.05
Table 1 shows each condition and the mechanical strength of the catalyst 7 obtained.

The obtained catalyst 7 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2.
<Example 6>
In Example 5, the rotational speed of the rolling granulator was changed to 15 rpm, the supply amount of the catalyst active component precursor powder was changed to 0.50 m ³ / hr, and the supply amount of the carrier was changed to 0.18 m ³ / hr. Was prepared in the same manner to obtain Catalyst 8. The loading ratio of the catalyst 8 was about 190% by mass, the yield was 92% by mass, and the metal element composition excluding oxygen was the same as that of the catalyst 7. Table 1 shows each condition and the mechanical strength of the catalyst 8 obtained.

  The obtained catalyst 8 was charged into a reactor in the same manner as in Example 1, and an oxidation reaction was performed under the same conditions. The results are shown in Table 2.

Claims (7)

  A method for producing an unsaturated aldehyde and / or unsaturated carboxylic acid production catalyst comprising a catalytically active component containing molybdenum, bismuth and iron as essential components on an inert carrier, wherein the catalytically active component is provided on the inert carrier. And / or in the supporting treatment step for supporting the precursor particles, the catalyst active component and / or the precursor particles and the inert carrier are added to the supporting treatment apparatus used in the supporting treatment step. The catalyst active component and / or precursor particles thereof are supplied in a range of 1 to 10 times (volume basis) per hour with respect to the capacity of the supported processing apparatus while being continuously supplied. To produce an unsaturated aldehyde and / or unsaturated carboxylic acid production catalyst.   The catalyst for producing an unsaturated aldehyde and / or unsaturated carboxylic acid according to claim 1, wherein the supported catalyst or precursor thereof obtained in the supporting treatment step is continuously discharged from the supporting treatment apparatus. Manufacturing method.   In the supporting treatment step, after supplying at least a part of the inert carrier to the supporting treatment device in advance, supply of the catalytically active component and / or precursor particles and the remaining inert carrier to the supporting treatment device. The manufacturing method of the catalyst for unsaturated aldehyde and / or unsaturated carboxylic acid manufacture of Claim 1 or 2 which starts.   Ratio of supply amount (volume basis) of catalytically active component and / or precursor powder and inert carrier continuously supplied into the supporting treatment apparatus (catalytic active component and / or precursor powder thereof) The production method according to any one of claims 1 to 3, wherein a supply amount of the granules: a supply amount of the inert carrier is 1: 0.3 to 1: 1.5. The manufacturing method according to any one of claims 1 to 4, wherein the catalytically active component is represented by the following general formula (1).
_{Mo 12 Bi a Fe b A c} B d C e D f O x (1)
(Where Mo is molybdenum, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is at least one element selected from alkali metals, alkaline earth metals and thallium, C is at least one element selected from tungsten, silicon, aluminum, zirconium and titanium, D is at least one element selected from phosphorus, tellurium, antimony, tin, cerium, lead, niobium, manganese, arsenic, boron and zinc The element, O is oxygen, a, b, c, d, e, f and x represent the atomic ratios of Bi, Fe, A, B, C, D and O, respectively, and 0 <a ≦ 10, 0 < b ≦ 20, 2 ≦ c ≦ 20, 0 <d ≦ 10, 0 ≦ e ≦ 30, 0 ≦ f ≦ 4, and x is a numerical value determined by the oxidation state of each element.   A catalyst for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid produced by the method according to any one of claims 1 to 5.   In producing a corresponding unsaturated aldehyde and / or unsaturated carboxylic acid by using catalytic at least one compound selected from propylene, isobutylene or tertiary butyl alcohol as a raw material, and catalytic vapor phase oxidation in the presence of molecular oxygen. A method for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid, wherein the catalyst according to claim 6 is used.