JP2015188800A - Molded catalyst and method for producing the same as well as method for producing unsaturated aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded catalyst capable of obtaining an unsaturated aldehyde from olefin and/or alcohol at a high yield and a method for producing the same, and to provide a method for producing an unsaturated aldehyde using a molded catalyst.SOLUTION: There is provided a method for producing a molded catalyst used in producing an unsaturated aldehyde from olefin and/or alcohol, which comprises: a step of preparing a raw material slurry; a step of drying the raw material slurry to obtain a dried product; a step of calcining the dried product to obtain a calcined product; a step of molding the calcined product in a state where 0.10 to 5.0 mass% of a molding auxiliary agent is added based on 100 mass% of the calcined product to obtain a molded product; and a step of mainly calcining the molded product under an atmosphere of an oxygen concentration of 0.10 to 18 vol.% to obtain the molded catalyst.

Description

  The present invention relates to a molded catalyst, a method for producing the same, and a method for producing an unsaturated aldehyde.

  Conventionally, many proposals have been made on a method for producing a molded catalyst used in producing an unsaturated aldehyde from olefin and / or alcohol.

  For example, Patent Literature 1 discloses a molding method in which graphite is added as a molding aid at the time of catalyst preparation, and humidity is adjusted with water or ammonium nitrate water so that adhesion between powders is dense. Further, Patent Document 2 discloses a manufacturing method in which firing is performed at a temperature lower than the combustion temperature of graphite in order to facilitate control of heat generation during firing in a molding method in which graphite is added as a molding aid during catalyst preparation. Yes.

JP-A-60-150834 JP 2005-161309 A

  However, in the catalyst obtained by the above method, the addition of a molding aid has a role as a lubricant for promoting adhesion between powders as an improvement in moldability, but the activity and selectivity of the catalyst are often impaired. . When a molded body containing the temporary fired body and the molding aid is fired in an air atmosphere, heat is generated when the molding aid is scattered. This heat generation is considered to deteriorate the activity and selectivity of the resulting molded catalyst.

  In addition, if the pre-fired body and the molding aid are not uniformly mixed and the molding aid is segregated, an excessive thermal load is applied to the catalyst. As a result, the specific surface area of the catalyst is reduced, and the activity and selectivity of the catalyst are reduced. Due to these problems, the yield of unsaturated aldehyde by the molded catalyst is not yet sufficient, and development of a catalyst capable of obtaining the target product in high yield and a method for producing the same are desired.

  The present invention has been made in view of the above problems, a molded catalyst capable of obtaining an unsaturated aldehyde from an olefin and / or alcohol in high yield, a method for producing the same, and an unsaturated aldehyde using the molded catalyst. It aims at providing the manufacturing method of.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a method for producing a molded catalyst having a predetermined process, and have completed the present invention.

That is, the present invention is as follows.
[1]
A method for producing a molded catalyst for use in producing an unsaturated aldehyde from olefin and / or alcohol,
A preparation step of preparing a raw slurry;
A drying step of drying the raw slurry to obtain a dried body;
A pre-baking step of pre-baking the dried body to obtain a pre-fired body;
A molding step of obtaining a molded body by molding in a state where 0.10 to 5.0% by mass of a molding auxiliary agent is added to 100% by mass of the temporarily fired body;
A main firing step of subjecting the molded body to main firing in an atmosphere having an oxygen concentration of 0.10 to 18% by volume to obtain the molded catalyst,
A method for producing a molded catalyst.
[2]
The method for producing a shaped catalyst according to [1] above, wherein the shaped catalyst has a specific surface area of 2.0 to 4.0 m ² / g.
[3]
The method for producing a molded catalyst according to [1] or [2] above, wherein the raw slurry contains molybdenum, bismuth, iron, an element having an ionic radius larger than 0.96 kg, and cobalt.
[4]
The method for producing a molded catalyst according to any one of [1] to [3], wherein the temperature of the dried body is gradually raised from 100 ° C to 300 ° C in the temporary calcination step.
[5]
In the molding step, the molded body is obtained by tableting in a state where 0.10 to 5.0 mass% of the molding aid is added to 100 mass% of the temporarily fired body, [1] to [4] ] The manufacturing method of the shaping | molding catalyst of any one of.
[6]
The method for producing a molded catalyst according to any one of [1] to [5], wherein the molded catalyst has a composition represented by the following composition formula (1).
_{Mo 12 Bi a Fe b A c} Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius greater than 0.96 （(except potassium, cesium and rubidium), and Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1.0 ≦ a ≦ 5.0, and Fe atomic ratio b is 1 .5 ≦ b ≦ 6.0, the atomic ratio c of the element A is 1.0 ≦ c ≦ 5.0, the atomic ratio d of Co is 1.0 ≦ d ≦ 8.0, and the element B The atomic ratio e of 0 ≦ e <3.0, The atomic ratio f of element C is 0 ≦ f ≦ 2.0, the ratio of Fe / Co is 0.80 ≦ b / d, and g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. is there.)
[7]
It has the oxidation process which oxidizes an olefin and / or alcohol, and manufactures an unsaturated aldehyde using the molding catalyst manufactured by the manufacturing method of the molding catalyst of any one of [1]-[5] above. And a method for producing an unsaturated aldehyde.
[8]
A molded catalyst produced by the production method according to any one of [1] to [5] above.

  ADVANTAGE OF THE INVENTION According to this invention, the shaping | molding catalyst which can obtain unsaturated aldehyde from olefin and / or alcohol with a high yield, its manufacturing method, and the manufacturing method of unsaturated aldehyde using a shaping | molding catalyst can be provided.

  Hereinafter, the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is.

[Method for producing molded catalyst]
The method for producing a molded catalyst according to this embodiment is a method for producing a molded catalyst used when producing an unsaturated aldehyde from olefin and / or alcohol, and includes a preparation step for preparing a raw slurry, and drying the raw slurry. A drying step for obtaining a dry body, a pre-baking step for pre-baking the dry body to obtain a pre-fired body, and adding 0.10 to 5.0% by weight of a molding aid to 100% by weight of the pre-fired body A molding step for obtaining a molded body by molding in this state, and a main firing step for subjecting the molded body to main firing in an atmosphere having an oxygen concentration of 0.10 to 18% by volume to obtain the molded catalyst.

  The method for producing a molded catalyst according to the present embodiment has the above-described configuration, thereby suppressing deterioration in catalyst performance and reduction in specific surface area caused by heat generation when a molded body containing a molding aid is finally fired. This gives a shaped catalyst that can yield high unsaturated aldehydes in high yield.

[Preparation process]
The preparation step is a step of preparing a raw slurry. The raw material slurry preferably contains a catalyst raw material for each metal element constituting the molded catalyst. Specifically, molybdenum, bismuth, cerium, iron, cobalt, potassium, cerium, rubidium, cesium, nickel, manganese, copper, zinc, magnesium, calcium, strontium, barium, tin, lead, lanthanum, praseodymium, neodymium, europium It is preferable that molybdenum, bismuth, iron, an element having an ionic radius larger than 0.96 Å, and cobalt are more preferable.

  The catalyst raw material for these metal elements is not particularly limited. For example, ammonium salts, nitrates, hydrochlorides, organic acid salts, oxides, hydroxides, or carbonates of these metal elements that are soluble in water or nitric acid. Etc.

  Content of the metal element in raw material slurry becomes like this. Preferably it is 10-50 mass%, More preferably, it is 20-40 mass%, More preferably, it is 25-35 mass%. When the content of the metal element is within the above range, the uniformity of the raw material slurry and the production amount of the oxide catalyst tend to be improved together.

  The raw slurry may contain a water-soluble polymer and / or an organic acid. By including the water-soluble polymer and / or organic acid, the raw slurry can be more uniformly dispersed. Although it does not specifically limit as a water-soluble polymer, For example, polyethyleneglycol, methylcellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide etc. are mentioned. The organic acid is not particularly limited, but examples thereof include polycarboxylic acids such as amines, aminocarboxylic acids, oxalic acid, malonic acid, and succinic acid, and organic acids such as glycolic acid, malic acid, tartaric acid, and citric acid. Etc.

  The content of the water-soluble polymer or organic acid is preferably 0 to 30% by mass, more preferably 1.0 to 20% by mass, and further preferably 2.0 to 10% by mass with respect to the metal oxide. %. When the content of the water-soluble polymer or organic acid is within the above range, the uniformity of the raw material slurry and the production amount of the oxide catalyst tend to be improved.

  The method for preparing the raw slurry is not particularly limited as long as it is a commonly used method. For example, a solution in which an ammonium salt of molybdenum is dissolved in warm water, and water or bismuth, cerium, iron, cobalt, alkali metal as nitrate. The method of preparing by mixing the solution dissolved in nitric acid aqueous solution is mentioned.

[Aging process]
The method for producing a molded catalyst may have an aging step for aging the raw slurry. “Aging” means stirring the raw material slurry at a predetermined temperature for a predetermined time. This aging increases the viscosity of the raw material slurry, relieves sedimentation of the solid components in the raw material slurry, and is particularly effective in suppressing the unevenness of the components in the subsequent drying process. The catalytic activity such as the raw material conversion rate and selectivity of the oxide catalyst tends to be better.

  The aging temperature is preferably 30 to 90 ° C, more preferably 40 to 80 ° C, and further preferably 45 to 70 ° C. When the aging temperature is within the above range, the viscosity of the raw material slurry is increased, the sedimentation of the solid component in the raw material slurry is alleviated, and particularly effective in suppressing the unevenness of the components in the next drying step, The catalytic activity such as the raw material conversion rate and selectivity of the composite oxide catalyst which is the final product obtained tends to be further improved.

  The aging time is preferably 2 to 12 hours, more preferably 3 to 8 hours. When the aging time is 2 hours or more, the activity and selectivity of the resulting molded catalyst tend to be further improved. On the other hand, when the aging time is 12 hours or less, the productivity tends to be further improved.

  Any method can be adopted as the stirring method, and examples thereof include a method using a stirrer having a stirring blade and a method using external circulation using a pump.

  The median diameter of the solid particles in the raw material slurry obtained by the preparation step or the aging step is preferably 0.10 to 10 μm, more preferably 0.5 to 6 from the viewpoint of reducing the angle of repose of the temporarily fired body. It is 0.0 μm, and more preferably 1.0 to 4.0 μm. When the median diameter of the raw material slurry is 10 μm or less, the yield of unsaturated aldehyde tends to be further improved. Moreover, when the median diameter of the raw material slurry is 0.10 μm or more, the raw material slurry viscosity is lowered, and the line from the raw material slurry to the dryer can be further suppressed. The method for adjusting the median diameter of the solid particles in the raw slurry is not particularly limited. For example, the solid particles in the raw slurry may be pulverized using a homogenizer or the like. The median diameter (average particle diameter) of the solid particles in the raw slurry is measured with a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter, product name “LS230”), and the volume average (median diameter) is measured. ).

[Drying process]
A drying process is a process of drying a raw material slurry and obtaining a dried body. Although it does not specifically limit as a drying method, For example, the evaporative drying method, the spray drying method, the reduced pressure drying method etc. are mentioned. Among these, the spray drying method is preferable from the viewpoint of easily adjusting the median diameter of the dried body, the angle of repose of the calcined body, and the specific surface area of the molded catalyst.

  The spray-drying method can be performed by a centrifugal method, a two-fluid nozzle method, a high-pressure nozzle method, or the like that is usually performed industrially. As the drying heat source, it is preferable to use air heated by steam or an electric heater. Moreover, the temperature at the dryer inlet of the spray dryer is preferably 150 to 400 ° C, more preferably 200 to 300 ° C, and further preferably 230 to 260 ° C.

  The median diameter of the dried body is preferably 35 to 65 μm, more preferably 40 to 60 μm, and still more preferably 45 to 55 μm. When the median diameter of the dried product is 35 μm or more, aggregation of the dried product particles can be suppressed, the bulk density of the calcined product is appropriately increased, and the crushing strength of the resulting molded catalyst tends to be further improved. Further, when the median diameter of the spray-dried product is 65 μm or less, the activity of the molded catalyst tends to be further improved. The median diameter (average particle diameter) of the dried product is obtained as a volume average (median diameter) by measuring the particle diameter distribution using a laser diffraction / scattering particle size distribution measuring device (trade name “LS230” manufactured by Beckman Coulter). be able to.

[Temporary firing process]
The temporary firing step is a step of obtaining a temporary fired body by temporarily firing the dried body. The temporary firing can be performed using a firing furnace such as a rotary furnace, a tubular furnace, a tunnel furnace, a muffle furnace, or a fluidized firing furnace. It is preferable to use a rotary furnace from the viewpoint of productivity as an industrial catalyst. The method for pre-baking the dried body varies depending on the raw material used.

  The repose angle of the calcined body is preferably 20 ° to 35 °, preferably 23 ° to 32 °, and more preferably 25 to 30 °. When the angle of repose of the temporarily fired body is in the above range, the fluidity of the temporarily fired body is further improved, and thus the temporarily fired body and the molding aid tend to be mixed more uniformly. Moreover, when the angle of repose of the calcined product is 20 ° or more, there is a tendency that the decrease in the yield of unsaturated aldehyde due to the bulk density of the molded catalyst becoming too high can be further suppressed. The angle of repose of the calcined product can be controlled by adjusting the median diameter of the raw slurry and the dried product, the calcining conditions, and the like. Moreover, the angle of repose of the temporarily fired body can be measured by the method described in the examples.

  From the viewpoint of obtaining a temporarily fired body having such an angle of repose, it is preferable to gradually raise the temperature of the dried body from 100 to 300 ° C. in the temporary firing step. When the temperature is raised from 100 to 300 ° C., iron nitrate, bismuth nitrate, cerium nitrate, cobalt nitrate, and ammonium nitrate generated in the spray drying process can be decomposed and evaporated. In the present specification, “gradual increase in temperature” means that the temperature is increased to a set temperature over a period of 2.0 hours or more. The heating rate need not always be constant. From the viewpoint of reducing the angle of repose, the temperature raising time is preferably 2.0 h or more, more preferably 2.5 h to 8 h, and further preferably 3 h to 7 h. When the temperature rising time is within the above range, the angle of repose of the obtained temporary fired body tends to be further reduced. Moreover, it can suppress that dissolution and decomposition | disassembly of nitrate and ammonium nitrate advance rapidly because temperature rising time is 2.0 h or more. As a result, it is possible to suppress the temporary fired body from being cracked, the shape from being deteriorated, and the angle of repose from being increased.

  After raising the temperature to 300 ° C, it is preferable to hold the dried body at a temperature of 300 ° C to 350 ° C for 1 to 24 hours.

[Molding process]
The molding step is a step of obtaining a molded body by molding in a state where 0.10 to 5.0% by mass of a molding aid is added to 100% by mass of the temporarily fired body. The mixing method of the calcined product and the molding aid is not particularly limited, and can be performed using a known apparatus such as a double-arm kneader, a ribbon mixer, a Henschel mixer, or the like. By using a molding aid, it is possible to obtain a molded catalyst that is less prone to cracking and cracking during use.

  Although it does not specifically limit as a shaping | molding adjuvant, For example, inorganic fiber, such as cellulose derivatives, such as polyvinyl alcohol and carboxymethylcellulose, graphite, talc, inorganic silicic acid, carbon fiber, etc. are mentioned. The addition amount of the molding aid is 0.10 to 5.0% by mass, preferably 1.0 to 3.0% by mass, and more preferably 1.5 to 2.5% by mass. When the addition amount of the molding aid is 0.10% by mass or more, the molding aid exhibits a sufficient effect as a lubricant, and there is a tendency to obtain a molding catalyst that is not easily cracked or cracked during use. Moreover, since the addition amount of the molding aid is 5.0% by mass or less, in the main firing step, heat generated from the combustion of the molding aid can be suppressed, and the main firing temperature is excessively improved. The shrinkage | contraction of the shaping | molding catalyst by having ended can be suppressed.

  Although it does not specifically limit as a shaping | molding method, For example, the well-known tableting molding method, the extrusion molding method, a rolling granulation method etc. are mentioned. Among these, from the viewpoint of the productivity of the molded catalyst, it is preferable to obtain a molded body by molding a temporarily fired body by a tableting molding method or an extrusion molding method. Although it does not specifically limit a shaping | molding shape, For example, shapes, such as spherical shape, a column shape, a ring (cylindrical shape), and a star shape, are mentioned. Among these, a cylindrical shape and a ring shape having a high crushing strength of the molded catalyst are preferable.

[Main firing process]
The main firing step is a step of obtaining a molded catalyst by subjecting the molded body to main firing in an atmosphere having an oxygen concentration of 0.10 to 18% by volume. By performing the main baking, the crystal obtained by the temporary baking grows. The oxygen concentration in this baking process is 0.10-18 volume%, Preferably it is 3.0-15 volume%, More preferably, it is 5-12 volume%. When the oxygen concentration is 0.10% by volume or more, the molded catalyst can be prevented from being excessively reduced, and a molded catalyst having higher activity can be obtained. Moreover, when the oxygen concentration is 18% by volume or less, heat generation due to combustion of the molding aid can be suppressed, and a decrease in the specific surface area of the resulting molded catalyst can be suppressed.

  The main firing can be performed using a firing furnace such as a rotary furnace, a fixed furnace, a tubular furnace, a tunnel furnace, a muffle furnace, or a fluidized firing furnace. Among these, it is preferable to use a fixed furnace from the viewpoint of preventing the molded body from being destroyed.

  In the main baking step, from the viewpoint of controlling the specific surface area, it is preferable to perform two or more stages of multistage baking, and more preferably to perform three or more stages of multistage baking. By performing multi-stage firing of two or more stages, a decrease in specific surface area due to rapid heat generation of the molding aid can be suppressed, and a decrease in the activity of the resulting molded catalyst tends to be further suppressed.

Specifically, multi-stage firing under the following conditions can be mentioned.
1st stage: Temperature is raised from room temperature to 250 ° C. to 300 ° C. over 1 h and held for 1 h or more. Holding 3rd stage: The temperature is raised from the 2nd stage holding temperature to 530-560 ° C. over 1 h and held for 5 h or more.

More specifically, when graphite is used as a molding aid, multistage firing under the following conditions can be mentioned.
1st stage: Temperature is raised from room temperature to 270 ° C. over 1 h and held for 1 h 2nd stage: Temperature is raised over 2 h from 270 ° C. to 525 ° C. and held for 3 h 3rd stage: Over 1 h from 525 ° C. to 555 ° C. Temperature rise and hold for 9 hours

[Molded catalyst]
The molded catalyst of this embodiment is manufactured by the method for manufacturing a molded catalyst. The specific surface area of the obtained molded catalyst is preferably 2.0 to 4.0 m ² / g, more preferably 2.3 to 3.5 m ² / g, and further preferably 2.5 to 3.0 m. ² / g. When the specific surface area of the molded catalyst is 2.0 m ² / g or more, the yield of the unsaturated aldehyde tends to be further improved. Further, when the specific surface area of the molded catalyst is 4.0 m ² / g or less, the strength of the molded catalyst tends to be further improved. In order to precisely control the specific surface area, heat generated from the molding aid is suppressed as much as possible while gradually burning the molding aid in the main firing step.

The molded catalyst obtained in the method for producing a molded catalyst preferably has a composition represented by the following composition formula (1). By having such a composition, the selectivity of unsaturated aldehyde tends to be further improved.
_{Mo 12 Bi a Fe b A c} Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius greater than 0.96 （(except potassium, cesium and rubidium), and Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1.0 ≦ a ≦ 5.0, and Fe atomic ratio b is 1 .5 ≦ b ≦ 6.0, the atomic ratio c of the element A is 1.0 ≦ c ≦ 5.0, the atomic ratio d of Co is 1.0 ≦ d ≦ 8.0, and the element B The atomic ratio e of 0 ≦ e <3.0, The atomic ratio f of element C is 0 ≦ f ≦ 2.0, the ratio of Fe / Co is 0.80 ≦ b / d, and g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. is there.)

[Method for producing unsaturated aldehyde]
The method for producing an unsaturated aldehyde of the present embodiment includes an oxidation step of producing an unsaturated aldehyde by oxidizing an olefin and / or alcohol using the shaped catalyst produced by the method for producing a shaped catalyst. Hereinafter, although the specific example is demonstrated, the manufacturing method of this embodiment is not limited to the following specific examples.

  Although it does not specifically limit as an olefin, For example, a propylene and isobutylene are mentioned. Moreover, although it does not specifically limit as alcohol, For example, t-butyl alcohol and isobutanol are mentioned.

  Although it does not specifically limit as an oxidation method, For example, a vapor phase catalytic oxidation reaction can be used. The gas phase catalytic oxidation reaction proceeds by introducing an olefin and / or alcohol, a molecular oxygen-containing gas, and a dilution gas into the catalyst layer in the fixed bed reactor at a predetermined reaction temperature.

  The olefin and / or alcohol is preferably 1.0 to 10% by volume, more preferably 6.0 to 10% by volume, and still more preferably 7.0 to 9.0% by volume with respect to 100% by volume of the mixed gas. %.

The molecular oxygen-containing gas is not particularly limited, for example, pure oxygen gas, and N ₂ O, include gas containing oxygen such as air, air from an industrial point of view are preferred. The molecular oxygen concentration is preferably 1 to 20% by volume with respect to 100% by volume of the mixed gas.

  Although it does not specifically limit as a dilution gas, For example, nitrogen, a carbon dioxide, water vapor | steam, and these mixed gas are mentioned. It is preferable that water vapor is included from the viewpoint of preventing coking to the molded catalyst, but the water vapor concentration in the mixed gas should be as low as possible in order to suppress by-production of carboxylic acids such as acrylic acid, methacrylic acid, and acetic acid. Is preferably 0 to 30% by volume, more preferably 2 to 20% by volume, and further preferably 3 to 10% by volume with respect to 100% by volume of the mixed gas.

  The mixing ratio of the molecular oxygen-containing gas and the dilution gas preferably satisfies the condition of 0.01 <molecular oxygen / (molecular oxygen-containing gas + dilution gas) <0.3 by volume ratio.

  Reaction temperature becomes like this. Preferably it is 300-480 degreeC, More preferably, it is 350 degreeC-450 degreeC, More preferably, it is 400 degreeC-450 degreeC. The pressure is preferably normal pressure to 5 atm. The space velocity at which the source gas is introduced is preferably 400 to 4000 / hr (under normal temperature pressure (NTP) conditions).

  The molar ratio of oxygen to olefin and / or alcohol is preferably 1.0 to 2.0 from the viewpoint of controlling the outlet oxygen concentration of the reactor in order to improve the yield of unsaturated aldehyde, More preferably, it is 1.1-1.8, More preferably, it is 1.2-1.6.

  Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present embodiment is not limited to the examples described below. The atomic ratio of oxygen atoms in the oxide catalyst is determined by the valence conditions of other elements. In the examples and comparative examples, the atomic ratio of oxygen atoms in the formulas representing the composition of the catalyst is Omitted. Further, the composition ratio of each element in the molded catalyst was calculated from the composition ratio of preparation.

In Examples and Comparative Examples, the conversion rate, selectivity, and yield used to show the reaction results are defined by the following equations, respectively.
Conversion rate = (number of moles of reacted raw material / number of moles of supplied raw material) × 100
Selectivity = (number of moles of compound produced / number of moles of reacted raw material) × 100
Yield = (Mole number of produced compound / Mole number of supplied raw material) × 100

[Measurement method of repose angle]
The angle of repose of the pre-fired body was measured by an injection method, which is a method of measuring the angle of the powder when it is placed in a funnel and allowed to fall naturally and deposited on a horizontal surface.

[Method for measuring specific surface area]
The specific surface area of the molded catalyst was measured by an automatic specific surface area measuring device GEMINI 2360.

[Example 1]
67.5 g of ammonium heptamolybdate was dissolved in 202.6 g of warm water at about 90 ° C. (solution A). Also, 37.0 g of bismuth nitrate, 22.0 g of cerium nitrate, 51.3 g of iron nitrate, 0.55 g of cesium nitrate, and 37.2 g of cobalt nitrate were dissolved in 41.9 g of 18% by mass nitric acid aqueous solution, 206.2 g of warm water was added (Liquid B).

Both liquid A and liquid B were mixed, aqueous ammonia was added, the pH was adjusted to 4.1, and the mixture was aged at about 60 ° C. for about 4 hours to obtain a raw slurry. This raw material slurry was sent to a spray dryer and spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C. to obtain a dried product. The obtained dried body was heated from room temperature to 100 ° C. in air for 1 h, then heated from 100 ° C. to 300 ° C. over 4 h, and then held at 300 ° C. for 3 hours to obtain a temporarily fired body. After adding 2.2 wt% of graphite to the obtained calcined product and mixing, it was tableted into a ring shape having a diameter of 5 mm, a height of 4 mm, and an inner diameter of 2 mm to obtain a molded product. The molded body was calcined in three stages in a fixed furnace in which the oxygen concentration was adjusted to 9.5% by volume. In the first stage, the temperature was raised from room temperature to 270 ° C. over 1 h and held for 1 h. In the second stage, the temperature was raised from 270 ° C. to 525 ° C. over 2 hours and held for 3 hours. In the third stage, the temperature was raised from 525 ° C. to 555 ° C. over 1 h, and held at 555 ° C. for 9 h to obtain a molded catalyst.
The composition of the obtained molded catalyst was Mo12 Bi2.4 Fe4.0 Ce1.6 Co4.0 Cs0.09.

  As a reaction evaluation of the molded catalyst, 4.2 g of the molded catalyst was filled into a 14 mm diameter jacketed SUS reaction tube, and at a reaction temperature of 430 ° C., 8% by volume of isobutylene, 12.8% by volume of oxygen, 3.0% by volume of water vapor, and A mixed gas composed of 76.2% by volume of nitrogen was aerated at a flow rate of 120 mL / min (NTP) to perform a methacrolein synthesis reaction. The reaction evaluation results are shown in Table 1.

  Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 2]
A molded catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the main calcination was changed to 12% by volume. Under the same reaction conditions as in Example 1, 4.1 g of the molded catalyst was filled in a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the calcined body and the specific surface area of the molded catalyst after the main calcination, and Table 1 shows the reaction evaluation results of the molded catalyst.

[Example 3]
A molded catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the main calcination was changed to 0.1% by volume. Under the same reaction conditions as in Example 1, 4.5 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 4]
A molded catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the main calcination was changed to 3.0% by volume. Under the same reaction conditions as in Example 1, 4.3 g of the molded catalyst was filled in a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 5]
A molded catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the main calcination was changed to 14% by volume. Under the same reaction conditions as in Example 1, 3.9 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 6]
A molded catalyst was obtained under the same conditions as in Example 1 except that the oxygen concentration in the main calcination was changed to 18% by volume. Under the same reaction conditions as in Example 1, 3.8 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 7]
In the calcination step, a molded catalyst was obtained in the same manner as in Example 1 except that the dried body was heated in air from room temperature to 100 ° C. over 1 h and then heated from 100 ° C. to 300 ° C. over 2 h. Under the same reaction conditions as in Example 1, 3.9 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 8]
A molded catalyst was obtained under the same conditions as in Example 1 except that the amount of graphite added was changed to 5 wt%. Under the same reaction conditions as in Example 1, 3.8 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 9]
A molded catalyst was obtained under the same conditions as in Example 1 except that the aging time of the slurry was changed to 1 h. Under the same reaction conditions as in Example 1, 4.2 g of the molded catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 10]
In this calcination step, a molded catalyst was obtained under the same conditions as in Example 1 except that the first and second calcinations were not performed, the temperature was raised from room temperature to 555 ° C. over 0.5 hours, and maintained for 9 hours. . Under the same reaction conditions as in Example 1, 3.8 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Example 11]
A molded catalyst was obtained in the same manner as in Example 1 except that the dried body was heated in air from room temperature to 100 ° C. over 1 h and then heated from 100 ° C. to 300 ° C. over 1 h. Under the same reaction conditions as in Example 1, 3.9 g of the molded catalyst was charged into a reaction tube to carry out a methacrolein synthesis reaction. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Comparative Example 1]
A molded catalyst was obtained under the same conditions as in Example 1 except that the atmosphere of the main calcination was changed to air (oxygen concentration 21 vol%). Under the same reaction conditions as in Example 1, 4.2 g of the molded catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Comparative Example 2]
A molded catalyst was obtained under the same conditions as in Example 1 except that the atmosphere of the main calcination was changed to nitrogen (oxygen concentration 0 volume%). Under the same reaction conditions as in Example 1, 4.2 g of the molded catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Comparative Example 3]
A molded catalyst was obtained under the same conditions as in Example 1 except that graphite was not used. Under the same reaction conditions as in Example 1, 4.2 g of the molded catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

[Comparative Example 4]
A molded catalyst was obtained under the same conditions as in Example 1 except that the amount of graphite added was changed to 6 wt%. Under the same reaction conditions as in Example 1, 4.2 g of the molded catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed. Table 1 shows the angle of repose of the pre-fired body, the specific surface area of the molded catalyst, and the reaction evaluation results using the molded catalyst.

  The molded catalyst of the present invention has industrial applicability as a molded catalyst used when an unsaturated aldehyde is produced from olefin and / or alcohol.

Claims (8)

A method for producing a molded catalyst for use in producing an unsaturated aldehyde from olefin and / or alcohol,
A preparation step of preparing a raw slurry;
A drying step of drying the raw slurry to obtain a dried body;
A pre-baking step of pre-baking the dried body to obtain a pre-fired body;
A molding step of obtaining a molded body by molding in a state where 0.10 to 5.0% by mass of a molding auxiliary agent is added to 100% by mass of the temporarily fired body;
A main firing step of subjecting the molded body to main firing in an atmosphere having an oxygen concentration of 0.10 to 18% by volume to obtain the molded catalyst,
A method for producing a molded catalyst. The manufacturing method of the shaping | molding catalyst of Claim 1 whose specific surface area of the said shaping | molding catalyst is 2.0-4.0m < ² > / g.   The method for producing a molded catalyst according to claim 1 or 2, wherein the raw slurry contains molybdenum, bismuth, iron, an element having an ionic radius larger than 0.96 kg, and cobalt.   The manufacturing method of the shaping | molding catalyst of any one of Claims 1-3 which heats up the said dry body gradually from 100 to 300 degreeC in the said temporary calcination process.   The molding step according to any one of claims 1 to 4, wherein in the molding step, the molded body is obtained by tableting in a state where 0.10 to 5.0 mass% of the molding aid is added to 100 mass% of the temporarily fired body. A method for producing the molded catalyst according to claim 1. The method for producing a molded catalyst according to any one of claims 1 to 5, wherein the molded catalyst has a composition represented by the following composition formula (1).
_{Mo 12 Bi a Fe b A c} Co d B e C f O g (1)
(Wherein Mo is molybdenum, Bi is bismuth, Fe is iron, element A is an element having an ionic radius greater than 0.96 （(except potassium, cesium and rubidium), and Co Is cobalt, element B is at least one element selected from the group consisting of magnesium, zinc, copper, nickel, manganese, chromium, and tin, and element C is selected from the group consisting of potassium, cesium, and rubidium A to g are atomic ratios of each element to Mo12 atoms, Bi atomic ratio a is 1.0 ≦ a ≦ 5.0, and Fe atomic ratio b is 1 .5 ≦ b ≦ 6.0, the atomic ratio c of the element A is 1.0 ≦ c ≦ 5.0, the atomic ratio d of Co is 1.0 ≦ d ≦ 8.0, and the element B The atomic ratio e of 0 ≦ e <3.0, The atomic ratio f of element C is 0 ≦ f ≦ 2.0, the ratio of Fe / Co is 0.80 ≦ b / d, and g is the number of oxygen atoms determined by the valence of the constituent elements other than oxygen. is there.)   Unsaturation which has the oxidation process which oxidizes an olefin and / or alcohol and manufactures an unsaturated aldehyde using the shaping | molding catalyst manufactured by the manufacturing method of the shaping | molding catalyst of any one of Claims 1-5 Method for producing aldehyde.   The molded catalyst manufactured by the manufacturing method of any one of Claims 1-5.