JP5982214B2 - Method for producing oxidation product - Google Patents

Description

  The present invention relates to a method for producing an oxidation product from an olefin and / or an alcohol by performing a gas phase oxidation reaction using a catalyst containing molybdenum, bismuth, iron, cerium and cobalt.

The gas phase oxidation reaction is widely used as a method for producing industrially useful compounds. Aldehydes are representative examples of compounds that are industrially produced using gas phase oxidation reactions. It is considered that the productivity of the oxidation reaction is greatly affected by the olefin and / or alcohol concentration (hereinafter also referred to as the raw material concentration) and the reaction temperature. The higher the raw material concentration and the higher the reaction temperature, the higher the productivity is expected. Yes. However, when the raw material concentration and the reaction temperature are increased, it becomes difficult to maintain the production amount in the long term. The cause of this is that the catalytic activity of the oxide catalyst containing molybdenum, bismuth, iron, and cobalt is maintained by adjusting the redox degree of the catalyst itself. This is because the deterioration of the oxide catalyst is promoted. In view of such circumstances, it is well known in the gas phase oxidation reaction of aldehydes that the gas phase oxidation reaction is performed under conditions where the raw material concentration is 6% or less and the reaction temperature is less than 400 ° C.
In Patent Document 1, in a method for producing methacrolein from isobutylene using an oxide catalyst containing molybdenum, bismuth, iron and cobalt, the reaction is performed under reaction conditions of a reaction temperature of 350 ° C. and an isobutylene concentration of 6%. Have been described.
Although it is described that the oxide catalyst composition described in Patent Document 2 is excellent in thermal stability and reduction resistance, the reaction temperature is still 350 ° C. and the isobutylene concentration is about 6 vol%.

International Publication No. 1995/35273 Pamphlet International Publication 2003/053570 Pamphlet

It is true that daily research has improved oxide catalysts and improved thermal stability and resistance to reduction. However, it is extremely difficult to achieve high productivity under high temperature and high raw material concentration reaction conditions only by improving the catalyst itself. In the case of a high temperature and a high raw material concentration, various factors are hindered, including the fact that the catalyst is very rapidly deteriorated. Therefore, although it is considered that the higher the raw material concentration and the higher the reaction temperature, the higher the productivity, it is extremely difficult to achieve high productivity under high temperature and high concentration reaction conditions. For example, in the case of methacrolein, when isobutylene becomes a high concentration, the selectivity of methacrolein rapidly decreases.
As described above, when an oxidation product is produced from an olefin and / or an alcohol by performing a gas phase oxidation reaction using a catalyst, the target oxidation product is high in reaction conditions at high temperatures and high raw material concentrations. A production method that satisfies productivity has not been known so far. In view of the above circumstances, an object of the present invention is to provide a method for producing an oxidation product that exhibits higher productivity than conventional ones.

  In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies by paying attention to the balance between the oxygen concentration supplied to the catalyst layer and the reactor outlet oxygen concentration as a factor governing the deterioration of the oxide catalyst. As a result, when an oxide catalyst containing molybdenum, bismuth, iron, cerium and cobalt is used in the step of generating an oxidation product by performing a gas phase oxidation reaction from an olefin and / or alcohol using a catalyst, the catalyst It has been found that by setting the ratio of the layer supply oxygen concentration and the reactor outlet oxygen concentration within a specific range, the catalyst is not degraded even at a high raw material concentration and a high reaction temperature, and high productivity is exhibited. It came to complete.

That is, the present invention is as follows.
[1]
A method for producing an oxidation product from an olefin and / or alcohol by performing a gas phase oxidation reaction using a catalyst containing molybdenum, bismuth, iron, cerium and cobalt,
In the gas phase oxidation reaction step, the olefin and / or alcohol concentration is adjusted to 6 to 10 vol%, and the reaction temperature is adjusted to 430 to 500 ° C.
Oxygen is supplied to the catalyst layer at a molar ratio of 1.1 to 1.8 with respect to the olefin and / or alcohol, and the ratio of the catalyst layer supply oxygen concentration to the reactor outlet oxygen concentration is adjusted to 15 to 70. And a method for producing an oxidation product.
[2]
The method for producing an oxidation product according to the above [1], wherein the conversion rate of the olefin and / or alcohol in the gas phase oxidation reaction step is 90%.
[3]
The method for producing an oxidation product according to the above [1] or [2], wherein the oxygen concentration at the outlet of the reactor is 0.05 to 1.0 vol%.
[4]
The olefin is one or more compounds selected from the group consisting of propylene and isobutylene, and the alcohol is one or more compounds selected from the group consisting of propanol, isobutanol, and t-butyl alcohol. ] The manufacturing method of the oxidation product in any one of [3].
[5]
The method for producing an oxidation product according to any one of the above [1] to [4], wherein the oxidation product is acrolein and / or methacrolein.
[6]
The method for producing an oxidation product according to any one of the above [1] to [5], wherein the catalyst is an oxide catalyst having a composition represented by the following empirical formula (1).
_{Mo 12 Bi a Fe b Co c} Ce d A e B f C g O h (1)
(In the formula, Mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt, Ce is cerium, A is at least one element selected from the group consisting of potassium, cesium and rubidium, and B is manganese, cobalt , Nickel, copper, zinc, lead, magnesium, calcium, strontium and barium, at least one element selected from the group consisting of C, at least one element selected from rare earth elements, ag The atomic ratio of each element to the Mo12 atom is shown, 1 ≦ a ≦ 6, 3 ≦ b ≦ 6, 2 ≦ c ≦ 8, 1 ≦ d ≦ 6, 0.01 ≦ e ≦ 2, 0 ≦ f <2, 0 ≦ g ≦ 5, and h is the number of oxygen atoms determined by the valence of constituent elements other than oxygen.)

  According to the present invention, in the process of producing an oxidation product by vapor-phase oxidation of olefin and / or alcohol using an oxide catalyst containing molybdenum, bismuth, iron, cerium and cobalt, the deterioration of the catalyst is suppressed. And high productivity can be maintained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The method for producing an oxidation product in the present embodiment is as follows.
A method for producing an oxidation product from an olefin and / or alcohol by performing a gas phase oxidation reaction using a catalyst containing molybdenum, bismuth, iron, cerium and cobalt,
In the gas phase oxidation reaction step, the olefin and / or alcohol concentration is adjusted to 6 to 10 vol%, and the reaction temperature is adjusted to 430 to 500 ° C.
Oxygen is supplied to the catalyst layer at a molar ratio of 1.1 to 1.8 with respect to the olefin and / or alcohol, and the ratio of the catalyst layer supply oxygen concentration to the reactor outlet oxygen concentration is adjusted to 15 to 70. The manufacturing method.

[1] Production method of oxidation product (1) Raw material The olefin of the raw material is not particularly limited, and examples thereof include propylene, n-butene, isobutylene, n-pentene, n-hexene and cyclohexene. , Propylene and isobutylene are preferred. The alcohol as the raw material is not particularly limited, and examples thereof include propanol, butanol, isobutanol, t-butyl alcohol, etc. Among them, isobutanol and t-butyl alcohol are preferable.

  In the production method of the present embodiment, for example, when propylene and propanol are used as raw materials, acrolein and acrylic acid can be produced, and when isobutylene, isobutanol and t-butyl alcohol are used as raw materials, Methacrolein and methacrylic acid can be produced. It should be noted that there is no particular problem even if the olefin and alcohol contain propane, butane, isobutane or the like as water, nitrogen, or alkane.

  A molecular oxygen-containing gas can be used as an oxygen source in the gas phase oxidation reaction. Examples of the molecular oxygen-containing gas include pure oxygen gas and gas containing oxygen such as air, and air is preferable from an industrial viewpoint. As dilution gas, nitrogen, a carbon dioxide, water vapor | steam, and these mixed gas are mentioned, for example. Regarding the mixing ratio of the molecular oxygen-containing gas and the dilution gas in the mixed gas, the volume ratio of 0.01 <molecular oxygen / (molecular oxygen-containing gas + dilution gas) <0.3 may be satisfied. preferable.

  Although water vapor is necessary in terms of preventing coking of the catalyst, it is preferable to reduce the water vapor concentration in the dilution gas as much as possible in order to suppress by-products such as acetic acid. Usually, water vapor is used in the range of 0.01 to 30 vol% of the total gas supplied to the reactor.

(2) Reactor The reaction method of the gas phase oxidation reaction includes a fixed bed and a fluidized bed, but either type of reaction may be used in the production method of the present embodiment. The fixed bed reaction method is a heat exchange type multi-hole utilizing the advantage that the reaction yield can be increased when the gas flow state is close to the extrusion flow and sequential reactions occur or when there is a concern about decomposition in the empty column. A large number of industrial reactors are used. In the fluidized bed reaction system, the catalyst particles flow vigorously in the reactor, so that the heat transfer is high, and the temperature in the reactor is kept substantially uniform during the reaction accompanied by a large exotherm or endotherm, and the excessive reaction progress can be suppressed. Further, since local accumulation of energy is suppressed, there is an advantage that the raw material gas in the explosion range can be reacted, and the raw material concentration can be increased to improve the productivity.

(3) Reaction conditions In the manufacturing method of this embodiment, the reaction temperature of a gas phase oxidation reaction shall be 430-500 degreeC. When the reaction temperature is less than 430 ° C., the conversion rate of olefin and / or alcohol (hereinafter, also simply referred to as “conversion rate”) is low. Promoted. The reaction temperature is preferably in the range of 430 to 480 ° C, more preferably 430 to 450 ° C. By setting the reaction temperature to 430 ° C. or higher, the conversion rate and the reaction rate can be improved, and the production amount of the oxidation product tends to be further improved.

  Usually, since the gas phase oxidation reaction is an exothermic reaction, it is preferable to provide a cooling device for removing heat so that the reaction temperature becomes suitable. The reaction temperature can be adjusted to the above range by removing the heat of reaction using a cooling pipe or supplying heat using a heating device.

  In the production method of the present embodiment, the concentration of olefin and / or alcohol is adjusted to 6.0 to 10 vol% from the viewpoint of the productivity of the target oxidation product. About a minimum, Preferably it is 6.5 vol% or more, More preferably, it is 7 vol% or more.

  The method for introducing olefin and / or alcohol and oxygen is not particularly limited, and a gas containing olefin and / or alcohol and air or a gas having a high oxygen concentration are mixed in advance and introduced into a reactor filled with a catalyst. Alternatively, they may be introduced independently. Although the gas used for the reaction can be heated to a predetermined reaction temperature after being introduced into the reactor, it is usually preheated and introduced into the reactor for continuous and efficient reaction.

  When the reaction is carried out at a high temperature, the oxidation reaction tends to proceed and oxygen tends to be insufficient. Therefore, the oxygen supplied to the catalyst layer must be larger than that of the olefin and / or alcohol. Further, when the reaction is carried out at a high olefin and / or alcohol concentration, a sufficient amount of oxygen is necessary to supply sufficient oxygen to the catalyst layer and prevent overreduction. However, excessive supply of oxygen causes a decomposition reaction and a combustion reaction of the oxidation product, and reduces the production amount. Therefore, oxygen must be supplied at an appropriate rate. From the above viewpoint, in the manufacturing method in the present embodiment, the molar ratio of oxygen to the catalyst layer and the olefin and / or alcohol is adjusted to 1.1 to 1.8. The molar ratio of oxygen and olefin and / or alcohol supplied to the catalyst layer is preferably 1.2 to 1.7, more preferably 1.4 to 1.6 from the viewpoint of increasing the yield of the oxidation product. is there. When the molar ratio of oxygen supplied to the catalyst layer is less than 1.1 with respect to the olefin and / or alcohol, the concentration of the olefin and / or alcohol increases and the catalyst is reduced and deteriorated. On the other hand, if it exceeds 1.8, the concentration of oxygen supplied to the catalyst layer increases, and the catalyst is oxidized and deteriorated. The present inventors do not oxidize for the first time by adjusting not only the above-mentioned molar ratio of oxygen to olefin and / or alcohol, but also the ratio of the catalyst layer supply oxygen concentration and the reactor outlet oxygen concentration described later to a specific range. It has been found that oxidation deterioration and reduction deterioration of the catalyst can be suppressed without breaking the balance of the reduction degree.

  The catalyst layer supply oxygen concentration indicates the oxygen concentration in the gas supplied to the catalyst layer. The oxygen concentration supplied to the catalyst layer can be measured by sampling a gas immediately before the catalyst layer, but can also be obtained by calculation if the composition of the gas supplied to the reactor is clear. For example, when 64% by volume of air (including 20% by volume of oxygen), 8.0% by volume of isobutylene, 26% by volume of nitrogen, and 2.0% by volume of water are used, the catalyst layer supply oxygen concentration is calculated to be 12.8% by volume. The The range of oxygen concentration supplied to the catalyst layer is a range that does not affect the production amount and safety of the target oxidation product, and the molar ratio of oxygen to olefin and / or alcohol supplied to the catalyst layer is within an appropriate range. If there is, it will not be specifically limited. For example, when the olefin and / or alcohol concentration is 6.0 to 10 vol%, the catalyst layer supply oxygen concentration is about 7.0 to 18 vol%.

  The product gas containing the target oxidation product flows out of the reactor outlet. The oxygen concentration in the product gas flowing out from the reactor outlet and containing the target oxidation product is defined as the reactor outlet oxygen concentration. The oxygen concentration at the outlet of the reactor can be measured within a range in which the ratio of oxygen in the product gas does not change, and does not have to be strictly at or near the portion where the product gas flows out of the reactor. Therefore, the outlet oxygen concentration of the reactor may be measured in the gas from downstream of the reactor or immediately before flowing out of the reactor to immediately before being subjected to the purification operation. For example, when the product gas is quenched and then absorbed into water and purified by extractive distillation, the product gas for measuring the reactor outlet oxygen concentration is sampled in a pipe between the reactor and the quenching tower provided downstream of the reactor. be able to. The oxygen concentration at the outlet of the reactor can be measured by gas chromatography equipped with a thermal conductivity detector (TCD).

  Since the oxygen concentration at the outlet of the reactor affects the decomposition and secondary reaction of oxidation products in the reactor, the molar ratio of oxygen to olefin and / or alcohol supplied to the catalyst layer is controlled so that it falls within an appropriate range. To do. The reactor outlet oxygen concentration can be adjusted by changing the amount of oxygen-containing gas supplied to the catalyst layer, the reaction temperature, the pressure in the reactor, the amount of catalyst, and the total amount of gas supplied to the reactor. . Especially, it is preferable to adjust by controlling the amount of molecular oxygen-containing gas supplied to the catalyst layer, for example, air. The range of the oxygen concentration at the outlet of the reactor is not particularly limited as long as it does not affect the production amount of the target oxidation product, but is preferably 0.05 to 1.0 vol%, more preferably It is 0.2-0.5 vol%, More preferably, it is 0.3-0.5 vol%.

  In the production method of the present embodiment, the ratio of the catalyst layer supply oxygen concentration to the reactor outlet oxygen concentration (catalyst layer supply oxygen concentration / reactor outlet oxygen concentration) from the viewpoint of preventing the catalyst from deteriorating in the reactor for a long period of time. Is adjusted to 15-70. The ratio between the catalyst layer supply oxygen concentration and the reactor outlet oxygen concentration is preferably 20 to 60, more preferably 25 to 50. When the ratio of the catalyst layer supply oxygen concentration to the reactor outlet oxygen concentration exceeds 70, the catalyst is excessively reduced. When the ratio is less than 15, the catalyst is excessively oxidized. Decreases.

  Usually, the value of the catalyst layer supply oxygen concentration and the value of the reactor outlet oxygen concentration are closely related. Therefore, if the supplied oxygen concentration is increased or decreased, the oxygen concentration at the outlet also increases or decreases accordingly. However, in order to maintain the ratio between the catalyst layer supply oxygen concentration and the reactor outlet oxygen concentration at 15 to 70, it is necessary to increase the catalyst layer supply oxygen concentration on the one hand and decrease the reactor outlet oxygen concentration on the other hand. . Therefore, the ratio of the medium layer supply oxygen concentration to the reactor outlet oxygen concentration cannot be made 15 to 70 simply by adjusting the raw material ratio.

  In order to make the ratio of the oxygen concentration supplied to the catalyst layer and the oxygen concentration at the outlet of the reactor within this range, at least the oxygen needs to react sufficiently in the reactor to consume the oxygen. From the above viewpoint, the conversion rate of olefin and / or alcohol is preferably 90% or more, more preferably 92 vol% or more, and still more preferably 95 vol% or more. The conversion can be set to an arbitrary value by adjusting conditions such as reaction temperature and raw material concentration.

The conditions for adjusting the ratio of the catalyst layer supply oxygen concentration and the reactor outlet oxygen concentration include catalyst amount, contact time, reaction pressure, space velocity and the like in addition to the conversion rate. By adjusting these conditions in combination, the ratio of the catalyst layer supply oxygen concentration and the reactor outlet oxygen concentration can be adjusted to an arbitrary value. When the reaction temperature is adjusted to 430 ° C. to 500 ° C. and the olefin and / or alcohol concentration is adjusted to a range of 6 to 10 vol%, the contact time defined by the following formula is 5.0 (g · sec / cc). It is preferable to adjust so that it may become the following ranges, More preferably, it adjusts to 4.0 (g * sec / cc) or less, More preferably, it adjusts to 3.0 (g * sec / cc) or less.
Contact time (g · sec / cc) = W / F * 60 * 273.15 / (273.15 + T) * (P * 1000 + 101.325) /101.325
In the formula, W represents the catalyst filling amount (g), F represents the raw material mixed gas flow rate (cc / min, NTP conversion), T represents the reaction temperature (° C.), and P represents the reaction pressure (MPa).

  The reaction pressure is preferably normal pressure to 5 atmospheres, and the space velocity is preferably 400 to 4000 / hr (under normal temperature pressure (NTP) conditions).

[2] Catalyst (1) Structure The catalyst used in the gas phase oxidation reaction in the present embodiment includes molybdenum (Mo), bismuth (Bi), iron (Fe), cerium (Ce), and cobalt (Co). The composition of Mo, Bi, Fe, Ce and Co is preferably adjusted to form the desired oxide, and the oxidation product from the olefin and / or alcohol by oxidation reaction by lattice oxygen in the oxide. Manufactured. In general, when lattice oxygen in the catalyst is consumed in the oxidation reaction, oxygen vacancies are generated in the oxide. As a result, the reduction of the oxide also proceeds as the reaction proceeds. It is necessary to reoxidize. Oxides containing Mo, Bi, Fe, Ce and Co are consumed lattices by dissociating and adsorbing molecular oxygen in the gas phase in addition to reactivity to oxidation from olefins and / or alcohols. It is thought that it is excellent also in the reoxidation effect | action which reproduces | regenerates oxygen. Therefore, even when the reaction is carried out over a long period of time, it is considered that the reoxidation action of lattice oxygen is maintained, and the oxidation product can be stably produced from the olefin and / or alcohol without deactivating the catalyst.

From the viewpoint of achieving higher productivity, the catalyst in the present embodiment is preferably an oxide catalyst having a composition represented by the following empirical formula (1).
_{Mo 12 Bi a Fe b Co c} Ce d A e B f C g O h (1)
(In the formula, Mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt, Ce is cerium, A is at least one element selected from the group consisting of potassium, cesium and rubidium, and B is manganese, cobalt , Nickel, copper, zinc, lead, magnesium, calcium, strontium and barium, at least one element selected from the group consisting of C, at least one element selected from rare earth elements, ag The atomic ratio of each element to the Mo12 atom is shown, 1 ≦ a ≦ 6, 3 ≦ b ≦ 6, 2 ≦ c ≦ 8, 1 ≦ d ≦ 6, 0.01 ≦ e ≦ 2, 0 ≦ f <2, 0 ≦ g ≦ 5, and h is the number of oxygen atoms determined by the valence of constituent elements other than oxygen.)

The presence of Mo, Bi, Fe, and Ce is indispensable from the viewpoint of compounding each metal element in the Mo-Bi metal oxide. Bi and Mo form Bi—Mo—O complex oxides such as Bi ₂ Mo ₃ O ₁₂ and Bi ₂ MoO ₆ which are active species such as gas phase catalytic oxidation and oxidative dehydrogenation. The atomic ratio a of Bi to Mo12 atoms is preferably 1 ≦ a ≦ 6, more preferably 2 ≦ a ≦ 5, and more preferably from the viewpoint of further increasing the selectivity of the oxidation product. 2 ≦ a ≦ 4. From the same viewpoint, the atomic ratio d of Ce is preferably 1 ≦ d ≦ 6, more preferably 1 ≦ d ≦ 5, and further preferably 1 ≦ d ≦ 4.

  Fe is an element essential for industrially synthesizing a target oxidation product, similarly to Mo and Bi. The atomic ratio b of Fe to Mo12 atoms in the oxide catalyst in the present embodiment is preferably 3 ≦ b ≦ 6, more preferably 3 ≦ b ≦ 5.5, and further preferably 3 ≦ b ≦ 5. By increasing the Fe content and using trivalent and divalent redox, it tends to be a reduction-resistant catalyst even in a reactor with a small amount of oxygen.

Co is an element essential for synthesizing a target oxidation product industrially in the same manner as described above, forms a complex oxide with Mo such as complex oxide CoMoO ₄ , takes in oxygen from the gas phase, It is thought that it plays a role of supplying Bi-Mo-O and the like. Further, it is considered that the activity is greatly improved by dissolving the above-described Fe in the composite oxide CoMoO ₄ . Further, Co is considered to play a role in solid solution in Bi—Mo—O, promoting the desorption of the target oxidation product from the catalyst, and suppressing the combustion decomposition of the target oxidation product. In order to obtain the target oxidation product in a high yield, it is preferable to complex Co with Mo to form a complex oxide CoMoO _{4 and} to form a solid solution in Bi—Mo—O. From the viewpoint of reducing the formation of a single oxide, the atomic ratio c of Co is preferably 2 ≦ c ≦ 8, more preferably 2.5 ≦ c ≦ 7, and further preferably 2 ≦ c ≦ 6.

The role of the components represented by A and B is not limited, but in the field of oxide catalysts having Mo, Bi, Fe, Ce and Co as essential components, it is presumed as follows.
A represents at least one element selected from the group consisting of potassium, cesium, and rubidium, and shows a role of neutralizing acid sites such as MoO ₃ that have not been complexed by the catalyst in the catalyst for producing an oxidation product. it is conceivable that. The atomic ratio of element A to Mo12 atoms is preferably 0.01 ≦ e ≦ 2 from the viewpoint of catalytic activity. The reason for adjusting to the above numerical range is that if the amount of alkali element is more than this, the catalyst becomes basic, and the raw material olefin and / or alcohol is difficult to be adsorbed by the catalyst, and there is a tendency that sufficient catalytic activity cannot be expressed. It is.

B represents at least one element selected from the group consisting of manganese, cobalt, nickel, copper, zinc, lead, magnesium, calcium, strontium and barium, and is substituted with a part of the element A in the catalyst. It is considered that there is a role of stabilizing the crystal structure of the composite oxide CoMoO ₄ and suppressing the phase transition due to pressure and temperature. Element B is positioned as an optional component whose content may be zero (f = 0) because it improves the activity of the catalyst or stabilizes the crystal structure of CoMoO _{4 in} the catalyst.

  C represents at least one element selected from rare earth elements, and is an optional component whose content may be zero (g = 0) because it improves the activity of the catalyst or improves the heat resistance in the catalyst. It is positioned as.

  In the case of a catalyst used in a fluidized bed reaction, the above-described oxide may be supported on a carrier, and in that case, the proportion of the carrier is preferably 30 to 70% by mass, more preferably based on the total of the carrier and the oxide. Can be used effectively in the range of 40 to 60% by mass. The support is preferably at least one selected from the group consisting of silica, alumina, titania and zirconia, and a more preferable support is silica. Silica is an inert carrier compared to other carriers, and has a good bonding action with an oxide without deteriorating the activity and selectivity of the catalyst with respect to the oxidation product. In addition, by supporting the oxide on the support, physical properties suitable for fluidized bed reaction such as particle shape / size / distribution, fluidity, and mechanical strength can be imparted.

(2) Method for producing catalyst The method for producing the catalyst in the present embodiment is not particularly limited, and can be produced by a known method. The supported catalyst containing an oxide containing Mo, Bi, Fe, Ce and Co is, for example, a first step of preparing a raw slurry, a second step of spray drying the raw slurry, and a second step. It can be obtained by a method including a third step of firing the obtained dried product. The preferable aspect of the manufacturing method of the catalyst including the 1st-3rd process is demonstrated.

  In the first step, a raw material slurry is prepared using a catalyst raw material. Molybdenum, bismuth, iron, cerium, cobalt, manganese, nickel, copper, zinc, lead, alkali metal elements, magnesium, calcium, strontium, barium, rare earth elements as element sources are soluble in water or nitric acid Examples thereof include ammonium salts, nitrates, hydrochlorides, sulfates, and organic acid salts. In particular, ammonium salts as molybdenum sources, bismuth, iron, cerium, manganese, cobalt, nickel, copper, zinc, lead, alkali metal elements, magnesium, calcium, strontium, barium, and rare earth elements Nitrate is preferred. As described above, oxides such as silica, alumina, titania, and zirconia can be used as the oxide carrier, but silica is preferably used as the carrier, and silica sol is preferable as the silica source. The raw slurry is prepared by adding, for example, an ammonium salt of molybdenum dissolved in water to a silica sol, and then bismuth, iron, cerium, manganese, cobalt, nickel, copper, zinc, lead, alkali metal elements, magnesium, It can be performed by adding a solution prepared by dissolving nitrates of calcium, strontium, barium, and rare earth elements in water or an aqueous nitric acid solution. At that time, the order of the addition may be changed.

  In the second step, the raw material slurry obtained in the first step is spray-dried to obtain dry particles. The atomization of the raw material slurry can be performed by a method such as a centrifugal method, a two-fluid nozzle method, and a high-pressure nozzle method which are usually carried out industrially, but is preferably performed by a centrifugal method. Next, the obtained particles are dried. As the drying heat source, it is preferable to use air heated by steam, an electric heater or the like. The temperature at the inlet of the dryer is preferably 100 to 400 ° C, more preferably 150 to 300 ° C.

  In the third step, the desired catalyst is obtained by calcining the dried particles obtained in the second step. The dried particles are preferably calcined at 150 to 400 ° C. as necessary, and then subjected to main calcination at a temperature range of 400 to 700 ° C., preferably 500 to 700 ° C. for 1 to 20 hours. During firing or after firing, extrusion molding or tableting molding may be performed as necessary. Firing can be performed using a firing furnace such as a rotary furnace, a tunnel furnace, or a muffle furnace. The catalyst particle size is preferably distributed in the range of 10 to 150 μm.

[3] Method for Producing Oxidation Product An oxidation product can be produced by performing a gas phase oxidation reaction of olefin and / or alcohol using the catalyst in the present embodiment. Hereinafter, specific examples thereof will be described, but the manufacturing method in the present embodiment is not limited to the following specific examples.

(1) Method for producing methacrolein Methacrolein can be obtained by conducting a gas phase catalytic oxidation reaction of isobutylene, isobutanol and / or t-butyl alcohol using an oxide catalyst. In the gas phase catalytic oxidation reaction, the molecular oxygen concentration in the catalyst layer in the fixed bed reactor is 1.0 to 10 vol% of isobutylene, isobutanol and / or t-butyl alcohol in the presence of an oxide catalyst. A raw material gas composed of a mixed gas to which a molecular oxygen-containing gas and a dilution gas are added is introduced so as to be 1.0 to 20 vol%. The pressure is adjusted to normal pressure to 5.0 atm, and the space velocity is adjusted to 400 to 4000 / hr (under normal temperature pressure (NTP) conditions).

(2) Method for producing acrolein Acrolein can be obtained by conducting a gas phase catalytic oxidation reaction of propylene using an oxide catalyst. Conditions for producing acrolein by vapor-phase catalytic oxidation of propylene are not particularly limited, and can be performed by a method generally used for producing acrolein by vapor-phase catalytic oxidation of propylene. For example, a mixed gas composed of propylene 1.0 to 15 vol%, molecular oxygen 3.0 to 30 vol%, water vapor 0.01 to 60 vol%, inert gas 20 to 80 vol% such as nitrogen and carbon dioxide, etc. The catalyst layer may be introduced at 250 to 450 ° C. under a pressure of 0.1 to 1 MPa at a space velocity (SV) of 300 to 5000 / hr. As the reactor, a known fixed bed reactor, fluidized bed reactor or moving bed reactor is used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. 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 oxide catalyst was calculated from the composition ratio of preparation.

In Examples and Comparative Examples, the conversion rate, selectivity, and yield used to represent reaction results are defined by the following equations. The “number of moles of raw material” in the formula is the number of moles of olefin and / or alcohol.
Conversion rate (%) = (number of moles of reacted raw material / number of moles of supplied raw material) × 100
Selectivity (%) = (number of moles of oxidized product formed / number of moles of reacted raw material) × 100
Yield (%) = (number of moles of produced oxidation product / number of moles of supplied raw material) × 100

The productivity of the oxidized product was defined by the following equation assuming that the amount of oxidized product produced per 1 t of each catalyst was calculated, and then the continuous operation was performed for 8000 hours with the catalyst 10 t.
Production amount (t) = ({moles of raw material supplied per hour (mol / h) × yield) / catalyst amount (t)} × 10 (t) × 8000 (hr) / molecular weight of oxidation product

The oxygen concentration supplied to the catalyst layer was obtained by calculation from the composition of the gas supplied to the reactor.
The analysis of olefin and / or alcohol, oxidation product and reactor outlet oxygen concentration was performed using three gas chromatographs directly connected to the reactor.
<TCD-1> Measurement of olefin and / or alcohol, acrolein, methacrolein Gas chromatography: GC-14B, analytical column: packed column / SUS-4m * 3 mmφ / Polapack QS-80-100 mesh, carrier gas: helium, Column temperature: After gas injection, hold at 80 ° C. for 10 minutes, then heat up to 180 ° C. at 4 ° C./minute, hold for 30 minutes, then heat up to 200 ° C. at 20 ° C./minute, 30 minutes The sample was held and analyzed using a set temperature of 180 ° C.
<TCD-2> Measurement of oxygen concentration at outlet of reactor Gas chromatography: GC-14B, analytical column: packed column / SUS-4m * 3 mmφ • molecular sieve 5A-60-80 mesh, carrier gas: helium, column temperature: gas After injection, hold at 80 ° C. for 74 minutes, then heat up to 180 ° C. at 30 ° C./minute, hold for 10 minutes, then heat up to 200 ° C. at 20 ° C./minute and hold for 30 minutes , Using a preset temperature of 180 ° C.
<FID> Measurement of acrylic acid and methacrylic acid Gas chromatography: GC-8A, analytical column: G column G-300 Length 40m * 2.1.2 mm Film Thickness 1.0 μm, carrier gas: helium, column temperature: after gas injection, Hold at 40 ° C for 15 minutes, then heat up to 150 ° C at 3 ° C / minute, hold for 10 minutes, then heat up to 190 ° C at 20 ° C / minute, hold for 30 minutes, set temperature Analysis was performed using 200 ° C.

[Example 1]
67.0 g of ammonium heptamolybdate was dissolved in 201.0 g of hot water at about 90 ° C. (solution A). Also, 46.3 g of bismuth nitrate, 17.8 g of cerium nitrate, 50.0 g of iron nitrate, 0.55 g of cesium nitrate, and 26.9 g of cobalt nitrate were dissolved in 37.6 g of an 18% by mass nitric acid aqueous solution, Warm water 201.7g was added (the B liquid). After mixing both liquid A and liquid B, using a homogenizer and treating at 20000 rpm for 1 hour, the mixture was aged by continuing stirring with a magnetic stirrer at about 65 ° C. for about 4 hours, Obtained. This raw material slurry is sent to a spray dryer, spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C., and the resulting spray-dried catalyst precursor is heated from room temperature at a heating rate of 1.4 ° C./min. And calcined at 250 ° C. for 3 hours. The obtained preliminary calcined catalyst precursor was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and was calcined at 530 ° C. for 4 hours. The composition of the obtained oxide catalyst was Mo ₁₂ Bi _3.0 Ce _1.3 Co _2.9 Fe _3.9 Cs _0.09 .
As an initial reaction evaluation of the catalyst, 3.0 g of a catalyst was packed in a 14 mm diameter jacketed SUS reaction tube, and a mixed gas composed of isobutylene, oxygen, water vapor and nitrogen shown in the reaction conditions of Table 1 was 120 mL / min (NTP). Of the methacrolein synthesis reaction. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 2]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 2.9 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 3]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 2.9 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 4]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 2.8 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 5]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 6]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 7]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 8]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 9]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 10]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 11]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.3 g of the catalyst was charged in a reaction tube, and a methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 12]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.8 g of the catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 13]
65.4 g of ammonium heptamolybdate was dissolved in 196.3 g of warm water at about 90 ° C. (solution A). Moreover, 18 mass% nitric acid aqueous solution of 40.6 g of bismuth nitrate, 16.1 g of cerium nitrate, 38.8 g of iron nitrate, 0.54 g of cesium nitrate, 16.0 g of lanthanum nitrate, 4.7 g of magnesium nitrate and 27.1 g of cobalt nitrate. It melt | dissolved in 37.8g and 208.6g of warm water of about 90 degreeC was added (B liquid). After mixing both liquid A and liquid B, using a homogenizer and treating at 20000 rpm for 1 hour, the mixture was aged by continuing stirring with a magnetic stirrer at about 65 ° C. for about 4 hours, Obtained. This raw material slurry is sent to a spray dryer, spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C., and the resulting spray-dried catalyst precursor is heated from room temperature at a heating rate of 1.4 ° C./min. And calcined at 250 ° C. for 3 hours. The obtained preliminary calcined catalyst precursor was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and was calcined at 530 ° C. for 4 hours. The composition of the obtained oxide catalyst was Mo ₁₂ Bi _2.7 Ce _1.2 Co _3.0 Fe _3.1 La _1.2 Mg _0.6 Cs _0.09 .
Using this catalyst, as an initial reaction evaluation of the catalyst, 3.2 g of catalyst was filled in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 14]
68.3 g of ammonium heptamolybdate was dissolved in 204.9 g of warm water at about 90 ° C. (solution A). Also, 33.0 g of bismuth nitrate, 29.4 g of cerium nitrate, 44.4 g of iron nitrate, 1.61 g of rubidium nitrate, 3.1 g of copper nitrate and 28.3 g of cobalt nitrate were dissolved in 37.6 g of 18% by mass nitric acid aqueous solution. Then, 198.6 g of warm water at about 90 ° C. was added (Liquid B). After mixing both liquid A and liquid B, using a homogenizer and treating at 20000 rpm for 1 hour, the mixture was aged by continuing stirring with a magnetic stirrer at about 65 ° C. for about 4 hours, Obtained. This raw material slurry is sent to a spray dryer, spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C., and the resulting spray-dried catalyst precursor is heated from room temperature at a heating rate of 1.4 ° C./min. And calcined at 250 ° C. for 3 hours. The obtained preliminary calcined catalyst precursor was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and was calcined at 530 ° C. for 4 hours. The composition of the obtained oxide catalyst was _{Mo 12 Bi 2.1 Ce 2.1 Co 3.0} Fe 3.4 Cu 0.4 Rb 0.34.
Using this catalyst, as an initial reaction evaluation of the catalyst, 3.1 g of the catalyst was charged into a reaction tube, and a methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Example 15]
(Production example of acrolein)
67.5 g of ammonium heptamolybdate was dissolved in 202.4 g of warm water at about 90 ° C. (solution A). Also, 43.5 g of bismuth nitrate, 20.7 g of cerium nitrate, 50.3 iron nitrate, 0.19 g of cesium nitrate, and 27.0 g of cobalt nitrate were dissolved in 37.6 g of an 18% by mass nitric acid aqueous solution, 200.7 g of warm water was added (Liquid B). After mixing both liquid A and liquid B, using a homogenizer and treating at 20000 rpm for 1 hour, the mixture was aged by continuing stirring with a magnetic stirrer at about 65 ° C. for about 4 hours, Obtained. This raw material slurry is sent to a spray dryer, spray dried at an inlet temperature of 250 ° C. and an outlet temperature of about 140 ° C., and the resulting spray-dried catalyst precursor is heated from room temperature at a heating rate of 1.4 ° C./min. And calcined at 250 ° C. for 3 hours. The obtained preliminary calcined catalyst precursor was tablet-molded into a cylindrical shape having a diameter of 5 mm and a height of 4 mm, and was calcined at 530 ° C. for 4 hours. The composition of the obtained oxide catalyst was Mo ₁₂ Bi _2.8 Ce _1.5 Co _2.9 Fe _3.9 Cs _0.03 .
As an initial reaction evaluation of the catalyst, 16.0 g of the catalyst was filled in a 15 mm diameter jacketed SUS reaction tube, and a mixed gas composed of propylene, oxygen, water vapor and nitrogen shown in the reaction conditions of Table 3 was 600 mL / min (NTP). The acrolein synthesis reaction was carried out at a flow rate of. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 4.

[Comparative Example 1]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.3 g of the catalyst was charged in a reaction tube, and a methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 2]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 2.7 g of the catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 3]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 4]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 5]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of catalyst was charged in a reaction tube, and methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 6]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 4.0 g of catalyst was charged in a reaction tube, and a methacrolein synthesis reaction was performed under the reaction conditions shown in Table 1. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 7]
Using the same catalyst as in Example 1, as an initial reaction evaluation of the catalyst, 3.0 g of a catalyst was filled in a 14 mm diameter jacketed SUS reaction tube, and consisted of isobutylene, oxygen, water vapor and nitrogen shown in the reaction conditions of Table 1. The mixed gas was aerated at a flow rate of 100 mL / min (NTP) to perform a methacrolein synthesis reaction. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 2.

[Comparative Example 8]
Using the same catalyst as in Example 15, as an initial reaction evaluation of the catalyst, 20.0 g of the catalyst was charged into a 15 mm diameter jacketed SUS reaction tube and made of propylene, oxygen, water vapor, and nitrogen as shown in the reaction conditions of Table 3. The mixed gas was aerated at a flow rate of 600 mL / min (NTP) to perform acrolein synthesis reaction. Subsequently, 2000 hours of continuous operation was performed under the same conditions. The reaction evaluation results are shown in Table 4.

  According to the present invention, in the process of producing an oxidation product by vapor-phase oxidation of olefin and / or alcohol using an oxide catalyst containing molybdenum, bismuth, iron, cerium and cobalt, the deterioration of the catalyst is suppressed. And high productivity can be maintained.

Claims (5)

A method for producing an oxidation product from an olefin and / or alcohol by performing a gas phase oxidation reaction using a catalyst containing molybdenum, bismuth, iron, cerium and cobalt,
In the gas phase oxidation reaction step, the olefin and / or alcohol concentration is adjusted to 6 to 10 vol%, and the reaction temperature is adjusted to 430 to 500 ° C.
Oxygen is supplied to the catalyst layer at a molar ratio of 1.1 to 1.8 with respect to the olefin and / or alcohol, and the ratio of the catalyst layer supply oxygen concentration to the reactor outlet oxygen concentration is adjusted to 15 to 70. ,
The manufacturing method of the oxidation product whose said catalyst is an oxide catalyst which has a composition represented by following Experimental formula (1) .
_{Mo 12 Bi a Fe b Co c} Ce d A e B f C g O h (1)
(In the formula, Mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt, Ce is cerium, A is at least one element selected from the group consisting of potassium, cesium and rubidium, and B is manganese, cobalt , Nickel, copper, zinc, lead, magnesium, calcium, strontium and barium, at least one element selected from the group consisting of C, at least one element selected from rare earth elements, ag The atomic ratio of each element to the Mo12 atom is shown, 1 ≦ a ≦ 6, 3 ≦ b ≦ 6, 2 ≦ c ≦ 8, 1 ≦ d ≦ 6, 0.01 ≦ e ≦ 2, 0 ≦ f <2, 0 ≦ g ≦ 5, and h is the number of oxygen atoms determined by the valence of constituent elements other than oxygen.) The method for producing an oxidation product according to claim 1, wherein a conversion rate of the olefin and / or alcohol in the gas phase oxidation reaction step is 90% or more .   The manufacturing method of the oxidation product of Claim 1 or 2 whose said reactor exit oxygen concentration is 0.05-1.0 vol%.   The olefin is one or more compounds selected from the group consisting of propylene and isobutylene, and the alcohol is one or more compounds selected from the group consisting of propanol, isobutanol, and t-butyl alcohol. The manufacturing method of the oxidation product of any one of -3.   The manufacturing method of the oxidation product of any one of Claims 1-4 whose said oxidation product is acrolein and / or methacrolein.