CN110809494B - Method for producing catalyst, method for producing unsaturated carboxylic acid, method for producing unsaturated aldehyde and unsaturated carboxylic acid, and method for producing unsaturated carboxylic acid ester - Google Patents
Method for producing catalyst, method for producing unsaturated carboxylic acid, method for producing unsaturated aldehyde and unsaturated carboxylic acid, and method for producing unsaturated carboxylic acid ester Download PDFInfo
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- CN110809494B CN110809494B CN201880041543.4A CN201880041543A CN110809494B CN 110809494 B CN110809494 B CN 110809494B CN 201880041543 A CN201880041543 A CN 201880041543A CN 110809494 B CN110809494 B CN 110809494B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
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Abstract
The present invention provides a catalyst capable of producing a target product with high selectivity. The present invention relates to a method for producing a catalyst containing at least molybdenum and phosphorus, which is used for producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen, and which comprises a step of exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure and calcining the catalyst precursor.
Description
Technical Field
The present invention relates to a method for producing a catalyst, a method for producing an unsaturated carboxylic acid, a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, and a method for producing an unsaturated carboxylic acid ester.
Background
A large amount of research has been conducted on methods for producing catalysts. The catalyst is generally produced by preparing a raw material liquid such as an aqueous solution or an aqueous slurry containing the elements constituting the catalyst, and drying and calcining the raw material liquid.
As the above-mentioned calcination, for example, calcination using a gas containing ammonia or water vapor is described in patent documents 1 to 3, calcination using a non-oxidizing gas is described in patent document 4, and calcination using a gas containing an oxygen-containing organic compound is described in patent document 5. Patent document 6 describes a firing method including a plurality of steps for changing the gas used and the firing temperature. Patent document 7 describes a gas flow rate for the catalyst precursor.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. Sho 58-61833
Patent document 2: japanese patent laid-open publication No. 58-67643
Patent document 3: japanese patent laid-open publication No. Sho 58-79545
Patent document 4: japanese patent laid-open publication No. 59-66349
Patent document 5: japanese patent laid-open No. 59-69148
Patent document 6: japanese patent laid-open No. 2012-2458432
Patent document 7: japanese patent laid-open publication No. 2009-213969
Disclosure of Invention
However, the catalysts produced by the methods described in patent documents 1 to 7 have a problem that the selectivity of the target product is insufficient when used in the following reaction: the unsaturated aldehyde is subjected to vapor phase catalytic oxidation with molecular oxygen to produce an unsaturated carboxylic acid, or at least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether is subjected to vapor phase catalytic oxidation with molecular oxygen to produce an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to each of them. Therefore, it is desired to develop a method for producing a catalyst capable of producing a target product with a higher selectivity. The present invention has been made in view of the above circumstances, and an object thereof is to provide a catalyst capable of producing a target product with high selectivity.
The above problems are solved by the following inventions [1] to [16 ].
[1] A process for producing a catalyst containing at least molybdenum and phosphorus, which is used for producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen, comprising the step of exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure and calcining the catalyst precursor.
[2] A process for producing a catalyst containing at least molybdenum and bismuth, which is used for producing an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to each of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether by vapor-phase catalytic oxidation of at least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether with molecular oxygen, comprising the step of exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure and calcining the catalyst precursor.
[3] The method for producing a catalyst according to item [1] or [2], wherein the unsaturated aldehyde is acrolein or methacrolein.
[4] The method for producing a catalyst according to any one of [1] to [3], wherein the calcination of the catalyst precursor is performed under a flow of at least 1 gas selected from an oxygen-containing gas and an inert gas.
[5] The method for producing a catalyst according to any one of [1] to [4], wherein the pressure is 10kPa (G) to 100kPa (G).
[6] The method for producing a catalyst according to [5], wherein the pressure is 20kPa (G) to 80kPa (G).
[7] The method for producing a catalyst according to any one of [1] to [6], wherein the maximum temperature during the calcination is 300 ℃ to 700 ℃.
[8] The method for producing a catalyst according to [7], wherein the maximum temperature during the calcination is 350 to 400 ℃.
[9] The method for producing a catalyst according to any one of [1] to [8], wherein the nitrogen-containing component is at least 1 selected from ammonium and nitrate.
[10] The process according to [1], wherein the catalyst precursor contains a heteropoly acid structure.
[11] The process for producing a catalyst according to [10], wherein the heteropoly acid structure is a Keggin-type heteropoly acid structure.
[12] A process for producing an unsaturated carboxylic acid, which comprises subjecting an unsaturated aldehyde to vapor phase catalytic oxidation with molecular oxygen in the presence of the catalyst produced by the process according to [1 ].
[13] A process for producing an unsaturated carboxylic acid, which comprises producing a catalyst by the process described in [1], and subjecting an unsaturated aldehyde to vapor-phase catalytic oxidation with molecular oxygen in the presence of the catalyst to produce an unsaturated carboxylic acid.
[14] A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which comprises subjecting at least 1 member selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether to vapor-phase catalytic oxidation with molecular oxygen in the presence of the catalyst produced by the process described in [2], to thereby produce an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to each member.
[15] A process for producing an unsaturated aldehyde and an unsaturated carboxylic acid by the process according to [2], wherein at least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether is subjected to vapor-phase catalytic oxidation with molecular oxygen in the presence of the catalyst to produce an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to each of them.
[16] A method for producing an unsaturated carboxylic acid ester, comprising esterifying an unsaturated carboxylic acid produced by the method according to any one of [12] to [15 ].
According to the present invention, a catalyst capable of producing a target product with high selectivity can be provided.
Detailed Description
[ method for producing catalyst ]
A first embodiment of the method for producing a catalyst according to the present invention is a method for producing a catalyst containing at least molybdenum and phosphorus, which is used in producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen. The method comprises a step of exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure to perform calcination.
In addition, a second embodiment of the method for producing a catalyst according to the present invention is a method for producing a catalyst containing at least molybdenum and bismuth, which is used for producing an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to at least 1 selected from propylene, isobutylene, primary butanol, tertiary butanol, and methyl tertiary butyl ether by vapor-phase catalytic oxidation with molecular oxygen. The method comprises a step of exposing a catalyst precursor containing a nitrogen-containing component to a pressure exceeding atmospheric pressure to perform calcination.
The method according to the present invention focuses on the pressure at the time of calcination of the catalyst precursor, and by exposing the catalyst precursor containing the nitrogen-containing component to a pressure exceeding atmospheric pressure and performing calcination, a catalyst capable of producing the desired product with high selectivity can be obtained. The reason is considered as follows. That is, the structure of the catalyst precursor is changed during the desorption of the nitrogen-containing component during the calcination, and a catalytically active site advantageous for the intended reaction is formed. In this case, the desorption of the nitrogen-containing component can be suppressed by exposing the catalyst precursor to a pressure higher than atmospheric pressure. As a result, it is presumed that the structure of the catalyst is changed at a slower rate than that in the case of calcination under a pressure of atmospheric pressure or less, and a more homogeneous active site structure is formed on the surface of the catalyst. In the prior art, the influence of the pressure during the calcination has not been studied in detail.
The method of the present invention is used for producing a catalyst containing at least molybdenum and phosphorus (hereinafter also referred to as a catalyst for producing an unsaturated carboxylic acid) used for producing an unsaturated carboxylic acid by vapor-phase catalytic oxidation of an unsaturated aldehyde with molecular oxygen. By carrying out the reaction using this catalyst, an unsaturated carboxylic acid can be produced with a higher selectivity. When the unsaturated aldehyde is acrolein or methacrolein, acrylic acid or methacrylic acid can be produced with a higher selectivity, which is preferable. In addition, the catalyst containing a heteropoly acid structure, particularly a Keggin type heteropoly acid structure, can produce unsaturated carboxylic acid with higher selectivity, and is therefore preferable.
The process of the present invention is used for producing a catalyst containing at least molybdenum and bismuth (hereinafter also referred to as a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid) used for producing an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to at least 1 selected from propylene, isobutylene, primary butanol, tertiary butanol, and methyl tertiary butyl ether by vapor-phase catalytic oxidation with molecular oxygen. By carrying out the reaction using this catalyst, an unsaturated aldehyde and an unsaturated carboxylic acid can be produced with a higher selectivity. From the viewpoint of selectivity, it is preferable that the unsaturated aldehyde is acrolein or methacrolein and the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
The composition of the catalyst obtained by the method of the present invention is not particularly limited, and in the case where the catalyst is the catalyst for producing an unsaturated carboxylic acid, the catalyst preferably has a composition represented by the following formula (1) from the viewpoint that an unsaturated carboxylic acid can be produced with a higher selectivity.
P α1 Mo α2 V α3 Cu α4 A α5 E α6 G α7 O α8 (1)
In the formula (1), P, mo, V, cu and O are symbols of elements representing phosphorus, molybdenum, vanadium, copper and oxygen, respectively. A represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron. E represents at least 1 element selected from potassium, rubidium, cesium, thallium, magnesium and barium. G represents at least 1 element selected from iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum. α 1 to α 8 represent the atomic ratio of each element, α 1=0.5 to 3, α 3=0.01 to 3, α 4=0.01 to 2, α 5=0 to 3, preferably 0.01 to 3, α 6=0.01 to 3, α 7=0 to 4, and α 8 is the atomic ratio of oxygen necessary to satisfy the valence of each element described above when α 2= 12.
In addition, when the catalyst obtained by the method of the present invention is the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, the catalyst preferably has a composition represented by the following formula (2) from the viewpoint that the unsaturated aldehyde and the unsaturated carboxylic acid can be produced with a higher selectivity.
Mo α9 Bi α10 Fe α11 X α12 A’ α13 E’ α14 G’ α15 Si α16 O α17 (2)
In the formula (2), mo, bi, fe, si and O are symbols of elements representing molybdenum, bismuth, iron, silicon and oxygen, respectively. X represents at least 1 element selected from cobalt and nickel. A' represents at least 1 element selected from chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc. E' represents at least 1 element selected from phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium. G' represents at least 1 element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. α 9 to α 17 represent atomic ratios of the elements, α 10 to 3 when α 9 is 12, α 11 to 0.01, α 12 to 1 to 12, α 13 to 0, α 14 to 0, α 15 to 0.001, and α 16 to 0 to 20, α 17 being an atomic ratio of oxygen necessary to satisfy the atomic valences of the elements.
The method for producing the catalyst according to the present invention is not particularly limited as long as it includes a step of exposing the catalyst precursor containing the nitrogen-containing component to a pressure exceeding atmospheric pressure to perform calcination (hereinafter, also referred to as calcination step). However, from the viewpoint of obtaining a catalyst capable of producing a target product with a higher selectivity, it is preferable that the method comprises the steps of: a step of preparing a raw material liquid containing each element constituting the catalyst (hereinafter also referred to as a raw material liquid preparation step), a step of drying the raw material liquid to obtain a catalyst precursor (hereinafter also referred to as a drying step), and a calcination step. The method may further include a step of molding the catalyst precursor (hereinafter, also referred to as a molding step) between the drying step and the calcination step, if necessary.
(raw Material solution preparation Process)
In the raw material liquid preparation step, a raw material liquid containing each element constituting the catalyst is prepared. In the production of the catalyst for unsaturated carboxylic acid production, the raw material liquid contains at least molybdenum and phosphorus. In the production of the catalyst for unsaturated aldehyde and unsaturated carboxylic acid, the raw material liquid contains at least molybdenum and bismuth. By containing these elements in the raw material liquid, a catalyst for producing an unsaturated carboxylic acid or a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which has a high selectivity for a target product, can be produced. When the catalyst is a catalyst for producing an unsaturated carboxylic acid, the kind and ratio of each element constituting the catalyst may be, for example, the element and atomic ratio represented by the above formula (1). When the catalyst is a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, the kind and the ratio of each element constituting the catalyst may be, for example, the element represented by the above formula (2) and the atomic ratio.
The method for preparing the raw material liquid is not particularly limited, but a method for preparing a slurry-like raw material liquid by adding raw materials of the respective elements into water, heating to 30 to 100 ℃, and stirring is preferred. The amount of water used is preferably 200 to 1000 parts by mass per 100 parts by mass of the total of the raw materials of the elements.
The raw materials of the elements are not particularly limited, and oxides, nitrates, carbonates, ammonium salts, and the like of the elements can be appropriately selected and used. For example, molybdic acid, molybdenum trioxide, ammonium paramolybdate, etc. can be used as the raw material of molybdenum, and molybdic acid and molybdenum trioxide are preferable. As the phosphorus raw material, orthophosphoric acid, phosphorus pentoxide, ammonium phosphate, or the like can be used. As the raw material of vanadium, ammonium metavanadate, vanadium pentoxide, or the like can be used. As a raw material of copper, copper nitrate, copper sulfate, copper carbonate, or the like can be used. As the raw material of bismuth, bismuth nitrate, bismuth oxide, bismuth acetate, bismuth hydroxide, and the like can be used. One kind of these raw materials may be used, or two or more kinds thereof may be used in combination.
In the method of the present invention, since the catalyst precursor contains a nitrogen-containing component, it is preferable that the raw material liquid contains a nitrogen-containing component. The nitrogen-containing component may be ammonium, nitrate, a nitrogen-containing heterocycle, or the like, but preferably at least 1 selected from ammonium and nitrate from the viewpoint of the selectivity of the target product. Here, the ammonium group in the present invention may be changed to ammonium ion (NH) 4 + ) Ammonia (NH) 3 ) And ammonium contained in an ammonium-containing compound such as an ammonium salt. Examples of the ammonium-containing compound include ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium acetate, ammonium vanadate, ammonium salts of catalyst constituent elements, and the like. In addition, nitrate in the present invention is nitrate ion (NO) 3 － ) Nitrite ion (NO) 2 － ) Plasma oxynitride ions are collectively referred to as oxynitride ions. The nitrate group includes, for example, a nitrate ion contained in a nitrate of a catalyst constituent element. One kind of them may be used, or two or more kinds thereof may be used in combination. The nitrogen-containing component can be contained in the raw material liquid by using ammonium salts or nitrate salts of the respective elements as the raw materials of the respective elements.
The scale of the preparation of the raw material liquid is not particularly limited, and the lower limit of the raw material amount of the main element is preferably 100g or more, and more preferably 1kg or more. The upper limit is preferably 10t or less, and more preferably 1t or less. By such a scale, a good raw material liquid can be stably prepared.
(drying step)
In the drying step, the raw material liquid obtained in the raw material liquid preparation step is dried to obtain a catalyst precursor. The method of drying the raw material liquid is not particularly limited, and examples thereof include an evaporation drying method, a spray drying method, a drum drying method, and a pneumatic drying method. The type and model of the dryer used for drying, the temperature and atmosphere during drying are not particularly limited, and examples thereof include conditions for drying at 100 to 180 ℃ for 0.1 to 20 hours in an air atmosphere. Since physical properties such as flowability, moldability, etc. of the catalyst precursor can be controlled by changing the drying conditions, it is preferable to set the conditions according to the purpose.
When the method according to the present invention is used for producing the catalyst for producing an unsaturated carboxylic acid, the obtained catalyst precursor preferably contains a heteropoly acid structure, more preferably a Keggin-type heteropoly acid structure, from the viewpoint that an unsaturated carboxylic acid can be produced with a higher selectivity. Whether or not the catalyst precursor contains a heteropoly acid structure (Keggin-type heteropoly acid structure) can be confirmed by measuring the catalyst precursor by infrared absorption analysis. For example, when the catalyst precursor contains a Keggin-type heteropoly acid structure, the infrared absorption spectrum obtained is 1060, 960, 870, 780cm －1 With characteristic peaks in the vicinity.
The amount of the nitrogen-containing component contained in the obtained catalyst precursor is not particularly limited, and may be, for example, 0.5 to 7.0 mass%.
(Molding Process)
In the molding step, the catalyst precursor obtained in the drying step is molded. The molding method is not particularly limited, and known dry and wet molding methods can be used. For example, tablet forming, press forming, extrusion forming, granulation forming, and the like can be given. The shape of the molded article is also not particularly limited, and examples thereof include a cylindrical shape, a toroidal shape, and a spherical shape. In addition, in the molding, it is preferable to mold only the catalyst precursor without adding a carrier or the like to the catalyst precursor, but if necessary, known additives such as graphite, talc, and the like may be added.
(calcination Process)
In the calcination step, the obtained catalyst precursor containing the nitrogen-containing component is exposed to a pressure exceeding atmospheric pressure to be calcined. The pressure at which the catalyst precursor is exposed is preferably 10kPa (G) or more, more preferably 20kPa (G) or more, and still more preferably 30kPa (G) or more. The pressure is preferably 100kPa (G) or less, more preferably 80kPa (G) or less, and still more preferably 70kPa (G) or less. When the pressure is 10kPa (G) or more, the desorption of the nitrogen-containing component is suppressed, and a more homogeneous active site structure can be formed on the catalyst surface. When the pressure is 100kPa (G) or less, the reaction rate of the catalyst can be suppressed from decreasing without excessively inhibiting the separation of the nitrogen-containing component from the catalyst precursor. Incidentally, "kPa (G)" represents gauge pressure, and atmospheric pressure + gauge pressure is an actual pressure.
The pressure is a pressure during the temperature raising process and during the temperature maintaining process in the calcination step. In addition, in a system having a spatial distribution of pressure such as a case where calcination is performed in a vessel having a spatial distribution of pressure, the pressure value is a value obtained by measuring any point in the vessel, and in a system having a spatial distribution of pressure such as a case where calcination is performed in the form of a gas flowing through a tubular calcination vessel, the pressure value is a value of the lowest portion in the system, such as the pressure at the outlet of the calcination gas. In the system, the term "in the range from the inlet of the calcining gas to the outlet of the calcining gas" in the calcining vessel "means. The method for measuring the pressure in the system is not particularly limited, and for example, the pressure can be measured by providing a pressure gauge at a position upstream of the calcined gas outlet and as close as possible to the calcined gas outlet. The method for increasing the pressure is not particularly limited, and in the case of calcining under gas flow as described below, for example, the calcination can be performed by a method such as extending a pipe for gas outlet, providing a pressure control valve at the gas outlet and screwing the valve, and connecting the gas outlet to a trap tank (12488125211248312503.
The type of the atmosphere gas used in the calcination of the catalyst precursor is not particularly limited, and an oxygen-containing gas such as air or an inert gas is preferred. The inert gas is a gas which does not lower the activity of the catalyst, and examples thereof include nitrogen, carbon dioxide, helium, argon, and the like. The gas is more preferably air, a mixed gas of nitrogen, oxygen and air, or a mixed gas thereof, and further preferably air. In addition, the gas may contain water vapor. The amount of water vapor is preferably 0.01 to 5 vol% based on the total gas to be circulated, and particularly preferably the lower limit is 0.05 vol% or more and the upper limit is 2 vol% or less. The method of supplying the atmosphere gas during the calcination is not particularly limited, and the calcination may be performed by filling the inside of the calcination vessel with the atmosphere gas and then sealing the vessel, or the calcination may be performed under a gas flow in which the atmosphere gas is continuously supplied into the calcination vessel.
The lower limit of the maximum temperature during the above calcination is preferably 300 ℃ or more, more preferably 320 ℃ or more, still more preferably 350 ℃ or more, and particularly preferably 370 ℃ or more. The upper limit of the maximum temperature is preferably 700 ℃ or lower, more preferably 450 ℃ or lower, still more preferably 400 ℃ or lower, and particularly preferably 390 ℃ or lower. The removal of the nitrogen-containing component can be promoted by the calcination temperature of 300 ℃ or more, and the reduction of the specific surface area due to thermal decomposition or sintering of the catalyst can be suppressed by the calcination temperature of 700 ℃ or less. The maximum value of the above temperature indicates the temperature of the portion having the highest value among the temperatures of the inner wall surfaces of the calcination vessel in contact with the catalyst precursor. The method of measuring the temperature is not particularly limited, but a method using a thermocouple is preferred.
The preferable range of the residual amount of the nitrogen-containing component in the catalyst to be obtained varies depending on the method of using the catalyst, etc., and may be, for example, 0.001 to 1mmol/g per unit mass of the catalyst.
The shape of the calcining container is not particularly limited, and it may be a box-like or tubular shape, and the cross-sectional area of 2 to 100cm is particularly preferably used 2 The tubular calcination vessel of (1). Passing through the cross-sectional area of 2cm 2 This improves the industrial productivity. Further, the cross-sectional area is 100cm 2 Hereinafter, the temperature can be easily controlled, and the occurrence of hot spots (hot spots) can be suppressed.
[ Process for producing unsaturated Carboxylic acid ]
The unsaturated aldehyde is subjected to vapor phase catalytic oxidation with molecular oxygen in the presence of the catalyst produced by the method of the present invention. That is, the process for producing an unsaturated carboxylic acid according to the present invention comprises: a step of producing a catalyst by the method of the present invention, and a step of subjecting an unsaturated aldehyde to vapor-phase catalytic oxidation with molecular oxygen in the presence of the catalyst. By using the catalyst produced by the method of the present invention, an unsaturated carboxylic acid can be produced with a higher selectivity than in the conventional method. As the unsaturated aldehyde, acrolein or methacrolein is preferable, and methacrolein is more preferable. Hereinafter, a case where methacrolein is used as the unsaturated aldehyde will be described. In this method, for example, a raw material gas containing methacrolein and molecular oxygen is brought into contact with a catalyst to catalytically oxidize methacrolein in a gas phase with the molecular oxygen, thereby obtaining methacrylic acid.
The concentration of the raw material compound in the raw material gas is not limited, and may be set to any concentration, but is preferably 1 to 20% by volume, more preferably 3% by volume or more at the lower limit, and 10% by volume or less at the upper limit. The molecular oxygen concentration in the raw material gas is preferably 0.5 to 4.0mol, and particularly preferably 1.0mol or more in the lower limit and 3.0mol or less in the upper limit, based on 1mol of the raw material compound. For dilution, an inert gas such as nitrogen or carbon dioxide may be added to the raw gas, or water vapor may be added. The reaction pressure may be set in the range of atmospheric pressure to several hundred kPa (G). The reaction temperature is preferably 230 to 450 ℃ from the viewpoint of the yield of the target product, and particularly preferably has a lower limit of 250 ℃ or more and an upper limit of 400 ℃ or less.
[ Process for producing unsaturated aldehyde and unsaturated carboxylic acid ]
At least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether is subjected to vapor phase catalytic oxidation with molecular oxygen in the presence of the catalyst produced by the process according to the present invention. That is, the process for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to the present invention comprises: the process for producing a catalyst by the method according to the present invention comprises a step of subjecting at least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol and methyl tertiary butyl ether to vapor-phase catalytic oxidation with molecular oxygen in the presence of the catalyst. By using the catalyst produced by the method of the present invention, an unsaturated aldehyde and an unsaturated carboxylic acid can be produced with a higher selectivity than in the conventional method. The unsaturated aldehyde is preferably acrolein or methacrolein, and more preferably methacrolein. The unsaturated carboxylic acid is preferably acrylic acid or methacrylic acid, more preferably methacrylic acid. The conditions for the vapor phase catalytic oxidation reaction may be the same as in the above-mentioned method for producing an unsaturated carboxylic acid.
[ Process for producing unsaturated Carboxylic acid ester ]
The method for producing an unsaturated carboxylic acid ester according to the present invention is a method for esterifying an unsaturated carboxylic acid obtained by the method according to the present invention. According to this method, an unsaturated carboxylic acid ester can be obtained using an unsaturated carboxylic acid obtained by vapor-phase catalytic oxidation of an unsaturated aldehyde or vapor-phase catalytic oxidation of at least 1 selected from the group consisting of propylene, isobutylene, primary butanol, tertiary butanol, and methyl tertiary butyl ether. Examples of the alcohol to be reacted with the unsaturated carboxylic acid include methanol, ethanol, isopropanol, n-butanol, and isobutanol. Examples of the unsaturated carboxylic acid ester to be obtained include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. The reaction may be carried out in the presence of an acidic catalyst such as a sulfonic acid type cation exchange resin. The reaction temperature is preferably 50 to 200 ℃.
Examples
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. "parts" in examples and comparative examples represent parts by mass. The molar ratio of the catalyst composition can be calculated by analyzing the components obtained by dissolving the catalyst in aqueous ammonia by ICP emission spectrometry.
The raw material gas and the product in the production of methacrylic acid were analyzed by gas chromatography. From the results of the gas chromatography, the ratio of conversion of methacrolein and the selectivity for methacrylic acid were determined by the following formulas.
Reaction rate (%) of methacrolein = (R/F) × 100
Selectivity (%) of methacrylic acid (= (P/R) × 100
Wherein F is the number of moles of methacrolein supplied per unit time, R is the number of moles of methacrolein reacted per unit time, and P is the number of moles of methacrylic acid produced per unit time.
The selectivity of methacrylic acid varies depending on the reaction rate of methacrolein. Therefore, it is preferable to compare the selectivities of methacrylic acid in the gas-phase catalytic oxidation reaction using the respective catalysts so that the reaction rates of methacrolein become the same value. Therefore, the following examples and comparative examples show the result that the reaction rate of methacrolein is made uniform to about 40% by changing the contact time by appropriately adjusting the amount of the catalyst used in the reaction under the condition that the reaction gas flow rate is constant.
[ example 1]
(1) Raw Material liquid preparation Process
To 400 parts of pure water were added 100 parts of molybdenum trioxide, 4.06 parts of ammonium metavanadate, 6.67 parts of 85 mass% phosphoric acid, 0.84 part of antimony trioxide and 2.80 parts of copper nitrate. This was stirred to prepare a slurry, and the obtained slurry was heated at 90 ℃ for 3 hours. While this was kept at 90 ℃, a solution prepared by dissolving 11.3 parts of cesium carbonate in 40.3 parts of pure water was added thereto, and the mixture was kept for 30 minutes. Next, a solution of 8.34 parts of ammonium carbonate dissolved in 37.5 parts of pure water was added. Then, the mixture was held at 90 ℃ for 30 minutes to obtain a raw material solution.
(2) Drying step
The obtained raw material solution was heated at 101 ℃ and stirred, evaporated and dried. Thereafter, the obtained solid matter was dried at 90 ℃ for 16 hours to obtain a catalyst precursor. The obtained catalyst precursor contains a Keggin type heteropoly acid structure. In addition, the catalyst precursor had a composition of Mo other than oxygen 12 V 0.6 P 1.0 Sb 0.1 Cu 0.2 Cs 1.2 (NH 4 ) 3.0 。
(3) Shaping step
The obtained catalyst precursor was molded into a ring shape having an outer diameter of 5mm, an inner diameter of 2mm and a length of 5mm by a tablet molding machine.
(4) Calcination Process
The resulting molded product of the catalyst precursor was packed in a stainless steel tube having an inner diameter of 27.5mm and a length of 6m at a space velocity of 370h －1 The catalyst precursor was calcined at 380 ℃ under the circulation of air to obtain a catalyst. At this time, the calcination gas outlet was connected to an exhaust component collection tank filled with water, and the pressure in the calcination step was set to 64kPa (G). The holding time at 380 ℃ in the calcination was additionally made 16 hours. In the calcination, the maximum temperature was 380 ℃. From the obtained catalyst, a nitrogen-containing component in an amount of 0.001 to 1.0mmol/g per unit mass of the catalyst was detected.
The obtained catalyst was filled in a reaction tube, and a reaction gas was introduced to carry out production of methacrylic acid by gas-phase catalytic oxidation under the following reaction conditions. The results are shown in Table 1.
(reaction conditions)
Reaction gas: mixed gas of methacrolein 4% by volume, oxygen 10% by volume, water vapor 15% by volume, and nitrogen 71% by volume
Reaction temperature: 310 deg.C
Reaction pressure: 101kPa (G)
Contact time: 1.8 seconds.
Comparative example 1
A catalyst was produced in the same manner as in example 1, except that the amount of water in the exhaust gas component collection vessel connected to the calcination gas outlet was made smaller than in example 1, and the pressure in the calcination step was set to 0kPa (G), and the catalyst precursor was calcined at 380 ℃ for 12 hours. The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.
Comparative example 2
A catalyst was produced in the same manner as in example 1, except that the amount of water in the exhaust component collection vessel connected to the calcination gas outlet was made smaller than in example 1, and the pressure in the calcination step was set to 0kPa (G). The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.2 seconds using the obtained catalyst. The results are shown in Table 1.
[ example 2]
A catalyst was produced in the same manner as in example 1, except that the pressure in the calcination step was set to 64kPa (G) at the calcination gas outlet, and the catalyst precursor was calcined at 382 ℃ for 16 hours. The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
[ example 3]
A catalyst was produced in the same manner as in example 1, except that the amount of water in the exhaust component collection vessel connected to the calcination gas outlet was made smaller than in example 1, and the pressure in the calcination step was set to 54kPa (G), and the catalyst precursor was calcined at 382 ℃ for 14 hours. The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.7 seconds using the obtained catalyst. The results are shown in Table 1.
[ example 4]
A catalyst was produced in the same manner as in example 2, except that the pressure in the calcination step was controlled to 10kPa (G) by a pressure control valve and the catalyst precursor was calcined at 380 ℃ for 16 hours. The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.4 seconds using the obtained catalyst. The results are shown in Table 1.
[ example 5]
A catalyst was produced in the same manner as in example 4, except that the pressure in the calcination step was controlled to 30kPa (G) by a pressure control valve. The reaction was carried out in the same manner as in example 1 except that the contact time was changed to 1.5 seconds using the obtained catalyst. The results are shown in Table 1.
[ Table 1]
As shown in table 1, in examples 1 to 5 in which the catalyst was produced by the method of the present invention, methacrylic acid could be produced with a higher selectivity than in comparative examples 1 and 2.
Claims (9)
1. A method for producing a catalyst, which is used for producing methacrylic acid by gas-phase catalytic oxidation of methacrolein with molecular oxygen, contains at least molybdenum and phosphorus, and has a composition represented by the following formula (1),
the method for producing the catalyst comprises: a step of exposing the catalyst precursor containing ammonium groups to a pressure of 10kPa (G) or more and 80kPa (G) or less in a gas flow containing an oxygen-containing gas and calcining the catalyst precursor,
P α1 Mo α2 V α3 Cu α4 A α5 E α6 G α7 O α8 (1)
in formula (1), P, mo, V, cu, and O are each an element symbol representing phosphorus, molybdenum, vanadium, copper, and oxygen, a represents at least 1 element selected from antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten, and boron, E represents at least 1 element selected from potassium, rubidium, cesium, thallium, magnesium, and barium, G represents at least 1 element selected from iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium, and lanthanum, α 1 to α 8 represent an atomic ratio of each element, and when α 2=12, α 1=0.5 to 3, α 3=0.01 to 3, α 4=0.01 to 2, α 5=0 to 3, α 6=0.01 to 3, α 7=0 to 4, and α 8 is an atomic ratio satisfying the valence of each element.
2. The method for producing a catalyst according to claim 1, wherein the pressure is 20kPa (G) or more.
3. The method for producing a catalyst according to claim 2, wherein the pressure is 30kPa (G) or more and 70kPa (G) or less.
4. The method for producing a catalyst according to any one of claims 1 to 3, wherein the maximum value of the temperature during the calcination is 300 ℃ to 700 ℃.
5. The method for producing a catalyst according to claim 4, wherein the maximum value of the temperature during the calcination is 350 to 400 ℃.
6. The method for producing a catalyst according to claim 1, wherein the catalyst precursor contains a heteropoly acid structure.
7. The method for producing a catalyst according to claim 6, wherein the heteropoly acid structure is a Keggin-type heteropoly acid structure.
8. A process for producing methacrylic acid by subjecting methacrolein to gas phase catalytic oxidation with molecular oxygen in the presence of the catalyst produced by the process according to claim 1.
9. A method for producing a methacrylic acid ester, comprising esterifying methacrylic acid produced by the method according to claim 8.
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| PCT/JP2018/025649 WO2019013116A1 (en) | 2017-07-10 | 2018-07-06 | Method for manufacturing catalyst, method for manufacturing unsaturated carboxylic acid, method for manufacturing unsaturated aldehyde and unsaturated carboxylic acid, and method for manufacturing unsaturated carboxylic acid ester |
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| CN1131583A (en) * | 1994-11-29 | 1996-09-25 | Basf公司 | Preparation of catalyst consisting of carrier and catalytically active oxide material applied to surface of carrier |
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| CN103370591A (en) * | 2011-02-18 | 2013-10-23 | 旭化成化学株式会社 | Burning apparatus, process for producing oxide catalyst, and process for producing unsaturated acid or unsaturated nitrile |
| JP2014226614A (en) * | 2013-05-23 | 2014-12-08 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid |
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| JPS5861833A (en) | 1981-10-09 | 1983-04-13 | Mitsubishi Rayon Co Ltd | Calcining method of phosphorus and molybdenum type catalyst |
| JPS5867643A (en) | 1981-10-15 | 1983-04-22 | Mitsubishi Rayon Co Ltd | Preparation of unsaturated acid |
| JPS5879545A (en) | 1981-11-04 | 1983-05-13 | Mitsubishi Rayon Co Ltd | Calcining method for phosphorus-molybdenum catalyst |
| JPS5966349A (en) | 1982-10-05 | 1984-04-14 | Ube Ind Ltd | Preparation of catalyst used in manufacture of methacrylic acid |
| JPS5969148A (en) | 1982-10-12 | 1984-04-19 | Ube Ind Ltd | Activating method of catalyst for producing methacrylic acid |
| KR100557640B1 (en) * | 2004-01-09 | 2006-03-10 | 주식회사 엘지화학 | Novel Heteropoly Acid Catalyst and Preparing Method Thereof |
| JP5069152B2 (en) | 2008-03-07 | 2012-11-07 | 三菱レイヨン株式会社 | Unsaturated carboxylic acid synthesis catalyst, method for producing the same, and method for producing unsaturated carboxylic acid using the catalyst |
| EP2179790A1 (en) * | 2008-10-21 | 2010-04-28 | Sued-Chemie AG | Bismuth-containing mixed oxide catalysts |
| JP5793345B2 (en) | 2011-05-25 | 2015-10-14 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid and method for producing methacrylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131583A (en) * | 1994-11-29 | 1996-09-25 | Basf公司 | Preparation of catalyst consisting of carrier and catalytically active oxide material applied to surface of carrier |
| CN1178138A (en) * | 1996-04-29 | 1998-04-08 | 隆萨公开有限公司 | Process for transformation of vanadium/phophorus mixed catalyst precursor into active catalyst for production of maleic anhydride |
| CN103370591A (en) * | 2011-02-18 | 2013-10-23 | 旭化成化学株式会社 | Burning apparatus, process for producing oxide catalyst, and process for producing unsaturated acid or unsaturated nitrile |
| JP2014226614A (en) * | 2013-05-23 | 2014-12-08 | 住友化学株式会社 | Method for producing catalyst for producing methacrylic acid, and method for producing methacrylic acid |
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