WO1993013042A1 - Procede de production d'acide methacrylique et d'aldehyde methacrylique - Google Patents

Procede de production d'acide methacrylique et d'aldehyde methacrylique Download PDF

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Publication number
WO1993013042A1
WO1993013042A1 PCT/JP1989/000510 JP8900510W WO9313042A1 WO 1993013042 A1 WO1993013042 A1 WO 1993013042A1 JP 8900510 W JP8900510 W JP 8900510W WO 9313042 A1 WO9313042 A1 WO 9313042A1
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Prior art keywords
methacrylic acid
isobutane
reaction
producing
gas
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PCT/JP1989/000510
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English (en)
Japanese (ja)
Inventor
Setsuo Yamamatsu
Tatsuo Yamaguchi
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Setsuo Yamamatsu
Tatsuo Yamaguchi
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Application filed by Setsuo Yamamatsu, Tatsuo Yamaguchi filed Critical Setsuo Yamamatsu
Priority to PCT/JP1989/000510 priority Critical patent/WO1993013042A1/fr
Priority to US07/400,117 priority patent/US5191116A/en
Publication of WO1993013042A1 publication Critical patent/WO1993013042A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups

Definitions

  • the present invention relates to a method for producing methacrylic acid and methacryloline in a single step by subjecting isobutane to gas phase catalytic oxidation. More specifically, the present invention relates to isobutane in the presence of molecular oxygen in the presence of a heteropolyacid and a erosion medium having a P / As-Mo-V / Cu system composition in a low temperature gas phase.
  • saturated hydrocarbons such as isobutane have been considered inert gases.
  • Japanese Patent Application Laid-Open No. 55-2619 describes that it is used as a diluent for a reaction gas in oxidation of olefins and aldehydes. Since isobutane is poor in reactivity, it is converted to isobutylene using a dehydrogenation catalyst or an oxidative dehydrogenation catalyst, and then oxidized to metacrolein or methanol. In general, a method of converting to lactic acid was used (for example, Japanese Patent Application Laid-Open No. 58-189130).
  • U.S. Pat. No. 4,260,822 is the first to show that methacrylic acid can be produced in a single step from isobutane.
  • a specific catalyst consisting of oxides of antimony, molybdenum and phosphorus is used, and methacrylic acid is obtained with high selectivity from isobutane in one step.
  • the isobutane concentration is 10 mol%
  • 10% of the isobutane will react and 50% of it will be converted to methacrylic acid.
  • the content of methacrylic acid in the reaction gas is as low as 0.5 mol%, and the productivity per unit weight of the edible medium is extremely low.
  • the isobutane strain is increased and the reaction is performed at 28 mol%, the reaction yield tends to decrease. Therefore, it is still insufficient for an industrial production method in terms of productivity per unit weight of the medium.
  • Japanese Patent Application Laid-Open No. Sho 62-1323282 discloses that heteropolyacid is used as an erosion medium, and isobutane having a low concentration of 30 to 60 mol% is reacted to produce methacrylic acid.
  • Methods have been proposed to produce with high yields and high productivity.
  • high efficiency is obtained by a very distinctive method, in which a heteropolyacid containing molybdenum is used as a catalyst with phosphorus as the central element, and isobutane and oxygen are alternately brought into contact with the erosion medium. Rate and wealth productivity.
  • a special reaction apparatus is required to alternately bring isobutane and oxygen into contact with the catalyst, and the operation is complicated. For this reason, an industrial production method may be economically disadvantageous in this point as compared with a normal production method in which a mixed gas containing isobutane and oxygen is simply brought into contact with a catalyst.
  • a mixed gas containing isobutane and oxygen is brought into gaseous phase contact with the catalyst at a reaction temperature of 350 ° C or less, more preferably 320 ° C or less, to stably produce methacrylic acid for a long time.
  • the present inventors provide a gas phase contact of a mixed gas containing isobutane and oxygen with a catalyst at a reaction temperature of 350 ° C or less, more preferably 320 ° C or less.
  • a catalyst that shows excellent reaction performance just by performing a simple reaction
  • we conducted intensive research on a heteropoly catalyst found that many elements and innumerable combinations were obtained.
  • the erosion medium containing a heteropolyacid containing P and / or As as a central element, containing Mo as a coordinating element, and having a P / As-Mo-V / Cu system composition.
  • methacrylic acid and methacrolein can be produced with high selectivity simply by bringing a mixed gas containing isobutane and oxygen into gaseous phase into contact with a catalyst.
  • the combination of at least one of alkali metals, alkaline earth metals, and T 1 as a corrosion medium makes it possible to obtain methacrylic acid and methacrylate even at low reaction temperatures below 320 ° C. It has been found that mouth lanes can be produced with high reaction yields and high productivity.
  • corrosion media containing at least one of alkali metals, alkaline earth metals, and T 1 have the effect of lowering the reaction temperature, as well as the decrease in activity over time and the selection of methacrylic acid. It has been found that the rate of decrease in the rate over time is extremely small, and that the catalyst becomes a very excellent corrosion medium with a long catalyst life. The present invention has been completed based on these findings.
  • the present invention contains a heteropolyacid containing P and / or As as a central element and containing Mo as a coordinating element, and has the following formula (1):
  • A represents P and / or As, Mo represents molybdenum, B represents V and Z or Cu.
  • C represents an alkali metal, alkaline It represents at least one of the earth metals, T 1.
  • D is Ag, Zn, T i, Z r, b.
  • the catalyst having the above composition as a catalyst, and high productivity can be achieved by bringing a mixed gas containing isobutane and oxygen into gas phase contact with the catalyst of the present invention.
  • Methacrylic acid and methacrolein can be obtained with high yield and high yield.
  • Lack of essential components in the above composition, that is, P / As-Mo-V / Cu If the composition deviates from the above range, as will be apparent from Comparative Examples 1 to 14, the reaction method in which a mixed gas containing isobutane and oxygen is brought into gaseous phase contact with the catalyst. The selectivity for methacrylic acid is significantly reduced.
  • V and / or Cu forms a stable salt with the heteropolyacid or replaces a part of the coordination element of the heteropolyacid, resulting in excessive oxidation of methacrylic acid and methacrylone. It is considered that the formation of oxygen species on the catalyst, which may cause the occurrence of oxidization, is specifically suppressed.
  • the reaction temperature can be lowered, and the reaction can be carried out at a temperature at which thermal decomposition of the heteropolyacid is difficult to occur. Further increase the activity at low temperatures, 320.
  • the catalyst contains at least one of an alkali metal, an alkaline earth metal and T 1. In this case, the effect of improving the thermal stability of the catalyst can also be obtained, and when combined with the effect of lowering the reaction temperature, at least one of the alkali metals, the alkaline earth metals, and T 1 is used.
  • a catalyst containing one or more catalysts is an erosion medium with a long catalyst life and low durability.
  • the use of at least one of the alkali metals, argali earth metals, and T1 in combination with vanadium and Z or saw increases the selectivity of metaacrylic acid. While maintaining the above values, excellent effects such as a high isobutane conversion and a low reaction temperature can be obtained. In addition, by lowering the reaction temperature, the reaction products such as methacrylic acid and methacryloline are sequentially oxidized to be effectively suppressed from being oxidized to carbon dioxide. There is also a secondary effect of improving the selectivity of combining methacrylic acid with the methacrylic acid lane.
  • the reaction product when this reaction is carried out in a fluidized-bed reactor, the reaction product is generally liable to be further excessively oxidized, and the selectivity of methacrylic acid is reduced as compared with a fixed-bed reaction. Often.
  • the reaction can be carried out at a low temperature, so that dimethacrylic acid selectivity can be obtained even in a fluidized bed reactor.
  • the catalyst used in the present invention contains P and Z or As as a central element, contains heteropolyacid containing Mo as a coordinating element, and contains V and V as catalyst constituent elements. Or contain Cu.
  • the atomic ratio of the catalyst constituent elements to each other is Mo: 12, P and / or As is 0.5 to 3, V and Z or Cu are 0.01 to 3, preferably 0.05 to 2.0. It is. More favorable results can be obtained by using at least one of alkali metal, alkaline earth metal and T1 in the above composition.
  • At least one kind selected from Li, Na, K, Rb and Cs can be used as the alkali metal. Or at least one selected from Mg, C a, S r, and B a.
  • These Al metal, Al earth metal and T1 are 0.01 to 3, Preferably, it is added in the range of 0.1 to 2.
  • Ag, Zn, Cd, Ti, Zr, N "b, Ta, Cr, W, Mn, Fe, Co, Ni, Rh, Sn, Bi When at least one selected from the group consisting of Se, Te, Y, La, Ce, Pr, and Nd is added as a catalyst element, the value should be 0.01 to 3. It is particularly preferred that the value be 0.05 to 1.
  • Heteropolyacids containing P and Z or As as central elements and containing Mo as a coordinating element include linmolybdic acid, arsenic molybdic acid, and linsenic molybdic acid. It is known to adopt various structures (Chemistry, Vol. 29, No. 853, Sasaki, Matsumoto), and the ratio of central element to coordinating element is 1/12, 1/11, 1 / Various structures such as 10, 1/9, 2/17, and 2/18 are known. Among them, those having a 1/12 structure called a Keggin structure are particularly suitable.
  • Vanadium preferably substitutes a part of the coordinating element of linmolybdic acid, arsenic molybdic acid, and arsenic molybdic acid. As such, it may exist in a state outside the heteropolyacid. ⁇ may be present as a metal salt of heteropoly acid or in the form of an oxide or oxyacid, although the chemical state is extremely complicated and the details are not clear. It may exist in a state other than heteropolyacid. Further, the constituent elements of the heteropolyacid may be partially substituted. Preferably, the oxide or heteropolyacid gold is used. It should be present as a genus salt. Alkali metals, alkaline earth metals, and T 1 exist mainly in the form of heteropolyacid salts. Also, A g, Z n, C d, T i, Z r, N b, T a,
  • Se, Te, Y, La, Ce, Pr and Nd may be present as a metal salt of a heteropolyacid like Cu, or may be an oxide or oxyacid. Thus, it may exist in a state other than the heteropolyacid. Further, the constituent elements of the heteropolyacid may be partially substituted.
  • the catalyst used in the present invention can be easily prepared by a known method (preparation operation).
  • linmolybdenic acid, limbana domolybdic acid, arsenic molybdic acid, arsenic acid When a heteropolyacid or salt thereof, such as nadomolibdenic acid, is in solution or slurry, or under conditions where these polyhedral polyacids are formed, Oxides, hydroxides, carbonates, nitrates, chlorides, oxyacids, phosphates, oxalates, acetates, organic compounds containing compounds containing the necessary elements as catalyst constituent elements After adding in the form of a compound or metal, evaporate to dryness.
  • the obtained catalyst is calcined at 250 to 500 ° C. for 2 to 24 hours in an air atmosphere to obtain a target catalyst.
  • the catalyst preparation method and starting materials for catalyst preparation are not limited to those described above, and other preparation methods and starting materials may be used.
  • salts of various nitrogen-containing compounds of heteropolyacid as starting materials Can be used.
  • Useful ⁇ include ammonium salts or organic amine salts with pyridine, quinoline, piperazine and the like.
  • such various nitrogen-containing compounds may be added.
  • a water-soluble ammonium salt such as ammonia water, ammonium chloride, or ammonium nitrate is used as an ammonium ion source.
  • ammonium salts or organic amine salts are used as an etchant after baking at 300 to 600 ° C. to remove one or all of the nitrogen-containing compounds. Firing in an inert gas is more preferable. After calcination in an inert gas, calcination with an oxygen-containing gas can also be performed.
  • erosion media can be used in the form of being supported on a carrier or diluted and mixed.
  • the carrier include silica, ⁇ -alumina, silicon carbide, titania, zircon air, silica earth, silica alumina, water-soluble silica sol, and silicon carbide.
  • a high porosity inert carrier with a large number of macropores is preferred. In the presence or absence of water on these carriers, usually up to the same weight as the carrier! : Adhere or mix.
  • the shape of the erosion medium is preferably formed into an arbitrary size and shape, such as a pellet or a granule, depending on the use state, and the erosion medium is preferably used with a certain mechanical strength.
  • a tableting machine, an extrusion molding machine, a Malmerizer (trade name of Fuji Padal Co., Japan), a rolling granulator, etc. are used. It is not clear how much the catalyst used in the present invention works in the reduced state under the reaction conditions, but the catalyst in the high reducing state shows a yellow-green color over the reaction time. The color often changes to a color close to that of a heteropolyacid, and it does not exhibit the navy blue color known as heteropoly blue. It is presumed to be in the following low reduction state. However, the degree of reduction is not limited to this range, since the reduction state changes greatly depending on the catalyst composition, reaction gas composition, reaction temperature, and the like.
  • a mixed gas containing isobutane and oxygen is used as a source gas to be supplied to the reaction.
  • the appropriate degree of isobutane is from 10 to 80 mol. If the concentration of isobutane is less than 10 moles, the production of methacrylic acid per reactor becomes extremely small, and the economics that can be implemented industrially cannot be obtained. . More preferably, it is in the range of 20 to 60 mol.
  • Isobutane used for the corrosion reaction does not need to be particularly high-purity, so paraffin-based hydrocarbons that do not affect the reaction coexist at about twice the molar amount with isobutane. Can be used.
  • isobutane in LPG butane, FCC butane or n-butane isomerization reaction product is isolated by distillation and used.
  • the olefin is mixed in about 0.1 times or more with respect to isobutane, by-products and the like are increased. Therefore, the mixing of olefins other than isobutylene should be avoided.
  • the molar ratio of oxygen to isobutane used in the present invention is preferably 0.05 to 1 to 1 to 1, more preferably 0.1 to 1 to 0.6 to 1. If the oxygen molar ratio is high, complete oxidation proceeds too much, and the generation of carbon dioxide increases.
  • the molecular oxygen used for the corrosion reaction may be pure oxygen gas, but it is generally economical to use air because it does not need to be particularly high in purity.
  • inert gases such as helium, argon, and carbon dioxide, which do not adversely affect the reaction, are used as diluents for the source gas to prevent the gas composition from entering the explosion range. Can be prevented. In this case, these inert gases are often selected in a molar ratio of 1/10 to 10/1 with respect to isobutane.
  • reaction temperature is selected from the range of 240 to 350 ° C. A range of 270 to 320 ° C is particularly preferred. If the reaction temperature is high, decomposition of the catalyst and complete oxidation of the reaction product are likely to occur.
  • the reaction temperature is 320 ° C or less, the methacrylic acid can be obtained.
  • the reaction pressure can be set widely from decompression to pressurization, but it is industrially advantageous from atmospheric pressure to about 1 MPa.
  • the contact time between the feed gas and the catalyst (the value obtained by dividing the bulk volume of the catalyst by the reaction temperature of the feed gas and the volumetric gas flow rate at the reaction pressure) varies depending on the isobutane roughness or the reaction temperature. 1 to 10 seconds, preferably 0.5 to 5 seconds is suitable.
  • a fixed bed, a fluidized bed, a moving bed and other types of reactors can be appropriately selected as a reactor to be used. Ind is separated from other oxidation products by a known series of methods such as cooling, extraction, and distillation, and can be purified by any known method.
  • Example 2 By the same catalyst preparation method as in Example 1, a catalyst having a composition of PLiMowV ⁇ : was obtained. Of the starting materials described in Example 1, -II chloride and cesium nitrate were not used. A contact reaction was performed under the same reaction conditions as in Example 1. After 20 hours, the reaction gas was analyzed by gas chromatography. As a result, 5.3% of isobutane was converted, the selectivity of methacrylic acid was 41.1%, and Was 19.2%.
  • Example 2 ⁇ the same catalyst preparation method as in Example 1 to obtain a catalyst having the composition ⁇ ⁇ 12 C u 0. 5 . ! PM o as a starting material; to Ri I or 3 V to 12-mode Li blanking drill down acid (H 3 PM 0 12 ⁇ 4-neck ⁇ 30 ⁇ 2 ⁇ : Nippon Muki Kagaku) was used.
  • cesium nitrate was not used.
  • the contact reaction was carried out under the same reaction conditions as in Example 1. After 20 hours, the reaction gas is supplied to the gas chromatograph. As a result, 5.4% of isobutane was converted, the selectivity for methacrylic acid was 42.1%, and the selectivity for methacoline was 22.5%.
  • a catalyst having a composition of P 3 M 0 12 V G - 5 AsiCu u j- 2 was obtained.
  • Na us starting materials used for catalyst preparation in other than those described in Example 1 12 mode Li blanking de-phosphate (H 3 PM o 12 0 4D -30H 2 0: manufactured by Nippon No machine Chemical) using arsenate CH 3 a s 0 4).
  • the corrosion reaction was performed under the same reaction conditions as in Example 1 except that the reaction temperature was 340 ° C. After 20 hours, the reaction gas was analyzed by gas chromatography.It was found that 10.0% of the isobutane was converted, the selectivity for methacrylic acid was 47.2%, and the selectivity for the methanol mouth lane was 19.3. %.
  • Comparative Examples 2 to 14 By the same catalyst preparation method as in Example 1, a catalyst having a composition shown in Table 1 having a catalyst composition outside the scope of the present invention was produced, and a part of the reaction temperature was shown in Table 1. The contact reaction was carried out under the same reaction conditions as in Example 1 except that the temperature was changed to the described temperature. Table 1 shows the reaction growth after the reaction for 20 hours.
  • the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 340 ° C. Six hours later, the reaction gas was analyzed by gas chromatography, and it was found that 8.8% of isobutane was converted, the selectivity for methacrylic acid was 46.2%, and the selectivity for methanol mouth lane was 25.1%. %Met. After the reaction, the catalyst was yellowish blue.
  • Example 5 instead of adding arsenic acid, add antimony trioxide and, instead of adding pyridine, add 13 g of quinoline.
  • the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was set to 340 ° C using this etching medium. As a result, 9.1% of isobutane was converted, and the selectivity for methacrylic acid was 42.3%, and the selectivity for methacrolein was 19.4%.
  • Catalysts having the catalyst composition shown in Table 2 were prepared in the same manner as in Example 1 except that the reaction temperature was 340 ° C, and the reaction was carried out in the same manner as in Example 1. The reaction cable after a reaction for 20 hours is shown. No.
  • a solution prepared by dissolving 0.48 g in 20 ml of water was added, and 1.17 g of ammonium metavanadate was further added.
  • an aqueous solution in which 6.4 g of ammonium nitrate was dissolved in 100 ml of water was added to the solution, and the resulting slurry solution was heated, shrunk while stirring, and then evaporated to dryness on an evaporating dish.
  • the solidified product was further dried at 120 ° C. for 12 hours to obtain a solid.
  • This solid was pulverized to select particles of 10 to 20 mesh. This was calcined at 450 ° C for 3 hours in a nitrogen stream to obtain a catalyst.
  • the composition of this catalyst was P] M o 12 V ⁇ C u Q. 2 K 1.
  • Example 2 8 Water 200 ml 12-Mo Li Budo-phosphate (H 3 PM o 12 0 4 D'30H 2 0: Nippon Muki Kagaku) was dissolved 23.5 g, while stirring this, main Tabanajin Sanna Application Benefits um 0.37g and 3 A s 2 ⁇ 5 ⁇ 5H 2 0 1.15g was added, and the mixture was stirred for 12 hours at 60 ° C. Further, a solution obtained by dissolving 0.5 g of rubidium nitrate and 1.33 g of sodium nitrate in 20 ml of water was added, and then an aqueous solution of 12.8 g of ammonium nitrate dissolved in 100 ml of water was added and stirred. .
  • the resulting slurry solution was concentrated while heating and stirring, then evaporated to dryness on an evaporating dish, and further dried at 120 ° C. for 12 hours to obtain a solid.
  • the solid was formed into a pellet at a pressure of about 100 kg / cm 2 and crushed to select particles of 10 to 20 mesh. This was fired at 450 ° C for 3 hours in a nitrogen stream to obtain a bowing medium.
  • the composition of this erosion medium is
  • Water 200Pai 12-mode Li blanking de-phosphate dissolving ( ⁇ 3 ⁇ ⁇ ⁇ 12 ⁇ 4 ⁇ 30 ⁇ 2 ⁇ . Nippon Muki Kagaku) 23.5 g, arsenic acid (H 3 A s ⁇ 4) 0.85 g And stirred at 60 ° C for 12 hours. Then, after adding 0.24 g of copper nitrate, a solution of 2.66 g of sodium nitrate and 1.31 g of barium nitrate dissolved in 40 ml of water was added. Further, an aqueous solution in which 13.7 g of pyridine was dissolved in 100 ml of water was added and stirred.
  • the obtained slurry was heated and shrunk while stirring, then evaporated to dryness on an evaporating dish, and further dried at 120 ° C for 12 hours to obtain a solid.
  • the solid was formed into a pellet at a pressure of about 100 kg / cm 2 and crushed to select particles of 10 to 20 mesh. This was calcined at 450 for 3 hours in a nitrogen stream to obtain a catalyst.
  • the composition of the catalyst was P] M o] 2 A s a. EC u o . I 1 ] B a 0. 5.
  • Example 3 Using the same method for preparing the convergent medium as in Example 1, the erosion medium having the catalyst composition shown in Table 3 was prepared, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 340 ° C. The reaction growth after 100 hours of reaction is shown.
  • a catalyst having the composition shown in Table 4 was prepared and reacted in the same manner as in Example 1. Table 4 shows the reaction after 100 hours.
  • An erosion medium having the composition shown in Table 5 was prepared, and an erosion reaction was performed under the same conditions as in Example 1.
  • Table 5 shows the reaction after 100 hours.
  • Example 6 The catalyst prepared in 9 (PM o:... I2 V; l C u CI; I C e 0 5 C s ⁇ 5 1 5) Use, 1000 under the same reaction conditions as in Example 1 The catalytic reaction was continued for a continuous time, but no catalyst deterioration was observed. At that time, the conversion of isobutane was 10.9 $, the selectivity for methacrylic acid was 56.3, and the The selectivity of the application was 15.3.
  • Example 5 4 The catalyst prepared in Example 5 4 ( ⁇ ⁇ ⁇ :. .. 2 V a C u 0. 2 A s ⁇ i B D jR b o 5) , and was charged into a SUS U-shaped tube having an inner diameter of 6 mm, the reaction At a pressure of 0.3 MPa and a reaction temperature of 280 ° C, a mixed gas of 25 mol% of isobutane, 55 mol% of air, and 20 mol% of steam was reacted with a contact time of 3.6 seconds. After 100 hours, when the reaction gas was analyzed by gas chromatography, 6.2% of the isobutane was converted, the selectivity for methacrylic acid was 50.3%, and the selectivity for methacrolein.
  • This edible medium was reacted at 320 ° C in a fluidized bed reactor with a 400 ml internal volume. I let you. A mixed gas of 30 mol% of isobutane, 50 mol% of air and 20 mol% of steam was supplied at a gas linear velocity of 20 cm / sec and a contact time of 3.6 seconds.
  • Example 6 9 The catalyst prepared in Example 6 9 ( ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ . ⁇ ⁇ ⁇ C s D. 5 ⁇ 1 D. 5) as same, press Catering diameter lmm ⁇ in molding machine length After adjusting the diameter to 5 mm, it was packed in a SUS fixed-bed reactor with an inner diameter of 15 mm and a height of 1.8 ⁇ . A heating medium of 320 ° C was circulated in the jacket of the reactor. A mixed gas of 30 mol% of isobutane, 15 mol% of oxygen, 20 mol% of water vapor, and 35 mol% of nitrogen was supplied to the reactor with a contact time of 3.6 seconds. The reaction pressure was maintained at 0.4 MPa.
  • the reaction gas was analyzed by gas chromatography and found that 10.3% of the isobutane was converted, the selectivity for methacrylic acid was 55.2%, and the The selectivity was 17.3%. Then, a mixed gas of 30 mol% of isobutane, 0.6 mol% of methacrolein, 15 mol% of oxygen, 20 mol% of steam, and 34.4 mol% of nitrogen was reacted. It should be noted that the methacrolein guides the product gas obtained by this reaction to a quenching tower and then to a methachlorine absorption tower, and from the obtained condensate and absorption liquid to a mechano-rerain area. Was purified by separation and used. Although the conversion of isobutane was reduced to 9.0% compared to the case where no methanol mouth lane was supplied, the selection of methacrylic acid was 65.2%. Approximately 60 of methacrolein have been converted to methacrylic acid.
  • the process of the present invention uses abundant and inexpensive isobutane as a raw material, can produce methacrylic acid and methacrylone from isobutane in a single step at low cost, and furthermore, the catalytic activity of the catalyst used is high This is an industrially superior method for producing methacrylic acid because it can be maintained for a long period of time.

Abstract

L'invention se rapporte à un procédé de production d'acide méthacrylique et d'aldéhyde méthacrylique, qui consiste à effectuer l'oxydation catalytique de l'isobutane en phase gazeuse en présence d'oxygène moléculaire afin de produire de l'acide méthacrylique et de l'aldéhyde méthacrylique en une étape, avec une productivité et un rendement élevés, au moyen d'un catalyseur contenant un hétéropolyacide et dont la composition est P/As-Mo-V/Cu, à des températures atteignant 350 °C, de préférence 320 °C, auxquelles ledit hétéropolyacide se décompose difficilement de sorte que l'activité catalytique est maintenue pour une longue durée.
PCT/JP1989/000510 1989-05-22 1989-05-22 Procede de production d'acide methacrylique et d'aldehyde methacrylique WO1993013042A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP1989/000510 WO1993013042A1 (fr) 1989-05-22 1989-05-22 Procede de production d'acide methacrylique et d'aldehyde methacrylique
US07/400,117 US5191116A (en) 1989-05-22 1989-05-22 Process for the preparation of methacrylic acid and methacrolein

Applications Claiming Priority (1)

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PCT/JP1989/000510 WO1993013042A1 (fr) 1989-05-22 1989-05-22 Procede de production d'acide methacrylique et d'aldehyde methacrylique

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS516647B1 (fr) * 1969-11-25 1976-03-01
JPS5283306A (en) * 1975-12-27 1977-07-12 Nippon Zeon Co Ltd Simultaneous preparation of 1,3-butadiene and methacrolein
JPS5562041A (en) * 1978-10-30 1980-05-10 Rohm & Haas Manufacture of methacrylic acid or acrylic acid
JPS62132832A (ja) * 1985-12-03 1987-06-16 Asahi Chem Ind Co Ltd メタクリル酸および／またはメタクロレインの製造方法
JPS63145249A (ja) * 1986-12-06 1988-06-17 Asahi Chem Ind Co Ltd メタクリル酸および／またはメタクロレインの製法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS516647B1 (fr) * 1969-11-25 1976-03-01
JPS5283306A (en) * 1975-12-27 1977-07-12 Nippon Zeon Co Ltd Simultaneous preparation of 1,3-butadiene and methacrolein
JPS5562041A (en) * 1978-10-30 1980-05-10 Rohm & Haas Manufacture of methacrylic acid or acrylic acid
JPS62132832A (ja) * 1985-12-03 1987-06-16 Asahi Chem Ind Co Ltd メタクリル酸および／またはメタクロレインの製造方法
JPS63145249A (ja) * 1986-12-06 1988-06-17 Asahi Chem Ind Co Ltd メタクリル酸および／またはメタクロレインの製法

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