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WO2018003289A1 - Procédé de production d'acide acrylique - Google Patents

Procédé de production d'acide acrylique Download PDF

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Publication number
WO2018003289A1
WO2018003289A1 PCT/JP2017/017429 JP2017017429W WO2018003289A1 WO 2018003289 A1 WO2018003289 A1 WO 2018003289A1 JP 2017017429 W JP2017017429 W JP 2017017429W WO 2018003289 A1 WO2018003289 A1 WO 2018003289A1
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Prior art keywords
acrylic acid
propane
stage
gas
reaction
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Ceased
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PCT/JP2017/017429
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English (en)
Japanese (ja)
Inventor
正雄 丹羽
明男 荒野
屠　新林
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to JP2018524930A priority Critical patent/JPWO2018003289A1/ja
Publication of WO2018003289A1 publication Critical patent/WO2018003289A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for reducing propionic acid in acrylic acid in the production of acrylic acid by vapor phase catalytic oxidation of propane.
  • Acrylic acid is widely used as a raw material for fibers, synthetic resins and flocculants.
  • acrylic acid produces acrolein by catalytic oxidation of propylene and oxygen at about 400 ° C. in the presence of a Mo—Bi catalyst, and then at about 300 ° C. in the presence of a Mo—V catalyst. It is manufactured by a catalytic oxidation reaction between acrolein and oxygen.
  • the production method is a two-stage oxidation reaction and requires a fixed bed reactor having two reaction zones.
  • a reactor for example, two reactors are connected in series, a first-stage reaction is performed in a first-stage reactor, a second-stage reaction is performed in a second-stage reactor, and a single reactor
  • a tandem reactor is used in which a temperature control device is provided in each of the upper and lower stages, and the first stage reaction is performed in the upper stage and the second stage reaction is performed in the lower stage.
  • propionic acid is by-produced when acrylic acid is produced, and if propionic acid is contained in acrylic acid, the quality of products made from acrylic acid is adversely affected. It is known.
  • concentration of propionic acid in crude acrylic acid (acrylic acid immediately after being obtained by the oxidation reaction) obtained by vapor phase catalytic oxidation of propylene is about several hundred ppm, and this value is within an allowable range.
  • the propionic acid concentration in the vapor-phase catalytic oxidation of propane is about several thousand ppm, it is required to reduce propionic acid in order to put vapor-phase catalytic oxidation of propane into practical use.
  • Patent Document 2 discloses a method of reducing propionic acid produced as a by-product by reducing the amount of steam supplied together with propane and oxygen in the gas-phase catalytic oxidation of propane.
  • Patent Document 3 the gas after the vapor-phase catalytic oxidation reaction of propane is reacted in the presence of an iron phosphate catalyst or a mixed metal oxide catalyst having CsMo 12 PAsV 0.2 Cu 0.2 Sb 0.1.
  • an iron phosphate catalyst or a mixed metal oxide catalyst having CsMo 12 PAsV 0.2 Cu 0.2 Sb 0.1 is disclosed.
  • Patent Document 4 the gas after the vapor-phase catalytic oxidation reaction of propane is passed through a composite oxide (Mo, Bi, Fe, Co, Ni, Na, B, K, Si) heated to 450 ° C. to produce propion.
  • a composite oxide Mo, Bi, Fe, Co, Ni, Na, B, K, Si
  • JP 2007-31400 A International Publication No. 2012/091869 Japanese Patent No. 5460759 Japanese Patent Laid-Open No. 10-218831
  • the object of the present invention is to produce acrylic acid by vapor-phase catalytic oxidation of propane, which does not require a large capital investment, reduces the decrease in acrylic acid yield due to combustion, and reduces propionic acid in acrylic acid. Is to provide a method.
  • the present inventors have determined that acrylic acid by vapor-phase catalytic oxidation of propane using propane, oxygen, steam and inert gas as raw materials using a catalyst having a specific composition.
  • propane, oxygen, steam and inert gas as raw materials using a catalyst having a specific composition.
  • the first invention in the present invention includes a step of vapor-phase catalytic oxidation of propane using propane, oxygen, steam and an inert gas as raw materials in the presence of a metal oxide catalyst represented by the following composition formula.
  • the gas-phase catalytic oxidation is a method for producing acrylic acid by using a reactor having a two-stage reaction region and supplying a part of a gas containing oxygen to be reacted to the entrance of the second-stage reaction region. .
  • the method for producing acrylic acid according to the first invention, wherein oxygen / inert gas 0.8 to 1.8 / 3.8 to 8.6 (molar ratio).
  • the third invention in the present invention includes a step of vapor-phase catalytic oxidation of propane using propane, oxygen, steam and an inert gas as raw materials in the presence of a metal oxide catalyst represented by the following composition formula,
  • a metal oxide catalyst represented by the following composition formula
  • the fourth invention in the present invention is the method for producing acrylic acid according to the third invention, wherein the reaction temperature in the second-stage reaction zone is 1 to 15 ° C. higher than the reaction temperature in the first-stage reaction zone.
  • the acrylic acid according to the third aspect or the fourth aspect of the present invention wherein a part of the gas containing oxygen used for the reaction is supplied to the entrance of the second stage reaction region. It is a manufacturing method.
  • the method for producing acrylic acid according to any one of the first to fifth aspects, wherein the vapor phase catalytic oxidation is carried out using a separate reactor in which two fixed bed reactors are connected in series. It is.
  • the present invention uses propane, oxygen, steam and an inert gas as raw materials in the presence of a metal oxide catalyst represented by the following composition formula, Including a step of vapor-phase catalytic oxidation of propane, and using a reactor having a two-stage reaction region for the vapor-phase catalytic oxidation, a part of the gas containing oxygen to be used for the reaction is introduced into the second-stage reaction region. Or a part of the gas containing oxygen to be used for the reaction is supplied to the inlet of the second stage reaction zone using a reactor having a two stage reaction zone. It is a manufacturing method of acrylic acid which performs either or both of these.
  • the gas phase catalytic oxidation of propane in the present invention will be described.
  • a reactor having a two-stage reaction zone is used, and vapor phase catalytic oxidation is continuously performed in the first-stage reaction zone and then in the second-stage reaction zone.
  • a reactor a separate reactor in which two reactors used in the gas phase catalytic oxidation of propylene are connected in series, or a tandem reactor equipped with a temperature control device in the upper / lower stages in one reactor, respectively. It is preferable to use a fixed bed reactor as the reactor. Since a source gas containing oxygen is easily supplied to the entrance of the second-stage reaction region, it is preferable to use a separate reactor in which two reactors are connected in series.
  • acrylic acid can be obtained by vapor-phase catalytic oxidation of propane. Is manufactured.
  • the raw materials may be separately introduced into the reactor and mixed in the reactor, or may be introduced into the reactor in a state where they are mixed in advance.
  • Oxygen is supplied in the form of pure oxygen and air, but it is economically preferable to use air.
  • examples of the inert gas include nitrogen, helium, argon, carbon dioxide gas, etc., but nitrogen is preferable for economic reasons. When air is used as an oxygen source, nitrogen can be supplied at the same time.
  • the ratio of oxygen supplied to the first-stage reactor is preferably 0.3 to 3.0, more preferably 0.5 to 2.5 in terms of molar ratio to propane. When it is 0.3 or more, the amount of oxygen is sufficient and the acrylic acid yield is improved, and when it is 3.0 or less, it is economically excellent.
  • the ratio of steam supplied to the first stage reactor is preferably 1.0 to 10.0, more preferably 2.0 to 8.0, in terms of molar ratio to propane. When the ratio is 1.0 or more, the sequential combustion reaction is suppressed and the acrylic acid yield is improved.
  • the ratio of the inert gas supplied to the first stage reactor is preferably 1.5 to 18.0, more preferably 2.4 to 14.0, relative to propane. Within the above range, the composition of the mixed gas does not fall within the explosion range, which is preferable from the viewpoint of safety.
  • Propionic acid can be effectively reduced by setting the ratio of oxygen to be supplied to 0.8 to 1.8 in terms of molar ratio to propane supplied to the first-stage reactor.
  • the ratio of the inert gas supplied to the second stage reactor is preferably 3.8 to 8.6 with respect to propane.
  • the reaction temperature is preferably 300 ° C. to 460 ° C., more preferably 350 ° C. to 420 ° C. for both the first and second stage reactors.
  • Propionic acid can be effectively reduced by making the reaction temperature of the second stage reactor higher than the temperature of the first stage reactor.
  • a preferable temperature difference is 1 ° C. to 15 ° C.
  • the reaction temperature means the highest temperature in the packed bed region of the metal oxide catalyst during the reaction.
  • the space velocity of the raw material mixed gas is suitably 500 to 4,000 hr ⁇ 1 .
  • the space time yield of acrylic acid is increased, and when it is 4,000 hr ⁇ 1 or less, the reaction rate of propane is improved.
  • unreacted propane contained in the reaction gas discharged from the reactor outlet and propylene as an intermediate product can be used as fuel as they are, but are separated from other components in the reaction gas and sent to the reactor. It can be returned and reused.
  • a known pressure swing adsorption method (PSA method) or an organic solvent adsorption method can be used as a known pressure swing adsorption method (PSA method) or an organic solvent adsorption method.
  • the ratio of oxygen supplied to the upper stage is the molar ratio to propane. Is preferably 0.3 to 3.0, more preferably 0.5 to 2.5. When it is 0.3 or more, oxygen is sufficiently supplied by the reaction to improve the yield of acrylic acid, and when it is 3.0 or less, it is economically excellent.
  • the ratio of the steam supplied to the upper stage is preferably 1.0 to 10.0, more preferably 2.0 to 8.0, as a molar ratio with respect to propane.
  • the ratio of the inert gas supplied to the upper stage is preferably 1.5 to 18.0 and more preferably 2.4 to 14.0 with respect to propane. Within the above range, the composition of the mixed gas does not fall within the explosion range, which is preferable from the viewpoint of safety.
  • the reaction temperature is preferably 300 ° C. to 460 ° C., more preferably 350 ° C. to 420 ° C. for both the upper stage (first stage reaction area) and the lower stage (second stage reaction area).
  • propionic acid can be effectively reduced by making the reaction temperature of the lower stage higher than that of the upper stage.
  • a preferable temperature difference is 1 ° C. to 15 ° C. If the lower reaction temperature is lower than the upper reaction temperature, propionic acid may increase.
  • the reaction temperature means the highest temperature in the packed bed region of the metal oxide catalyst during the oxidation reaction.
  • the space velocity of the raw material mixed gas is suitably 500 to 4,000 hr ⁇ 1 . If it is 500 hr -1 or more, excellent yield of acrylic acid, if it is 4,000 hr -1 or less, thereby improving the reaction rate of propane.
  • unreacted propane contained in the reaction gas discharged from the reactor outlet and propylene as an intermediate product can be used as fuel as they are, but are separated from other components in the reaction gas and sent to the reactor. It can be returned and reused.
  • a known pressure swing adsorption method (PSA method) or an organic solvent adsorption method can be used as a known pressure swing adsorption method (PSA method) or an organic solvent adsorption method.
  • An aqueous liquid containing Mo, V, metal A, and metal B can be obtained by producing an aqueous liquid containing Mo, V, and metal A by the following method and adding the metal B compound to the obtained aqueous liquid.
  • an aqueous liquid containing Mo, V and metal A In the production of an aqueous liquid containing Mo, V and metal A, the Mo compound and the V compound are mixed in an aqueous medium, and the resulting mixed liquid is heated with stirring. Thereafter, by adding metal A, an aqueous solution containing Mo, V and metal A is obtained.
  • a preferable temperature of the mixed solution by heating is 40 ° C. or more, and more preferably 40 ° C. to 100 ° C.
  • the heating time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
  • the Mo compound examples include ammonium molybdate, molybdenum oxide, and molybdic acid. Among these compounds, ammonium molybdate is preferable because it is water-soluble. As the V compound, ammonium metavanadate, vanadium pentoxide and the like are preferable.
  • the addition amount of the Mo compound, V compound, and metal A compound is such that the atomic ratio (a and b) of V and metal A to Mo is 0.01 to 1.5, respectively, and the atomic ratio of metal A to V (b / A) is 0.3 to 1.0. If the mixing ratio of Mo, V, and metal A is out of the above range, a metal oxide catalyst having high catalytic performance cannot be obtained.
  • Metal A is Te or Sb
  • Te compounds include metal tellurium, tellurium dioxide, orthotelluric acid, metatelluric acid, and ammonium tellurate.
  • the metal tellurium is preferably that which has been wet-pulverized in advance and particles having a particle size of 5.0 ⁇ m or less obtained by reducing tellurium dioxide and telluric acid with a reducing agent in an aqueous medium.
  • Sb compound metal antimony and antimony trioxide are preferable.
  • ammonia water in view of the performance of the obtained metal oxide catalyst.
  • the amount of ammonia water added is preferably 0.4 or more in terms of molar ratio of ammonia to metal A, and more preferably 0.8 to 4.0. If it is 0.4 or more, the effect is sufficiently obtained, and if it is 4.0 or less, the cost of waste gas treatment is suppressed.
  • An aqueous liquid containing Mo, V, metal A, and metal B is obtained by adding the metal B compound to the reaction liquid obtained by the above operation.
  • the metal B is Nb or Ta, and examples of the metal B compound include oxides, nitrates, carboxylates, oxoacid salts, and oxalates.
  • the insoluble metal B compound may be used after being dispersed in water. In this case, it can be dissolved in water by using oxalic acid or the like in combination.
  • the addition amount of the metal B compound is such that the metal B is 0.001 to 3.0 when Mo is 1 as the atomic ratio of the metal in the obtained metal oxide catalyst. In the same catalyst, if the ratio of metal B when Mo is 1 is less than 0.001, the resulting catalyst is likely to deteriorate, whereas if it exceeds 3.0, the resulting catalyst has a low activity. Propane conversion decreases.
  • the amount of ammonia water added is preferably 0.4 or more, and more preferably 0.8 to 3.0, in terms of molar ratio of ammonia to metal B. If it is 0.4 or more, a sufficient effect is obtained, and if it is 3.0 or less, the cost of waste gas treatment is suppressed.
  • nitric acid or ammonium nitrate it is preferable to add nitric acid or ammonium nitrate to the fine precipitate dispersion obtained by adding ammonia water and metal B compound.
  • the amount of nitric acid or ammonium nitrate added is preferably such that the nitrate ion is in a molar ratio to metal B of 2.0 to 6.0, more preferably 2.2 to 4.0. When it is in the above range, the effect of addition is sufficiently obtained.
  • the obtained aqueous liquid in the form of a slurry is heated to evaporate the moisture and dried.
  • a shelf dryer, spray drying, or the like can be used for drying.
  • the obtained dried product is preferably crushed to 500 ⁇ m or less, and in the presence of oxygen, preferably a temperature of 250 ° C. to 380 ° C., more preferably a heating temperature of 280 ° C. to 360 ° C., preferably 0.5 to 10 hours, More preferably, the first stage baking is performed with a heating time of 1 to 3 hours.
  • the solid obtained by the first-stage firing is preferably 480 ° C. to 640 ° C., more preferably 570 ° C. to 620 ° C., and preferably 0.1 to 5 hours under nitrogen flow. More preferably, the second baking is performed with a baking time of 0.2 to 1.5 hours.
  • a shuttle kiln, a roller haskiln, a rotary kiln or the like can be used.
  • the metal oxide catalyst obtained by the above operation is preferably pulverized so as to have a median diameter of 0.2 to 0.4 ⁇ m.
  • a wet / dry ball mill, jet mill, or the like can be used for the pulverization.
  • various alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like with oxalic acid added can be used.
  • the metal oxide catalyst is separated and washed and then dried. Filtration or centrifugation can be used for separation or washing, and a shelf dryer or rotary kiln can be used for drying.
  • the pulverized metal oxide catalyst is washed with an oxalic acid aqueous solution.
  • an aqueous oxalic acid solution and a metal oxide catalyst are added to a container and stirred.
  • the concentration of the oxalic acid aqueous solution is preferably 0.5 to 5.0% by mass, and the amount is preferably 1.0 to 5.0 times the weight of the metal oxide catalyst.
  • the stirring time is preferably 0.5 to 5.0 hours.
  • the metal oxide catalyst is separated from the aqueous solution, washed with water and dried. Filtration or centrifugation can be used for separation or washing, and a shelf dryer or rotary kiln can be used for drying.
  • the Si compound is adhered to the metal oxide catalyst obtained by the above operation in an atmosphere free of water.
  • the Si compound may be vaporized and the vapor may contact the metal oxide catalyst, or the organic solvent may be evaporated after the Si oxide is immersed in an anhydrous organic solvent in which the Si compound is dissolved.
  • the shape of the metal oxide catalyst used for the adhesion of the Si compound may be a powder or a supported product supported on a carrier. In the case of powder, particles having a particle size of 500 ⁇ m or less are preferable. In the case of a supported product, particles having a particle size of 1.0 to 6.0 mm are preferable.
  • Si compound examples include silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, trimethylsilane, triethylsilane, hexamethyldisilane, hexamethyldisilazane, hexamethylsiloxane, methylsilicate 51 (tetramethoxysilane). Silane tetramer) and ethyl silicate 40 (tetraethoxysilane pentamer).
  • the dehydration temperature is preferably 50 ° C to 300 ° C, more preferably 70 ° C to 250 ° C.
  • the dehydration temperature is 50 ° C. or higher, a sufficient dehydration effect is obtained, and when the dehydration temperature is 300 ° C. or lower, the change in the surface properties of the metal oxide catalyst is suppressed and the adhesion of the Si compound is excellent.
  • any conventionally known method can be adopted as long as the deposition can be performed in an atmosphere without water.
  • a simple method is to pass a dehydrated inert gas (hereinafter sometimes referred to as carrier gas) through a liquid Si compound to create a gas stream containing the vapor of the Si compound corresponding to the vapor pressure, which is then used for the metal oxidation. It is a method of contacting with an object.
  • the vapor pressure of the Si compound depends on the temperature and pressure of the atmosphere. In order to increase the vapor pressure, the temperature of the Si compound may be increased.
  • the flow rate of the carrier gas is preferably 1.0 to 1,000 ml / min.
  • the carrier gas flow rate and the vapor pressure of the Si compound it is preferable to form a mixed gas in which the vapor concentration of the Si compound is preferably 0.1 to 10,000 ppm, more preferably 1 to 1,000 ppm.
  • the carrier gas containing the Si compound at the above concentration into contact with the metal oxide catalyst, 0.002 to 0.5 mol of Si can be deposited per mol of Mo.
  • the adhesion of the Si compound to the metal oxide catalyst is preferably performed in a container that is shielded from the atmosphere, and is preferably performed by a fixed bed, a fluidized bed, or the like. Further, the temperature of the metal oxide catalyst when the Si compound is adhered is preferably room temperature to 350 ° C. When the vapor of the Si compound comes into contact with the metal oxide catalyst maintained at this temperature, the Si compound adsorbed on the surface is quickly converted into the metal oxide, and is reliably fixed on the surface of the metal oxide catalyst.
  • the organic solvent to be used is not particularly limited, and toluene, hexane, acetone, ethyl acetate, and the like can be used, and toluene and hexane are preferable.
  • the water content in the organic solvent is preferably 500 ppm or less, more preferably 300 ppm or less. When the amount of water in the organic solvent exceeds 2,000 ppm, it is preferable to apply a dehydration method by a known method, preferably a molecular sieve adsorption method.
  • the amount of the organic solvent used for the impregnation is preferably 0.5 to 100 times, more preferably 1 to 20 times in volume ratio to the catalyst.
  • the concentration of the Si compound contained in the organic solvent is preferably in the range of 0.01 to 300 ⁇ mol / ml, more preferably 0.1 to 150 ⁇ mol / ml.
  • stirring is preferable.
  • the stirring time is preferably 0.5 to 24 hours.
  • the metal oxide catalyst After impregnation with an organic solvent containing a Si compound, the metal oxide catalyst is separated from the solvent and the organic solvent is evaporated. It may be evaporated immediately after the separation, or may be evaporated after washing the metal oxide catalyst with a dehydrated organic solvent.
  • a method for removing the organic solvent known methods such as distillation, centrifugation, and filtration can be employed. Thereafter, by heating the metal oxide catalyst to, for example, 50 ° C. to 300 ° C., the deposited Si compound can be converted into an oxide and fixed on the surface of the metal oxide catalyst.
  • the content of each metal component in the metal oxide catalyst of the present invention obtained by fixing Si oxide can be measured by fluorescent X-ray analysis.
  • the metal oxide catalyst obtained by the above operation may be used in the form of powder particles, or may be used by being supported on a carrier.
  • Silica, alumina, silica alumina, silicon carbide, and the like can be used as the type of carrier for carrying.
  • the particle size of the carrier is preferably 0.5 to 5.0 mm.
  • the amount supported is not particularly limited, but is preferably 20 to 70% by mass.
  • a rolling granulator or the like can be used.
  • As the binder used for loading water, methanol, ethanol, ethylene glycol, glycerin, silica sol and the like can be used, and aqueous solutions such as polyvinyl alcohol, starch and polyacrylic acid can also be used.
  • the particle size of the supported product is preferably 1.0 to 6.0 mm.
  • the obtained metal oxide was pulverized with a dry jet mill.
  • the median diameter after pulverization was 0.28 ⁇ m.
  • the pulverized metal oxide was added to a 1.0% oxalic acid aqueous solution, stirred for 1 hour, filtered and washed with water, and dried at 120 ° C. for 3 hours.
  • 200 g of the metal oxide obtained by the above operation was pulverized to 250 ⁇ m or less, placed in a flask, attached to a rotary evaporator, and dried under reduced pressure at 80 ° C. for 0.5 hours. Thereafter, the pressure was returned to normal pressure, a nitrogen gas line was introduced into the flask, and the evaporator was rotated.
  • Nitrogen having a flow rate of 21.0 ml / min was passed through 8.0 g of tetramethoxysilane, the vapor was introduced into the flask through a nitrogen gas line, and the metal oxide was brought into contact with the vapor over 53 hours.
  • 200 g of the metal oxide obtained by the above-described operation was supported on a 2.6-mm alumina ball 200 g using a rolling granulator using a 7.5% starch aqueous solution as a binder. Thereafter, it was dried at 120 ° C. for 1 hour to obtain a metal oxide supported product having a particle size of 4.0 mm.
  • a mixed gas of oxygen / nitrogen 0.2 / 1.0 (molar ratio) was supplied together with the first-stage reaction gas to produce acrylic acid.
  • the composition of the gas after the reaction was analyzed by gas chromatography (GC), and the propane conversion and the acrylic acid yield were calculated on a molar basis by the following formula.
  • the concentration of propionic acid was quantified by FID-GC.
  • the propane conversion was 75.5%, the acrylic acid yield was 59.2%, and the propionic acid concentration was 1,600 ppm.
  • the results are shown in Table 1.
  • Propane conversion (%) 100 ⁇ [(supplied propane-unreacted propane) / supplied propane]
  • Acrylic acid selectivity (%) 100 ⁇ [generated acrylic acid / (supplied propane-unreacted propane)]
  • Acrylic acid yield (%) (propane conversion ⁇ acrylic acid selectivity) / 100
  • Example 1 The reaction was performed under the same conditions as in Example 1 except that the oxygen / nitrogen mixed gas was not supplied to the second stage.
  • the propane conversion was 76.3% and the acrylic acid yield was 59.2%.
  • the propionic acid concentration was 2,050 ppm, which exceeded 2,000 ppm, which is a guideline for the allowable range of propionic acid.
  • Example 2 The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature, the molar ratio of the raw material gases and the space velocity were as follows.
  • the propane conversion was 77.7%
  • the acrylic acid yield was 59.3%
  • the propionic acid concentration was 1676 ppm.
  • Example 3 The reaction was carried out under the same conditions as in Example 2 except that the molar ratio and amount of the second stage supply gas were as follows.
  • a mixed gas of oxygen / nitrogen 0.9 / 4.4 (molar ratio) was supplied together with the first-stage reaction gas to produce acrylic acid.
  • the propane conversion was 77.0%, the acrylic acid yield was 59.7%, and the propionic acid concentration was 1,106 ppm.
  • the propane conversion was 76.6% and the acrylic acid yield was 58.9%.
  • the propionic acid concentration was 793 ppm.
  • the propane conversion was 76.4% and the acrylic acid yield was 58.8%.
  • the propionic acid concentration was 1,215 ppm.
  • the propane conversion was 76.3% and the acrylic acid yield was 59.2%.
  • the propionic acid concentration was 1,481 ppm.

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Abstract

L'objectif de la présente invention est de fournir un procédé de réduction de l'acide propionique dans un acide acrylique pendant la production de l'acide acrylique par oxydation catalytique en phase vapeur du propane sans nécessiter une grande quantité d'investissement dans l'équipement, tout en supprimant la diminution du rendement de l'acide acrylique due à la combustion. Un procédé de production d'un acide acrylique selon la présente invention comprend une étape consistant à soumettre du propane à une oxydation catalytique en phase vapeur en présence d'un catalyseur d'oxyde métallique représenté par la formule de composition présentée ci-dessous, tout en utilisant du propane, de l'oxygène, de la vapeur et un gaz inerte comme matériaux de départ. L'oxydation catalytique en phase vapeur est effectuée à l'aide d'un réacteur ayant des régions de réaction de deux étages; et une partie d'un gaz contenant de l'oxygène devant être offert pour la réaction est fournie à l'entrée d'une région de réaction du second étage. Formule de composition : MoVaAbBcSidOe Dans a formule, A représente Te ou Sb; B représente Nb ou Ta; chacun des a et b représentent un nombre de 0,01 à 1,5, avec b/a étant 0,3 à 1,0; c représente un nombre de 0,001 à 3,0; d représente un nombre de 0,002 à 0,5; et e représente un nombre qui est déterminé en accord avec l'état d'oxydation des autres éléments.
PCT/JP2017/017429 2016-06-30 2017-05-08 Procédé de production d'acide acrylique Ceased WO2018003289A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
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JP2004525172A (ja) * 2001-04-09 2004-08-19 ビーエーエスエフ アクチェンゲゼルシャフト アクリル酸の二段製造法及び装置
JP2005213225A (ja) * 2004-01-30 2005-08-11 Nippon Shokubai Co Ltd アクリル酸の製造方法
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JP2007031400A (ja) * 2005-07-29 2007-02-08 Nippon Kayaku Co Ltd アクリル酸の製造方法
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