WO2021200689A1 - 触媒、イソブチレンの製造方法、メタクリル酸の製造方法及びメタクリル酸メチルの製造方法 - Google Patents
触媒、イソブチレンの製造方法、メタクリル酸の製造方法及びメタクリル酸メチルの製造方法 Download PDFInfo
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- WO2021200689A1 WO2021200689A1 PCT/JP2021/012965 JP2021012965W WO2021200689A1 WO 2021200689 A1 WO2021200689 A1 WO 2021200689A1 JP 2021012965 W JP2021012965 W JP 2021012965W WO 2021200689 A1 WO2021200689 A1 WO 2021200689A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- isobutylene
- producing
- alumina
- methacrylic acid
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims description 48
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims description 21
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 142
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 20
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 230000018044 dehydration Effects 0.000 abstract description 12
- 238000006297 dehydration reaction Methods 0.000 abstract description 12
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
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Definitions
- the present invention relates to a catalyst, a method for producing isobutylene, a method for producing methacrylic acid, and a method for producing methyl methacrylate.
- the present application claims priority based on Japanese Patent Application No. 2020-064548 filed in Japan on March 31, 2020, the contents of which are incorporated herein by reference.
- Isobutylene is one of the important chemical raw materials converted into ethyl tert-butyl ether, para-xylene, methyl methacrylate and the like.
- methyl methacrylate can be produced by vapor-phase oxidation of isobutylene or tert-butyl alcohol hydrated with isobutylene to obtain methacrylic acid, and then esterifying with methanol.
- isobutylene As a method for producing isobutylene, for example, a method is known in which isobutanol is brought into contact with a catalyst such as alumina under pressure to dehydrate isobutanol to produce isobutylene (for example, Patent Document 1). However, it is difficult to produce isobutylene with a high selectivity by a conventional method such as Patent Document 1.
- the present invention provides a catalyst capable of producing isobutylene with a high selectivity in the production of isobutylene by dehydration of isobutanol, a method for producing isobutylene using the catalyst, a method for producing methacrylic acid, and a method for producing methyl methacrylate.
- the purpose is to do.
- the present invention has the following configurations.
- Alumina containing alumina composed of one or more crystal phases of uniclinical, square, or cubic is selected from the metal elements of Groups 6 to 14 of the 4th to 6th periods of the periodic table.
- a catalyst containing at least one metal [2] The catalyst according to [1], wherein the metal content is 0.025 mmol or more with respect to 1 g of the alumina.
- a method for producing isobutylene which comprises producing isobutylene from isobutanol using the catalyst according to [1] or [2].
- a method for producing methacrylic acid which produces methacrylic acid from isobutylene produced by the method for producing isobutylene according to [3].
- a method for producing methacrylic acid which comprises obtaining tert-butyl alcohol from isobutylene produced by the method for producing isobutylene according to [3], and then producing methacrylic acid from the obtained tert-butyl alcohol.
- a method for producing methyl methacrylate which comprises producing methyl methacrylate from methanol and methacrylic acid produced by the method for producing methacrylic acid according to [4] or [5].
- Alumina containing alumina composed of one or more crystal phases of uniclinical, square, or cubic is selected from the metal elements of Groups 6 to 14 of the 4th to 6th periods of the periodic table.
- a method for producing isobutylene which comprises producing isobutylene from isobutanol using a catalyst containing at least one metal.
- a method for producing methacrylic acid wherein the isobutylene produced by the method for producing isobutylene according to [7] is produced, and methacrylic acid is produced from the isobutylene.
- a method for producing methacrylic acid which comprises obtaining tert-butyl alcohol from isobutylene produced by the method for producing isobutylene according to [7], and then producing methacrylic acid from the obtained tert-butyl alcohol.
- a method for producing methyl methacrylate which comprises producing methyl methacrylate from methanol and methacrylic acid produced by the method for producing methacrylic acid according to [8] or [9].
- the present invention it is possible to provide a catalyst capable of producing isobutylene with a high selectivity in the production of isobutylene by dehydration of isobutanol. According to the present invention, it is possible to provide a method for producing isobutylene, a method for producing methacrylic acid, and a method for producing methyl methacrylate using the catalyst of the present invention.
- the catalyst of the present invention is a catalyst for producing isobutylene from isobutanol.
- alumina containing alumina composed of one or more crystal phases of uniclinical, square, or cubic is composed of metal elements of Groups 6 to 14 of the 4th to 6th periods of the periodic table. Contains at least one metal selected.
- the alumina crystal system used in the present invention is not particularly limited as long as it contains alumina composed of one or more of monoclinic, cubic, and cubic crystal phases.
- various aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and alumina hydrate can be used.
- ⁇ -alumina, ⁇ -alumina, ⁇ -alumina and ⁇ -alumina are preferable, and ⁇ -alumina and ⁇ -alumina are more preferable.
- Alumina in these crystal forms may be used alone or in combination of two or more. When two or more kinds are used in combination, those having different crystal forms may be used, or a mixed phase crystal state may be taken.
- the alumina used in the catalyst of the present invention can be easily produced by a known method including, for example, a thermal decomposition method, a precipitation method, a deposition method, a kneading method, or a method in which these methods are used in combination.
- the raw material for alumina include materials that produce alumina or alumina hydrate by heating or hydrolysis, such as nitrates, acetates, alkoxides, sulfates, chlorides, alkali aluminates, and myoban.
- the alkali used for hydrolysis include caustic alkali, alkali carbonate, aqueous ammonia, and ammonium carbonate.
- the alumina used in the catalyst of the present invention may contain other compounds.
- the purity of alumina is preferably 90.0% by mass or more, more preferably 95.0% by mass or more, further preferably 97.0% by mass or more, and 98.0% by mass or more. Is particularly preferable, 99.0% by mass or more is particularly preferable, and 99.5% by mass or more is most preferable.
- Other compounds include, for example, SiO 2 and Na 2 O.
- the content of SiO 2 in alumina is preferably 1.00% by mass or less, more preferably 0.75% by mass or less, still more preferably 0.50% by mass or less, and 0.40% by mass, based on the total mass of alumina. It is even more preferably mass% or less, particularly preferably 0.30 mass% or less, and most preferably 0.20 mass% or less. SiO 2 may not be contained in the alumina.
- the content of Na 2 O in alumina is preferably 0.20% by mass or less, more preferably 0.15% by mass or less, still more preferably 0.10% by mass or less, and 0. 075% by mass or less is even more preferable, 0.050% by mass or less is particularly preferable, and 0.025% by mass or less is most preferable.
- Na 2 O may not be contained in alumina.
- ICP-AES ICP emission spectroscopy
- BET specific surface area of the alumina is preferably at least 50.0 m 2 / g, more preferably not less than 60.0m 2 / g, more preferably not less than 70.0m 2 / g, 80 particularly preferred .0m 2 / g or more, 90.0m 2 / g or more it is most preferred.
- the upper limit of the BET specific surface area of alumina is not particularly limited, but is preferably 350 m 2 / g or less.
- BET specific surface area of the alumina is a value calculated from the N 2 adsorption-desorption isotherms, for example, it can be measured using a Tristar 3000 (product name, manufactured by Shimadzu Corporation).
- the metal contained in the catalyst of the present invention is at least one selected from the metal elements of Groups 6 to 14 of the 4th to 6th periods of the periodic table. At least one selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In and Sn because of the high selectivity of isobutylene.
- the metal contained in the catalyst may be one kind or two or more kinds.
- the metal content of the catalyst of the present invention is preferably 0.80 mmol or less, more preferably 0.70 mmol or less, further preferably 0.60 mmol or less, particularly preferably 0.50 mmol or less, and 0.40 mmol with respect to 1 g of alumina. The following are the most preferable.
- the content of the metal in the catalyst is not more than the above upper limit value, both the catalytic activity and the isobutylene selectivity can be achieved at the same time.
- 0.025 mmol or more is preferable, 0.050 mmol or more is more preferable, 0.075 mmol or more is further preferable, 0.10 mmol or more is particularly preferable, and 0.15 mmol or more is most preferable.
- the content of the metal in the catalyst is equal to or higher than the lower limit, the formation of linear butenes can be suppressed and a high isobutylene selectivity can be obtained.
- the upper and lower limits can be combined arbitrarily.
- the metal content of the catalyst of the present invention is preferably 0.025 mmol or more and 0.80 mmol or less, more preferably 0.050 mmol or more and 0.70 mmol or less, and further preferably 0.075 mmol or more and 0.60 mmol or less with respect to 1 g of alumina.
- 0.10 mmol or more and 0.50 mmol or less is particularly preferable, and 0.15 mmol or more and 0.40 mmol or less is particularly preferable.
- the method for producing the catalyst of the present invention is not particularly limited, and a known method can be used.
- a catalyst can be easily produced by a coprecipitation method, a deposition method, an impregnation method, a kneading method, or a method in which these are used in combination.
- the raw material of the metal contained in the catalyst is not particularly limited, and examples thereof include hydroxides, nitrates, acetates, and sulfates.
- the catalyst of the present invention may be molded if necessary.
- Examples of the method for molding the catalyst of the present invention include a method using a powder molding machine such as a tableting molding machine, an extrusion molding machine, and a rolling granulator.
- a powder molding machine such as a tableting molding machine, an extrusion molding machine, and a rolling granulator.
- shape for molding the catalyst of the present invention any shape such as a spherical shape, a ring shape, a columnar shape, and a star shape can be adopted.
- the molded catalyst may be ground and used as a powder. Additives may be mixed with the catalyst during molding.
- the method for producing isobutylene of the present invention is a method for producing isobutylene from isobutanol using the catalyst of the present invention.
- the isobutanol used as a starting material is not particularly limited, and may be biomass-derived isobutanol from the viewpoint of environmental protection.
- As the starting material isobutanol fossil-derived isobutanol and biomass-derived isobutanol can be mixed and used.
- Biomass-derived isobutanol is isobutanol purified from an organic compound obtained through a fermentation process using fermentable sugar of biomass, or any one of catalytic chemical conversion and thermochemical conversion of biomass. Isobutanol obtained by a process containing one or more. Biomass can be broadly divided into those derived from resource crops and those derived from waste. Examples of biomass derived from resource crops include food crops, wood, and flowers, and unused portions of these crops can also be used. Examples of biomass derived from waste include food waste, sludge such as sewage, livestock manure, and waste paper.
- Isobutanol dehydration may be carried out in the liquid phase or in the gas phase.
- a fixed bed, a fluidized bed, or the like can be adopted.
- the case where the reaction is carried out in the gas phase will be described, but the present invention is not limited thereto.
- the evaporator is not particularly limited, and for example, a jacket type, a natural circulation type horizontal tube type, a natural circulation type immersion tube type, a natural circulation type vertical short tube type, a vertical long tube rising film type, a horizontal tube descending film type, Examples include a forced circulation type horizontal tube type, a forced circulation type vertical tube type, and a coil type. It is also possible to simply wind a heating coil around the raw material supply pipe, evaporate the raw material moving in the raw material supply pipe in the raw material supply pipe before entering the reactor, and supply it into the reactor in a gaseous state. Is.
- the evaporator is not particularly limited.
- the conditions for vaporizing the raw material are not particularly limited, and for example, the temperature can be 108 ° C. or higher and 600 ° C. or lower, and the absolute pressure can be 0.05 MPa or higher and 1 MPa or lower.
- the isobutanol concentration can be adjusted by diluting isobutanol with a diluting gas.
- the raw material gas may be a gas consisting only of isobutanol.
- the diluting gas may be any gas that does not affect the dehydration of isobutanol, for example, nitrogen, helium, neon, krypton, xenone, radon, argon, methane, ethane, propane, butane, isobutane, carbon monoxide, etc. Examples thereof include carbon dioxide, nitric oxide, nitrogen dioxide, nitrous oxide, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide, and water vapor. Oxygen or hydrogen may be used as a diluting gas as long as it does not affect the dehydration of isobutanol.
- the dilution gas contained in the raw material gas may be one type or two or more types. Moisture may be contained in the raw material gas.
- the isobutanol concentration in the raw material gas is preferably 1.0% by volume or more, more preferably 3.0% by volume or more, still more preferably 5.0% by volume or more, and 15.0% by volume, based on the total volume of the raw material gas.
- volume or more is particularly preferable, 25.0% by volume or more is particularly preferable, and 45.0% by volume or more is most preferable.
- the isobutanol concentration is at least the above lower limit value, isomerization is easily suppressed and the selectivity of isobutylene is improved.
- the reactor can be easily miniaturized, the equipment cost can be reduced, and the energy cost required for the recovery of isobutylene can be reduced. There is no particular upper limit, and it is 100% by volume or less.
- the reaction temperature (temperature in the catalyst layer during the reaction) in dehydration of isobutanol is preferably 460 ° C. or lower, more preferably 440 ° C. or lower, further preferably 420 ° C. or lower, particularly preferably 400 ° C. or lower, and most preferably 380 ° C. or lower. preferable.
- the reaction temperature in dehydration of isobutanol is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, further preferably 240 ° C. or higher, particularly preferably 260 ° C.
- the reaction temperature in dehydration of isobutanol is preferably 200 ° C. or higher and 460 ° C. or lower, more preferably 220 ° C. or higher and 440 ° C. or lower, further preferably 240 ° C. or higher and 420 ° C. or lower, and particularly preferably 260 ° C. or higher and 400 ° C. or lower. 280 ° C. or higher and 380 ° C. or lower are particularly preferable.
- the lowest temperature of the catalyst layer in the reactor that can be confirmed after the reaction has reached a steady state is defined as the reaction temperature. Therefore, when the temperature of the catalyst layer varies, it is preferable to increase the number of measurement points or measure the temperature continuously in the catalyst filling direction.
- the method for controlling the reaction temperature is not particularly limited, and a known method can be adopted.
- the reaction pressure in dehydration of isobutanol is not particularly limited, but the absolute pressure is preferably 50 kPa or more.
- the reaction pressure is preferably 1000 kPa or less, more preferably 900 kPa or less, further preferably 800 kPa or less, particularly preferably 700 kPa or less, and most preferably 600 kPa or less.
- the value of the reaction pressure is a value measured by a pressure sensor installed at a position where the influence of the pressure loss can be ignored with respect to the pressure at the inlet of the reactor.
- the method for producing methacrylic acid of the present invention is a method for producing methacrylic acid using isobutylene produced by the method for producing isobutylene of the present invention.
- the following method (A) and method (B) can be mentioned.
- methacrylic acid can be produced from isobutylene with a high selectivity.
- (A) The step of producing isobutylene by the method for producing isobutylene of the present invention (a1) and the step of producing methacrylic acid by vapor phase oxidation of isobutylene (a2) are included.
- (B) A step of producing isobutylene by the method for producing isobutylene of the present invention (b1), a step of hydrating isobutylene to produce tert-butyl alcohol (b2), and a step of hydrating isobutylene to produce tert-.
- the step (b3) of producing methacrylic acid by vapor phase oxidation of butyl alcohol is included.
- the hydration of isobutylene in step (b2) can be performed by a known method.
- the acid catalyst used for hydration of isobutylene include an ion exchange resin and a heteropolyacid.
- a strongly acidic cation exchange resin is preferable as the acid catalyst because tert-butyl alcohol can be produced in a high yield.
- the vapor phase oxidation of isobutylene in the step (a2) and the vapor phase oxidation of tert-butyl alcohol in the step (b3) may be carried out in one step or in two steps. Two-stage vapor phase oxidation is preferable because of the high selectivity of methacrylic acid.
- first stage oxidation When gas phase oxidation is carried out in two stages, it is preferable to use a catalyst for first stage oxidation in the first stage gas phase oxidation (first stage oxidation).
- the catalyst used may be a known catalyst. Of these, a catalyst containing at least molybdenum and bismuth is preferable.
- a catalyst having a composition represented by the formula (1) is preferable.
- Mo, Bi, Fe and O represent molybdenum, bismuth, iron and oxygen, respectively.
- M represents at least one element selected from the group consisting of cobalt and nickel.
- X represents at least one element selected from the group consisting of chromium, lead, manganese, calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc.
- Y represents at least one element selected from the group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium.
- Z represents at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium.
- a3 1.0 ⁇ 12
- a4 0 ⁇ 8.0
- a5 0 ⁇ 5.0
- a6 0.001 ⁇ 2.0
- a7 satisfies the atomic value of each component. It is the atomic ratio of oxygen required for.
- First-stage oxidation can be performed on a fixed bed.
- the catalyst layer for the first-stage oxidation is not particularly limited, and may be an undiluted layer containing only the catalyst for the first-stage oxidation, or a diluted layer containing an inert carrier.
- the catalyst layer for the first-stage oxidation may be a single layer or a mixed layer composed of a plurality of layers.
- the concentration of isobutylene or tert-butyl alcohol in the raw material gas for the first-stage oxidation is preferably 1.0% by volume or more, more preferably 3.0% by volume or more.
- the concentration of isobutylene or tert-butyl alcohol in the raw material gas for the first-stage oxidation is preferably 20.0% by volume or less, more preferably 10.0% by volume or less.
- the upper and lower limits can be combined arbitrarily.
- the concentration of isobutylene or tert-butyl alcohol in the raw material gas for the first-stage oxidation is preferably 1.0% by volume or more and 20.0% by volume or less, and more preferably 3.0% by volume or more and 20.0% by volume or less. It is preferable, and more preferably 3.0% by volume or more and 10.0% by volume or less.
- reaction gas diluted with an inert gas such as nitrogen or carbon dioxide gas, water vapor or the like in addition to isobutylene or tert-butyl alcohol and molecular oxygen.
- inert gas such as nitrogen or carbon dioxide gas, water vapor or the like
- the reaction pressure for the first-stage oxidation is preferably in the range of atmospheric pressure to 200 kPaG.
- the reaction temperature of the first-stage oxidation is preferably 200 ° C. or higher and 450 ° C. or lower, and more preferably 250 ° C. or higher and 400 ° C. or lower.
- the contact time between isobutylene or tert-butyl alcohol and molecular oxygen in the first-stage oxidation is preferably 0.5 seconds or longer, more preferably 1.0 seconds or longer.
- the contact time between isobutylene or tert-butyl alcohol and molecular oxygen in the first-stage oxidation is preferably 10.0 seconds or less, more preferably 6.0 seconds or less. The upper and lower limits can be combined arbitrarily.
- the contact time between isobutylene or tert-butyl alcohol and molecular oxygen in the first-stage oxidation is preferably 0.5 seconds or more and 10.0 seconds or less, more preferably 0.5 seconds or more and 6.0 seconds or less. More preferably, it is 0.0 seconds or more and 6.0 seconds or less.
- Methacrolein and methacrylic acid are obtained by the first-stage oxidation. Methacrolein is converted to methacrylic acid by the second stage vapor phase oxidation (second stage oxidation).
- the catalyst for the second stage oxidation used in the second stage oxidation a known catalyst can be used.
- the catalyst used is preferably a catalyst containing at least molybdenum and phosphorus.
- a catalyst having a composition represented by the formula (2) is preferable.
- P, Mo, V, Cu and O represent phosphorus, molybdenum, vanadium, copper and oxygen, respectively.
- A represents at least one element selected from the group consisting of antimony, bismuth, arsenic, germanium, zirconium, tellurium, silver, selenium, silicon, tungsten and boron.
- E represents at least one element selected from the group consisting of potassium, rubidium, cesium, thallium, magnesium and barium.
- G is at least one selected from the group consisting of iron, zinc, chromium, calcium, strontium, tantalum, cobalt, nickel, manganese, titanium, tin, lead, niobium, indium, sulfur, palladium, gallium, cerium and lanthanum.
- the second stage oxidation can be performed on a fixed bed.
- the catalyst layer for the second-stage oxidation is not particularly limited, and may be an undiluted layer containing only the catalyst for the second-stage oxidation, or a diluted layer containing an inert carrier.
- the catalyst layer for the second stage oxidation may be a single layer or a mixed layer composed of a plurality of layers.
- the concentration of methacrolein in the reaction gas of the second stage oxidation is not limited and can be set to any concentration, but 1.0% by volume or more is preferable, and 3.0% by volume or more is more preferable.
- the concentration of methacrolein in the reaction gas for the second stage oxidation is preferably 20.0% by volume or less, more preferably 10.0% by volume or less.
- the upper and lower limits can be combined arbitrarily.
- the concentration of methacrolein in the reaction gas of the second stage oxidation is preferably 1.0% by volume or more and 20.0% by volume or less, more preferably 1.0% by volume or more and 10.0% by volume or less. More preferably, it is 0% by volume or more and 10.0% by volume or less.
- the concentration of molecular oxygen in the reaction gas for the second-stage oxidation is preferably 0.5 mol or more, more preferably 1.0 mol or more, with respect to 1.0 mol of methacrolein.
- the molecular oxygen concentration in the reaction gas for the second stage oxidation is preferably 4.0 mol or less, more preferably 3.0 mol or less, with respect to 1.0 mol of methacrolein. The upper and lower limits can be combined arbitrarily.
- the concentration of molecular oxygen in the second stage oxidation is preferably 0.5 mol or more and 4.0 mol or less, more preferably 1.0 mol or more and 4.0 mol or less, and 1.0 mol or more, with respect to 1.0 mol of methacrolein. 3.0 mol or less is more preferable.
- the reaction gas for the second stage oxidation preferably contains water (water vapor) in addition to methacrolein and molecular oxygen. By carrying out the reaction in the presence of water, methacrylic acid can be obtained in higher yields.
- the concentration of water vapor in the reaction gas for the second-stage oxidation is preferably 0.1% by volume or more, more preferably 1.0% by volume or more.
- the concentration of water vapor in the reaction gas of the second stage oxidation is preferably 50.0% by volume or less, more preferably 40.0% by volume or less.
- the upper and lower limits can be combined arbitrarily.
- the concentration of water vapor in the reaction gas of the second stage oxidation is preferably 0.1% by volume or more and 50.0% by volume or less, more preferably 1.0% by volume or more and 50.0% by volume or less, and 1.0. More preferably, it is by volume% or more and 40.0% by volume or less.
- Water water vapor
- methacrolein and molecular oxygen may be added as the reaction gas for the second stage oxidation in addition to methacrolein and molecular oxygen.
- the reaction pressure of the second stage oxidation can be set in the range from atmospheric pressure to several hundred kPaG.
- the reaction temperature of the second stage oxidation is preferably 230 ° C. or higher, more preferably 250 ° C. or higher.
- the reaction temperature of the second stage oxidation is preferably 450 ° C. or lower, more preferably 400 ° C. or lower.
- the upper and lower limits can be combined arbitrarily.
- the reaction temperature of the second stage oxidation is preferably 230 ° C. or higher and 400 ° C. or lower, more preferably 250 ° C. or higher and 450 ° C. or lower, and further preferably 250 ° C. or higher and 400 ° C. or lower.
- the method for producing methyl methacrylate of the present invention is a method for producing methyl methacrylate using methacrylic acid produced by using the method for producing methacrylic acid of the present invention.
- the method for producing methyl methacrylate of the present invention includes a step of producing methyl methacrylate by esterifying methacrylic acid produced using the method for producing methacrylic acid of the present invention with methanol. According to the method of the present invention, methyl methacrylate can be produced from isobutylene with a high selectivity.
- methacrylic acid produced by the production method of the present invention is recovered by extraction, distillation or the like, and esterified with methanol in the presence of an acid catalyst. It is preferable to use a catalyst for esterification.
- the catalyst to be used is preferably an acid catalyst, and for example, sulfuric acid or an ion exchange resin can be used.
- a strongly acidic cation exchange resin is preferable.
- the strongly acidic cation exchange resin include Diaion (registered trademark), PK216, RCP12H (manufactured by Mitsubishi Chemical Corporation), Levacit (registered trademark), K2431 (manufactured by Bayer), and Amberlist (registered trademark) 15WET (Rome). And Hearth Japan Co., Ltd.). One of these may be used alone, or two or more thereof may be used in combination.
- the flow direction of the reaction fluid in esterification may be either vertically upward or vertically downward, and can be appropriately selected.
- the flow direction of the reaction fluid is preferably vertically upward.
- the flow direction of the reaction fluid is preferably vertically downward.
- the amount of the raw material containing methacrylic acid and methanol is preferably 0.10 times or more in terms of the mass ratio to the amount of the ion exchange resin, and is 0. .20 times or more is more preferable.
- the amount of liquid flowing through the raw material is preferably 10.0 times or less, more preferably 5.0 times or less, in terms of mass ratio with respect to the amount of ion exchange resin.
- the upper and lower limits can be combined arbitrarily.
- the amount of liquid flowing through the raw material containing methacrylic acid and methanol is preferably 0.10 times or more and 10.0 times or less, and more preferably 0.20 times or more and 10.0 times or less in terms of mass ratio with respect to the amount of ion exchange resin. , 0.20 times or more and 5.0 times or less is more preferable.
- the reaction temperature for esterification is preferably 40 ° C. or higher and 130 ° C. or lower.
- the reaction temperature is 40 ° C. or higher, the reaction rate is high and esterification can be performed efficiently.
- the reaction temperature is 130 ° C. or lower, the deterioration rate of the ion exchange resin becomes low, and the ion exchange resin can be continuously esterified for a long time.
- the reaction temperature for esterification can be appropriately determined to be the optimum temperature from the viewpoint of chemical equilibrium.
- the raw material composition can be simplified by increasing the concentration of either methacrylic acid or methanol and increasing the conversion rate of the raw material having the lower concentration.
- a catalyst for producing isobutylene from isobutanol a catalyst containing a specific metal is used in alumina containing alumina composed of one or more crystal phases of uniclinical, square, and cubic.
- alumina containing alumina composed of one or more crystal phases of uniclinical, square, and cubic.
- the mass space velocity (WHSV) per unit time of the raw material gas is defined by the following equation (3).
- WHSV (/ h) W1 / W2 ... (3)
- W1 is the amount of isobutanol supplied per unit time (g / h).
- W2 is the amount of catalyst (g) used.
- Example 1 (Catalyst preparation method) In a cobalt acetate aqueous solution in which 0.885 g of cobalt (II) acetate dihydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 99.0%) is dissolved in 100 mL of pure water, it is in the form of a cylindrical pellet (diameter: 3.0 mm).
- cobalt (II) acetate dihydrate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 99.0%
- alumina alumina containing ⁇ -alumina having a square crystal phase as a main component, BET specific surface area: 243 m 2 / g, Na 2 O content: less than 0.050% by mass, SiO 2 content: 0 .10% by mass
- the solvent was removed while stirring with a rotary evaporator. After drying at 24 ° C. for 12 hours, the mixture was calcined at 600 ° C. for 3 hours using an electric furnace to obtain a catalyst A1 having a Co content of 0.10 mmol / g with respect to 1 g of alumina.
- reaction evaluation method A fixed bed reactor (vertical tubular reactor, inner diameter: 16.3 mm, length: 500 mm) immersed in a heat medium was filled with 20.1 g of catalyst A1 to form a catalyst layer. The heat medium temperature was adjusted to 340 ° C. Next, isobutanol (manufactured by Nacalai Tesque, the amount of water measured by the Karl Fischer method: 411 ppm) was adjusted to a flow rate of 0.341 ml / min using a double plunger pump and set to 200 ° C. Supplied to the evaporator. The isobutanol concentration in the raw material gas supplied to the catalyst layer was 100% by volume. The reaction evaluation was started 1 hour after the raw material gas was supplied to the reactor.
- the gas on the outlet side of the reactor is collected and gas chromatographed (manufactured by Shimadzu Corporation, product name: GC-8A) to isobutylene, isobutene, 1-butene, cis-2-butene, Quantification of trans-2-butene was performed.
- the reaction gas discharged from the outlet side of the reactor is trapped in ice-cooled water, and unreacted isobutanol, diisobutyl ether and gas chromatography (manufactured by Shimadzu Corporation, product name: GC-2014) are performed. Isobutyraldehyde was quantified.
- a pressure gauge for measuring the reaction pressure was installed between the evaporator and the reactor inlet. It was confirmed that the pressure loss from the evaporator to the reactor inlet was negligibly small in all the flow rate ranges under the conditions of Examples 1 to 24 and Comparative Examples 1 to 3.
- Example 2 Example 1 except that 1.23 g of manganese acetate (II) tetrahydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 99.0%) was used instead of cobalt (II) acetate dihydrate.
- catalyst B1 having a Mn content of 0.10 mmol / g with respect to 1 g of alumina was obtained.
- Isobutanol and catalyst B1 were brought into contact with each other in the same manner as in Example 1 except that 20.1 g of catalyst B1 was used instead of catalyst A1 and the isobutanol supply rate was changed to 0.308 ml / min to produce a product.
- Example 3 Example 1 except that 1.24 g of nickel (II) acetate tetrahydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 98.0%) was used instead of cobalt (II) acetate dihydrate.
- catalyst C1 having a Ni content of 0.10 mmol / g with respect to 1 g of alumina was obtained.
- Isobutanol and catalyst C1 were brought into contact with each other in the same manner as in Example 1 except that 20.0 g of catalyst C1 was used instead of catalyst A1 and the isobutanol supply rate was changed to 0.327 ml / min to produce a product.
- Example 4 Same as in Example 1 except that 1.10 g of zinc acetate dihydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 98.0%) was used instead of cobalt (II) acetate dihydrate.
- Isobutanol and catalyst D1 were brought into contact with each other in the same manner as in Example 1 except that 20.0 g of catalyst D1 was used instead of catalyst A1 and the isobutanol supply rate was changed to 0.266 ml / min to produce a product.
- Alumina formed into cylindrical pellets (diameter: 3.0 mm) (alumina mainly composed of ⁇ -alumina having a square crystal phase, BET specific surface area: 243 m 2 / g, Na 2 O content: 0.050 Less than mass%, SiO 2 content: 0.10 mass%) was calcined at 600 ° C. for 3 hours, and the catalyst E1 was used as 14.4 g, except that the isobutanol supply rate was changed to 2.57 ml / min. , Isobutanol and catalyst E1 were brought into contact with each other in the same manner as in Example 1 to obtain a product.
- Table 1 shows the reaction conditions and evaluation results of Examples 1 to 4 and Comparative Example 1. The measurement results of the conversion rate of isobutanol, the selectivity of C4 gas in the product, and the selectivity of isobutylene in C4 gas are shown in FIG.
- Examples 1 to 4 using the catalysts A1 to D1 containing Co, Mn, Ni, and Zn in alumina are comparative examples using the catalyst E1 containing no metal.
- the selectivity of isobutylene was higher than that of 1.
- Examples 5 to 12 Zinc acetate / dihydrate was used instead of cobalt (II) acetate / dihydrate, and the catalysts D2 to D9 were used in the same manner as in Example 1 except that the Zn content was changed as shown in Table 2. Obtained.
- the catalysts D2 to D9 were used instead of the catalyst A1, and the isobutanol supply amount and the WHSV to the reaction tube were adjusted as shown in Table 2 in the same manner as in Example 1. Butanol was brought into contact with the catalysts D2 to D9 to obtain a product.
- Example 2 The isobutanol and the catalyst E1 were contacted in the same manner as in Example 1 except that the amount of the catalyst used as the catalyst E1 and the amount of the catalyst to be filled in the reaction tube, the amount of isobutanol supplied to the reaction tube, and the WHSV were adjusted as shown in Table 2. The product was obtained.
- Table 2 shows the reaction conditions and evaluation results of Examples 5 to 12 and Comparative Example 2.
- a graph showing the selectivity of isobutylene in the C4 gas and WHSV of each example is shown in FIG.
- Examples 5 to 12 using the catalysts D2 to D9 containing Zn in alumina were more isobutylene than Comparative Example 2 using the catalyst E1 containing no metal.
- the selection rate was high. Further, the higher the Zn content, the higher the selectivity of isobutylene tended to be.
- Examples 13 to 17 Zinc acetate was used instead of cobalt (II) acetate dihydrate, the firing temperature was set to 700 ° C., and the Zn content was changed as shown in Table 3. Obtained D14.
- the catalysts D10 to D14 were used instead of the catalyst A1, and the isobutanol supply amount and the WHSV to the reaction tube were adjusted as shown in Table 3 in the same manner as in Example 1 except that the amount of catalyst to be filled in the reaction tube and the amount of isobutanol supplied to the reaction tube were adjusted. Butanol was brought into contact with the catalysts D10-D14 to give the product.
- Example 3 Alumina formed into cylindrical pellets (diameter: 3.0 mm) (alumina mainly composed of ⁇ -alumina having a square crystal phase, BET specific surface area: 243 m 2 / g, Na 2 O content: 0.050 The catalyst E2 was obtained by calcining less than mass%, SiO 2 content: 0.10 mass%) at 700 ° C. for 3 hours. A catalyst E2 was used instead of the catalyst A1, and isobutanol was used in the same manner as in Example 1 except that the amount of catalyst to be filled in the reaction tube, the amount of isobutanol supplied to the reaction tube, and WHSV were adjusted as shown in Table 3. Contact with catalyst E2 gave the product.
- Table 3 shows the reaction conditions and evaluation results of Examples 13 to 17 and Comparative Example 3.
- a graph showing the selectivity of isobutylene in the C4 gas and WHSV of each example is shown in FIG.
- Examples 13 to 17 using the catalysts D10 to D14 containing Zn in alumina were more isobutylene than Comparative Example 3 using the catalyst E2 containing no metal.
- the selection rate was high. Further, even when the firing temperature of the catalyst was 700 ° C., the higher the Zn content, the higher the selectivity of isobutylene tended to be.
- Catalysts D15 to D21 were obtained in the same manner as in Example 1 except that zinc acetate was used instead of cobalt acetate and the calcination temperature was changed as shown in Table 4.
- the catalysts D15 to D21 were used instead of the catalyst A1, and the isobutanol supply amount to the reaction tube, the amount of isobutanol supplied to the reaction tube, and the WHSV were adjusted as shown in Table 4 in the same manner as in Example 1. Butanol was brought into contact with the catalysts D15-D21 to give the product.
- Table 4 shows the reaction conditions and evaluation results of Examples 18 to 24.
- a graph showing the selectivity of isobutylene in the C4 gas and WHSV of each example is shown in FIG.
- Example 25 (Catalyst preparation method) Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 A catalyst was prepared in the same manner as in Example 4 except that O content: less than 0.0500% by mass and SiO 2 content: 0.160% by mass) was used, and the Zn content per 1 g of alumina was 0.10 mmol. A catalyst D22 was obtained.
- Alumina alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase
- reaction evaluation method A vertical tubular reaction tube having an inner diameter of 0.50 cm and a length of 40 cm was filled with 1.01 g of catalyst D22 (crushing and sizing so that the particle size was 800 to 1190 ⁇ m) to form a catalyst layer.
- the set temperature of the electric furnace for the reaction tube was adjusted so that the catalyst layer temperature became a predetermined temperature.
- isobutanol manufactured by Nacalai Tesque, measured by the Karl Fischer method: 411 ppm
- Nitrogen gas as a dilution gas was supplied into the evaporator at a flow rate of 11 ml (standard state) / minute using a mass flow meter, and supplied to the reactor together with the evaporated isobutanol.
- the isobutanol concentration in the raw material gas supplied to the catalyst layer was 79.9% by volume, and the temperature of the catalyst layer during the reaction (reaction temperature) was 340 ° C.
- the reaction evaluation was started 1 hour after the raw material gas was supplied to the reactor.
- the gas on the outlet side of the reactor is collected and gas chromatographed (manufactured by Shimadzu Corporation, product name: GC-8A) to isobutylene, isobutene, 1-butene, cis-2-butene, Quantification of trans-2-butene was performed.
- the reaction gas discharged from the outlet side of the reactor is trapped in ice-cooled acetonitrile and unreacted by gas chromatography (manufactured by Shimadzu Corporation, product name: GC-2010), isobutanol, diisobutyl ether and isobutyraldehyde. was quantified.
- Example 26 Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 A catalyst was prepared in the same manner as in Example 1 except that O content: less than 0.0500% by mass and SiO 2 content: 0.160% by mass) was used, and the Co content per 1 g of alumina was 0.10 mmol. A catalyst A2 was obtained. Isobutanol and catalyst A2 were brought into contact with each other in the same manner as in Example 25, except that 1.00 g of catalyst A2 was used instead of catalyst D22 to obtain a product.
- Example 27 Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 O content: less than 0.0500% by mass, SiO 2 content: 0.160% by mass) and copper (II) nitrate dihydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 99.0 to 104.0) %) was used in the same manner as in Example 25 except that 1.18 g was used to obtain a catalyst F1 having a Cu content of 0.10 mmol with respect to 1 g of alumina. Isobutanol and catalyst F1 were brought into contact with each other in the same manner as in Example 25, except that 1.52 g of catalyst F1 was used instead of catalyst D22 to obtain a product.
- alumina alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -a
- Example 28 Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 A catalyst was prepared in the same manner as in Example 2 except that O content: less than 0.0500% by mass and SiO 2 content: 0.160% by mass) was used, and the Mn content per 1 g of alumina was 0.10 mmol. A catalyst B2 was obtained.
- Isobutanol and catalyst B2 were brought into contact with each other in the same manner as in Example 25, except that 2.97 g of catalyst B2 was used instead of catalyst D22 in a vertical tubular reaction tube having an inner diameter of 0.75 cm and a length of 40 cm. The product was obtained.
- Example 29 Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 O content: less than 0.0500% by mass, SiO 2 content: 0.160% by mass) and iron (III) nitrate / 9 hydrate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., purity 99.0%) 1
- a catalyst was prepared in the same manner as in Example 25 except that .46 g was used, and a catalyst G1 having an Fe content of 0.10 mmol / g with respect to 1 g of alumina was obtained. Isobutanol and catalyst G1 were brought into contact with each other in the same manner as in Example 25, except that 1.51 g of catalyst G1 was used instead of catalyst D22 to obtain a product.
- Alumina (alumina composed of crystal phases of ⁇ , ⁇ , ⁇ -alumina phase) formed into a cylindrical pellet (diameter: 3.00 m), particle size: 800 to 1190 ⁇ m, BET specific surface area: 105 m 2 / g, Na 2 O content (less than 0.0500% by mass, SiO 2 content: 0.160% by mass) was crushed and sized so that the particle size was 800 to 1190 ⁇ m to obtain E2.
- Isobutanol and catalyst E2 were brought into contact with each other in the same manner as in Example 25, except that 1.01 g of catalyst E2 was used instead of catalyst D22 to obtain a product.
- Table 5 shows the reaction conditions and evaluation results of Examples 25 to 29 and Comparative Example 4. Further, FIG. 5 shows a graph showing the selectivity of isobutylene and the pass-through rate of isobutanol in the C4 gas of each example.
- Examples 25 to 29 using the catalyst containing Zn, Co, Cu, Mn, and Fe in alumina are Comparative Example 1 using the catalyst E2 containing no metal.
- the selectivity of isobutylene was higher than that of.
Abstract
Description
本願は、2020年3月31日に日本出願された特願2020-064548号に基づき優先権を主張し、その内容をここに援用する。
[1]単斜、正方、立方のいずれか1種以上の結晶相からなるアルミナを含むアルミナに、周期表第4周期~第6周期の第6族~第14族の金属元素から選択される少なくとも1種の金属を含む、触媒。
[2]前記アルミナ1gに対して、前記金属の含有量が0.025mmol以上含まれる、[1]に記載の触媒。
[3][1]又は[2]に記載の触媒を用いて、イソブタノールからイソブチレンを製造する、イソブチレンの製造方法。
[4][3]に記載のイソブチレンの製造方法によって製造されたイソブチレンからメタクリル酸を製造する、メタクリル酸の製造方法。
[5][3]に記載のイソブチレンの製造方法によって製造されたイソブチレンからtert-ブチルアルコールを得た後、得られたtert-ブチルアルコールからメタクリル酸を製造する、メタクリル酸の製造方法。
[6][4]又は[5]に記載のメタクリル酸の製造方法によって製造されたメタクリル酸とメタノールとからメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法。
[7]単斜、正方、立方のいずれか1種以上の結晶相からなるアルミナを含むアルミナに、周期表第4周期~第6周期の第6族~第14族の金属元素から選択される少なくとも1種の金属を含む、触媒を用いて、イソブタノールからイソブチレンを製造する、イソブチレンの製造方法。
[8][7]に記載のイソブチレンの製造方法によって製造されたイソブチレンを製造し、前記イソブチレンからメタクリル酸を製造する、メタクリル酸の製造方法。
[9][7]に記載のイソブチレンの製造方法によって製造されたイソブチレンからtert-ブチルアルコールを得た後、得られたtert-ブチルアルコールからメタクリル酸を製造する、メタクリル酸の製造方法。
[10][8]又は[9]に記載のメタクリル酸の製造方法によって製造されたメタクリル酸とメタノールとからメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法。
本発明の触媒は、イソブタノールからイソブチレンを製造するための触媒である。本発明の触媒では、単斜、正方、立方のいずれか1種以上の結晶相からなるアルミナを含むアルミナに、周期表第4周期~第6周期の第6族~第14族の金属元素から選択される少なくとも1種の金属を含む。本発明の触媒を用いることで、アルミナ上において、ジイソブチルエーテルを経由したイソブタノールの脱水が促進されるため、高い選択率でイソブチレンを製造できる。
アルミナのBET比表面積は、N2吸脱着等温線から算出される値であり、例えば、トライスター3000(製品名、島津製作所社製)を用いて測定できる。
本発明のイソブチレンの製造方法は、本発明の触媒を用いて、イソブタノールからイソブチレンを製造する方法である。
バイオマスは、資源作物に由来するものと、廃棄物に由来するものに大きく分けられる。資源作物に由来するバイオマスとしては、例えば、食用作物、木材、草花が挙げられ、それらの作物の未利用部分も使用できる。廃棄物に由来するバイオマスとしては、例えば、食品廃棄物、下水等の汚泥、家畜糞尿、廃紙が挙げられる。
原料を気化させる際の条件は、特に限定されず、例えば、温度は108℃以上600℃以下、圧力としては絶対圧として0.05MPa以上1MPa以下とすることができる。
反応圧力の値は、反応器の入口の圧力に対して、圧力損失の影響を無視できる位置に設置した圧力センサーで測定される値である。
本発明のメタクリル酸の製造方法は、本発明のイソブチレンの製造方法によって製造したイソブチレンを用いてメタクリル酸を製造する方法である。以下の方法(A)と方法(B)とが挙げられる。方法(A)及び方法(B)によれば、イソブチレンから高い選択率でメタクリル酸を製造できる。
(B)本発明のイソブチレンの製造方法によりイソブチレンを製造する工程(b1)と、イソブチレンを水和してtert-ブチルアルコールを製造する工程(b2)と、イソブチレンを水和して製造したtert-ブチルアルコールの気相酸化によりメタクリル酸を製造する工程(b3)と、を含む。
Mo12Bia1Fea2Ma3Xa4Ya5Za6Oa7 ・・・(1)
ただし、式(1)中、Mo、Bi、Fe及びOはそれぞれモリブテン、ビスマス、鉄及び酸素を示す。Mは、コバルト及びニッケルからなる群から選ばれる少なくとも1種の元素を表す。Xは、クロム、鉛、マンガン、カルシウム、マグネシウム、ニオブ、銀、バリウム、スズ、タンタル及び亜鉛からなる群から選ばれる少なくとも1種の元素を表す。Yは、リン、ホウ素、硫黄、セレン、テルル、セリウム、タングステン、アンチモン及びチタンからなる群から選ばれる少なくとも1種の元素を表す。Zは、リチウム、ナトリウム、カリウム、ルビジウム、セシウム及びタリウムからなる群から選ばれる少なくとも1種の元素を表す。a1~a7は各元素の原子比率を表し、a1、a2、a3、a4、a5、a6、a7はMo12原子に対する各元素の原子比を示し、a1=0.01~3、a2=0.01~5、a3=1.0~12、a4=0~8.0、a5=0~5.0、a6=0.001~2.0であり、a7は各成分の原子価を満足するのに必要な酸素の原子比率である。
第一段酸化の反応温度は、200℃以上450℃以下が好ましく、250℃以上400℃以下がより好ましい。
第一段酸化におけるイソブチレン又はtert-ブチルアルコールと分子状酸素の接触時間は、0.5秒以上が好ましく、1.0秒以上がより好ましい。第一段酸化におけるイソブチレン又はtert-ブチルアルコールと分子状酸素の接触時間は、10.0秒以下が好ましく、6.0秒以下がより好ましい。前記の上限及び下限は任意に組み合わせることができる。例えば、第一段酸化におけるイソブチレン又はtert-ブチルアルコールと分子状酸素の接触時間は、0.5秒以上10.0秒以下が好ましく、0.5秒以上6.0秒以下がより好ましく、1.0秒以上6.0秒以下がさらに好ましい。
Pa8Moa9Va10Cua11Aa12Ea13Ga14Oa15 ・・・(2)
式(2)中、P、Mo、V、Cu及びOはそれぞれリン、モリブテン、バナジウム、銅及び酸素を示す。Aはアンチモン、ビスマス、砒素、ゲルマニウム、ジルコニウム、テルル、銀、セレン、ケイ素、タングステン及びホウ素からなる群から選択される少なくとも1種の元素を示す。Eはカリウム、ルビジウム、セシウム、タリウム、マグネシウム及びバリウムからなる群から選択される少なくとも1種の元素を示す。Gは鉄、亜鉛、クロム、カルシウム、ストロンチウム、タンタル、コバルト、ニッケル、マンガン、チタン、スズ、鉛、ニオブ、インジウム、硫黄、パラジウム、ガリウム、セリウム及びランタンからなる群から選択される少なくとも1種の元素を示す。a8~a15は各元素の原子比率を表し、a9=12のとき、a8=0.5~3、a10=0.01~3、a11=0.01~2、a12=0~3、好ましくは0.01~3、a13=0.01~3、a14=0~4であり、a15は各元素の原子価を満足するのに必要な酸素の原子比率である。
第二段酸化の反応ガス中の分子状酸素の濃度は、メタクロレイン1.0molに対して、0.5mol以上が好ましく、1.0mol以上がより好ましい。また、第二段酸化の反応ガス中の分子状酸素濃度は、メタクロレイン1.0molに対して、4.0mol以下が好ましく、3.0mol以下がより好ましい。前記の上限及び下限は任意に組み合わせることができる。例えば、第二段酸化の分子状酸素の濃度は、メタクロレイン1.0molに対して、0.5mol以上4.0mol以下が好ましく、1.0mol以上4.0mol以下がより好ましく、1.0mol以上3.0mol以下がさらに好ましい。
本発明のメタクリル酸メチルの製造方法は、本発明のメタクリル酸の製造方法を用いて製造したメタクリル酸を用いてメタクリル酸メチルを製造する方法である。
本発明のメタクリル酸メチルの製造方法は、本発明のメタクリル酸の製造方法を用いて製造したメタクリル酸をメタノールとエステル化させることによりメタクリル酸メチルを製造する工程を含む。本発明の方法によれば、イソブチレンから高い選択率でメタクリル酸メチルを製造できる。
エステル化には、触媒を用いることが好ましい。用いる触媒としては、酸触媒であることが好ましく、例えば、硫酸やイオン交換樹脂を用いることができる。イオン交換樹脂としては、強酸性陽イオン交換樹脂が好ましい。強酸性陽イオン交換樹脂としては、例えば、ダイヤイオン(登録商標)、PK216、RCP12H(三菱化学社製)、レバチット(登録商標)、K2431(バイエル社製)、アンバーリスト(登録商標)15WET(ロームアンドハースジャパン社製)が挙げられる。これらは1種を単独で用いてもよく、2種以上を併用してもよい。
反応温度が40℃以上であれば、反応速度が大きく、効率的にエステル化できる。反応温度が130℃以下であれば、イオン交換樹脂の劣化速度が小さくなり、長時間連続的にエステル化できる。エステル化の反応温度は、化学平衡の観点から、適宜最適な温度に決定できる。
イソブタノールの転化率(%)=(b/a)×100
C4ガスの選択率(%)=(j/b)×100
ジイソブチルエーテルの選択率(%)=(h/b)×2×100
イソブチルアルデヒドの選択率(%)=(i/b)×100
C4ガス中のイソブチレンの選択率(%)=(c/j)×100
C4ガス中のイソブタンの選択率(%)=(d/j)×100
C4ガス中の1-ブテンの選択率(%)=(e/j)×100
C4ガス中のtrans-2-ブテンの選択率(%)=(f/j)×100
C4ガス中のcis-2-ブテンの選択率(%)=(g/j)×100
a:供給したイソブタノールのモル数
b:反応したイソブタノールのモル数
c:生成したイソブチレンのモル数
d:生成したイソブタンのモル数
e:生成した1-ブテンのモル数
f:生成したtrans-2-ブテンのモル数
g:生成したcis-2-ブテンのモル数
h:生成したジイソブチルエーテルのモル数
i:生成したイソブチルアルデヒドのモル数
j:生成したC4ガス(イソブテン、イソブタン、1-ブテン、trans-2-ブテン、cis-2-ブテン)のモル数
WHSV(/h)=W1/W2・・・(3)
ただし、式(3)中、W1は、イソブタノールの単位時間当たりの供給量(g/h)である。W2は、使用した触媒量(g)である。
(触媒調製方法)
酢酸コバルト(II)・2水和物(富士フィルム和光純薬社製、純度99.0%)0.885gを純水100mLに溶解した酢酸コバルト水溶液に、円柱形ペレット状(直径:3.0mm)に成形されたアルミナ(正方結晶相を有するγ-アルミナを主成分とするアルミナ、BET比表面積:243m2/g、Na2O含有量:0.050質量%未満、SiO2含有量:0.10質量%)50.0gを加えた後、ロータリーエバポレーターでかき混ぜながら溶媒を除去した。24℃で12時間乾燥させた後、電気炉を用いて600℃で3時間焼成して、アルミナ1gに対するCo含有量が0.10mmol/gである触媒A1を得た。
触媒A1 20.1gを熱媒に浸された固定床反応器(縦型管状反応管、内径:16.3mm、長さ:500mm)に充填し、触媒層を形成した。熱媒温度は340℃に調整した。次に、イソブタノール(ナカライテスク社製、カールフィッシャー法によって測定された水の量:411ppm)を、ダブルプランジャーポンプを用いて、0.341ml/分の流量に調整し、200℃に設定した蒸発器に供給した。触媒層に供給した原料ガス中のイソブタノール濃度は100体積%であった。
原料ガスを反応器に供給して1時間経過後、反応評価を開始した。反応が定常状態に達した後、反応器出側のガスを採取し、ガスクロマトグラフィー(島津製作所社製、製品名:GC-8A)でイソブチレン、イソブタン、1-ブテン、cis-2-ブテン、trans-2-ブテンの定量を行った。また、反応器出側から排出される反応ガスを、氷冷した水にトラップし、ガスクロマトグラフィー(島津製作所(株)製、製品名:GC-2014)で未反応のイソブタノール、ジイソブチルエーテル及びイソブチルアルデヒドの定量を行った。反応圧力を測定するための圧力計は、蒸発器と反応器入り口の間に設置した。
なお、実施例1~24、比較例1~3の条件下のあらゆる流量範囲において、蒸発器から反応器入口までの圧力損失は無視できる程度小さいことを確認した。
酢酸コバルト(II)・2水和物の代わりに酢酸マンガン(II)・4水和物(富士フィルム和光純薬社製、純度99.0%)1.23gを用いた以外は、実施例1と同様にして、アルミナ1gに対するMn含有量が0.10mmol/gである触媒B1を得た。
触媒A1の代わりに触媒B1 20.1gを用いて、イソブタノール供給速度を0.308ml/分に変更したこと以外は、実施例1と同様にしてイソブタノールと触媒B1とを接触させ、生成物を得た。
酢酸コバルト(II)・2水和物の代わりに酢酸ニッケル(II)・4水和物(富士フィルム和光純薬社製、純度98.0%)1.24gを用いた以外は、実施例1と同様にして、アルミナ1gに対するNi含有量が0.10mmol/gである触媒C1を得た。
触媒A1の代わりに触媒C1 20.0gを用いて、イソブタノール供給速度を0.327ml/分に変更したこと以外は、実施例1と同様にしてイソブタノールと触媒C1とを接触させ、生成物を得た。
酢酸コバルト(II)・2水和物の代わりに酢酸亜鉛・2水和物(富士フィルム和光純薬社製、純度98.0%)1.10gを用いた以外は、実施例1と同様にして、アルミナ1gに対するZn含有量が0.10mmol/gである触媒D1を得た。
触媒A1の代わりに触媒D1 20.0gを用いて、イソブタノール供給速度を0.266ml/分に変更したこと以外は、実施例1と同様にしてイソブタノールと触媒D1とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.0mm)に成形されたアルミナ(正方結晶相を有するγ-アルミナを主成分とするアルミナ、BET比表面積:243m2/g、Na2O含有量:0.050質量%未満、SiO2含有量:0.10質量%)を600℃で3時間焼成したものを触媒E1 14.4gとして用いて、イソブタノール供給速度を2.57ml/分に変更したこと以外は、実施例1と同様にしてイソブタノールと触媒E1とを接触させ、生成物を得た。
酢酸コバルト(II)・2水和物の代わりに酢酸亜鉛・2水和物を用い、Zn含有量を表2に示す通りに変更した以外は、実施例1と同様にして触媒D2~D9を得た。
触媒A1の代わりに触媒D2~D9を用い、反応管に充填する触媒量、反応管へのイソブタノール供給量、WHSVを表2に示す通りに調節した以外は、実施例1と同様にしてイソブタノールと触媒D2~D9とを接触させ、生成物を得た。
触媒E1として用い、反応管に充填する触媒量、反応管へのイソブタノール供給量、WHSVを表2に示す通りに調節した以外は、実施例1と同様にしてイソブタノールと触媒E1とを接触させ、生成物を得た。
酢酸コバルト(II)・2水和物の代わりに酢酸亜鉛を用い、焼成温度を700℃とし、Zn含有量を表3に示す通りに変更した以外は、実施例1と同様にして触媒D10~D14を得た。
触媒A1の代わりに触媒D10~D14を用い、反応管に充填する触媒量、反応管へのイソブタノール供給量、WHSVを表3に示す通りに調節した以外は、実施例1と同様にしてイソブタノールと触媒D10~D14とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.0mm)に成形されたアルミナ(正方結晶相を有するγ-アルミナを主成分とするアルミナ、BET比表面積:243m2/g、Na2O含有量:0.050質量%未満、SiO2含有量:0.10質量%)を700℃で3時間焼成したものを触媒E2とした。
触媒A1の代わりに触媒E2を用い、反応管に充填する触媒量、反応管へのイソブタノール供給量、WHSVを表3に示す通りに調節した以外は、実施例1と同様にしてイソブタノールと触媒E2とを接触させ、生成物を得た。
酢酸コバルトの代わりに酢酸亜鉛を用い、焼成温度を表4に示す通りに変更した以外は、実施例1と同様にして触媒D15~D21を得た。
触媒A1の代わりに触媒D15~D21を用い、反応管に充填する触媒量、反応管へのイソブタノール供給量、WHSVを表4に示す通りに調節した以外は、実施例1と同様にしてイソブタノールと触媒D15~D21とを接触させ、生成物を得た。
(触媒調製方法)
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)を使ったこと以外は実施例4と同様に触媒を調製し、アルミナ1gに対するZn含有量が0.10mmolである触媒D22を得た。
内径0.50cm、長さ40cmの縦型管状反応管に、触媒D22(粒子径が800~1190μmとなる様、破砕・整粒)1.01gを充填し、触媒層を形成した。反応器については、触媒層温度が所定温度となるように、反応管用の電気炉の設定温度を調整した。次に、イソブタノール(ナカライテスク社製、カールフィッシャー法によって測定された水の量:411ppm)をシリンジポンプで0.18ml/分、200℃で加熱された気化器に導入し、蒸発させた。希釈ガスとしての窒素ガスはマスフローメーターを用いて流量11ml(標準状態)/分として当該蒸発器内に供給し、蒸発したイソブタノールと共に反応器に供給した。触媒層に供給した原料ガス中のイソブタノール濃度は79.9体積%、反応中の触媒層の温度(反応温度)は340℃であった。
原料ガスを反応器に供給して1時間経過後、反応評価を開始した。反応が定常状態に達した後、反応器出側のガスを採取し、ガスクロマトグラフィー(島津製作所社製、製品名:GC-8A)でイソブチレン、イソブタン、1-ブテン、cis-2-ブテン、trans-2-ブテンの定量を行った。また、反応器出側から排出される反応ガスを、氷冷したアセトニトリルにトラップし、ガスクロマトグラフィー(島津製作所社製、製品名:GC-2010)で未反応のイソブタノール、ジイソブチルエーテル及びイソブチルアルデヒドの定量を行った。
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)を使ったこと以外は実施例1と同様に触媒を調製し、アルミナ1gに対するCo含有量が0.10mmolである触媒A2を得た。
触媒D22の代わりに触媒A2 1.00gを用いたこと以外は、実施例25と同様にしてイソブタノールと触媒A2とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)と硝酸銅(II)・2水和物(富士フィルム和光純薬社製、純度99.0~104.0%)を1.18g使ったこと以外は実施例25と同様に触媒を調製し、アルミナ1gに対するCu含有量が0.10mmolである触媒F1を得た。
触媒D22の代わりに触媒F1 1.52gを用いたこと以外は、実施例25と同様にしてイソブタノールと触媒F1とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)を使ったこと以外は実施例2と同様に触媒を調製し、アルミナ1gに対するMn含有量が0.10mmolである触媒B2を得た。
内径0.75cm、長さ40cmの縦型管状反応管に、触媒D22の代わりに触媒B2 2.97gを用いたこと以外は、実施例25と同様にしてイソブタノールと触媒B2とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)と硝酸鉄(III)・9水和物(富士フィルム和光純薬社製、純度99.0%)を1.46g使ったこと以外は実施例25と同様に触媒を調製し、アルミナ1gに対するFe含有量が0.10mmol/gである触媒G1を得た。
触媒D22の代わりに触媒G1 1.51gを用いたこと以外は、実施例25と同様にしてイソブタノールと触媒G1とを接触させ、生成物を得た。
円柱形ペレット状(直径:3.00m)に成形されたアルミナ(γ、θ、α-アルミナ相の結晶相からなるアルミナ、粒子径:800~1190μm、BET比表面積:105m2/g、Na2O含有量:0.0500質量%未満、SiO2含有量:0.160質量%)を、粒子径が800~1190μmとなる様、破砕・整粒し、E2を得た。
触媒D22の代わりに触媒E2 1.01gを用いたこと以外は、実施例25と同様にしてイソブタノールと触媒E2とを接触させ、生成物を得た。
Claims (10)
- 単斜、正方、立方のいずれか1種以上の結晶相からなるアルミナを含むアルミナに、周期表第4~第6周期の第6族~第14族の金属元素から選択される少なくとも1種の金属を含む、触媒。
- 前記アルミナ1gに対して、前記金属の含有量が0.025mmol以上含まれる、請求項1に記載の触媒。
- 請求項1又は2に記載の触媒を用いて、イソブタノールからイソブチレンを製造する、イソブチレンの製造方法。
- 請求項3に記載のイソブチレンの製造方法によって製造されたイソブチレンからメタクリル酸を製造する、メタクリル酸の製造方法。
- 請求項3に記載のイソブチレンの製造方法によって製造されたイソブチレンからtert-ブチルアルコールを得た後、得られたtert-ブチルアルコールからメタクリル酸を製造する、メタクリル酸の製造方法。
- 請求項4又は5に記載のメタクリル酸の製造方法によって製造されたメタクリル酸とメタノールとからメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法。
- 単斜、正方、立方のいずれか1種以上の結晶相からなるアルミナを含むアルミナに、周期表第4周期~第6周期の第6族~第14族の金属元素から選択される少なくとも1種の金属を含む、触媒を用いて、イソブタノールからイソブチレンを製造する、イソブチレンの製造方法。
- 請求項7に記載のイソブチレンの製造方法によって製造されたイソブチレンからメタクリル酸を製造する、メタクリル酸の製造方法。
- 請求項7に記載のイソブチレンの製造方法によって製造されたイソブチレンからtert-ブチルアルコールを得た後、得られたtert-ブチルアルコールからメタクリル酸を製造する、メタクリル酸の製造方法。
- 請求項8又は9に記載のメタクリル酸の製造方法によって製造されたメタクリル酸とメタノールとからメタクリル酸メチルを製造する、メタクリル酸メチルの製造方法。
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