WO2013069630A1 - イソブタノールからt-ブタノールを製造する方法、イソブタノールからメタクロレイン及びメタクリル酸を製造する方法、並びにそれらの製造装置 - Google Patents
イソブタノールからt-ブタノールを製造する方法、イソブタノールからメタクロレイン及びメタクリル酸を製造する方法、並びにそれらの製造装置 Download PDFInfo
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- WO2013069630A1 WO2013069630A1 PCT/JP2012/078714 JP2012078714W WO2013069630A1 WO 2013069630 A1 WO2013069630 A1 WO 2013069630A1 JP 2012078714 W JP2012078714 W JP 2012078714W WO 2013069630 A1 WO2013069630 A1 WO 2013069630A1
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- Prior art keywords
- isobutanol
- butanol
- methacrylic acid
- methacrolein
- butenes
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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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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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
- C07C45/34—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 in unsaturated compounds
- C07C45/35—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 in unsaturated compounds in propene or isobutene
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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
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
Definitions
- the present invention relates to a method for producing t-butanol as a raw material for methacrylic resin from isobutanol, particularly biomass-derived isobutanol, a method for producing methacrolein and methacrylic acid from isobutanol, and an apparatus for producing them.
- methacrylic resin which is a kind of plastic, has excellent properties such as transparency and weather resistance, and is used in various applications.
- One method for producing methacrolein or methacrylic acid, which is a raw material of methyl methacrylate, which is a raw material of this methacrylic resin, is a catalytic gas phase oxidation method using t-butanol or isobutylene as a raw material.
- Patent Documents 1 and 2 describe a method for producing t-butanol (tertiary butanol) from butenes.
- Patent Document 3 describes a method for producing methacrolein from t-butanol.
- Patent Document 4 describes a method for producing methacrolein and methacrylic acid from isobutylene.
- Non-Patent Document 1 describes a method of synthesizing isobutylene from isobutanol.
- Patent Document 5 describes a method for producing methacrolein and methacrylic acid from isobutanol.
- T-Butanol is not directly produced by current fermentation methods, but isobutanol can also be obtained by fermentation methods.
- Non-patent document 1 describes a study assuming isobutanol obtained by fermentation, and describes that isobutanol is dehydrated to produce isobutylene as a methacrylic resin raw material, but the production of t-butanol is described. It has not been. Moreover, there is no description about the process of the impurity which has a bad influence on reaction at the time of manufacturing a methacrylic resin raw material.
- Patent Document 5 describes a method for producing methacrolein and methacrylic acid from isobutanol, but the selectivity to the target product is very low. Therefore, in order to efficiently produce a methacrylic resin raw material, it is difficult to directly apply the conventional technique using a petroleum-derived chemical as a starting material.
- an object of the present invention is to provide a method capable of efficiently producing t-butanol from isobutanol, a method capable of efficiently producing methacrolein and methacrylic acid from isobutanol, and a production apparatus thereof.
- the present invention relates to a process for producing t-butanol from isobutanol, Dehydrating isobutanol to obtain butenes (1), Step (2) of obtaining t-butanol by hydrating the butenes obtained in Step (1)
- a process for producing t-butanol characterized in that
- the present invention also provides a method for producing methacrolein and methacrylic acid from isobutanol, Step (3) of obtaining methacrolein and methacrylic acid by dehydration and oxidation of t-butanol obtained by the above method It is a method for producing methacrolein and methacrylic acid characterized by having
- the present invention provides an apparatus for producing t-butanol from isobutanol.
- Equipment for dehydrating isobutanol to obtain butenes (A)
- Apparatus (B) for hydrating butenes obtained in apparatus (A) to obtain t-butanol Is an apparatus for producing t-butanol.
- the present invention also provides an apparatus (C) for obtaining methacrolein and methacrylic acid by dehydrating and oxidizing t-butanol obtained by the above apparatus.
- An apparatus for producing methacrolein and methacrylic acid characterized in that
- the present invention it is possible to provide a method capable of efficiently producing t-butanol from isobutanol, a method capable of efficiently producing methacrolein and methacrylic acid from isobutanol, and production thereof. Furthermore, the present invention is particularly useful from the standpoint of environmental protection, since it is possible to carry out the reaction efficiently using isobutanol derived from biomass as a starting material.
- Step (1) in the present invention is a step of dehydrating isobutanol to obtain butenes.
- the dehydration reaction of isobutanol may be performed according to a conventionally known method.
- a dehydration catalyst such as an acid catalyst.
- the acid catalyst include alumina, silica alumina, solid phosphoric acid, titania, and zirconia.
- the reaction temperature is preferably 150 to 500 ° C.
- the apparatus (A) used for the step (1) may be an apparatus capable of dehydrating isobutanol to obtain butenes.
- any apparatus that can perform a dehydration reaction by supplying isobutanol into an apparatus loaded with a dehydration catalyst and take out butenes as a reaction product thereof may be used.
- isobutanol is not directly used in the dehydration and oxidation process, but isobutanol is once converted into butenes in step (1), and then isobutylene in the butenes is hydrated in step (2).
- the reaction is carried out in the order of t-butanol.
- methacrolein and methacrylic acid are the target products, the t-butanol obtained in step (2) is reacted in the order of dehydration and oxidation to methacrolein and methacrylic acid in step (3).
- step (2) only isobutylene in butenes can be selectively hydrated, and in step (3), t-butanol is dehydrated into isobutylene and water almost according to the theoretical yield. Therefore, butenes other than isobutylene are substantially not present in the raw material supplied to the oxidation step. Therefore, the influence of butenes other than isobutylene on the catalyst in the oxidation step can be avoided.
- the dehydration and oxidation steps can be performed with good yield and the catalyst can be operated with a long life. Can do.
- the isobutanol used as a starting material in the step (1) is not particularly limited. However, in the present invention, it is particularly effective to use biomass-derived isobutanol.
- the biomass-derived isobutanol may contain a small amount of other components such as alcohols and aldehydes other than isobutanol, but in the present invention, the reaction is performed in a specific order as described above. This is because the adverse effects of other alcohols and aldehydes can be avoided.
- the isobutylene concentration in butenes obtained by dehydrating isobutanol is generally higher than the isobutylene concentration (10 to 55% by mass) in butenes obtained from petroleum.
- the biomass-derived isobutanol is purified from an organic compound obtained through a fermentation process using fermentable sugar of plant biomass such as corn. Such biomass-derived isobutanol can also be obtained as a commercial product.
- Step (2) in the present invention is a step of obtaining t-butanol by hydrating the butenes obtained in step (1).
- the hydration reaction of butenes may be performed according to a conventionally known method.
- a hydration catalyst such as an acid catalyst.
- the acid catalyst include ion exchange resins and heteropolyacids. More preferably, a strongly acidic cation exchange resin is good.
- the reaction temperature is preferably 30 to 100 ° C.
- the apparatus (B) used in the step (2) may be an apparatus that can hydrate butenes to obtain t-butanol.
- any apparatus that can perform hydration reaction by supplying butenes into an apparatus loaded with a hydration catalyst and take out the reaction product t-butanol may be used.
- Step (3) in the present invention is a step of obtaining methacrolein and methacrylic acid by dehydrating and oxidizing the t-butanol obtained in step (2).
- the dehydration and oxidation reaction of t-butanol may be performed according to conventionally known methods.
- a dehydration catalyst such as an acid catalyst and an oxidation catalyst.
- Specific examples of the dehydration catalyst include the same catalyst as described in the step (1).
- the oxidation catalyst also functions as a dehydration catalyst, the dehydration catalyst is not necessarily used.
- a catalyst component containing at least molybdenum, bismuth and iron as a catalyst component and having a composition represented by the following general formula (1) is preferable.
- Mo, Bi, Fe, Si and O represent molybdenum, bismuth, iron, silicon and oxygen, respectively.
- M represents at least one element selected from cobalt and nickel.
- X represents chromium, lead and manganese.
- Z represents at least one element selected from lithium, sodium, potassium, rubidium, cesium and thallium
- the concentration of t-butanol in the raw material gas can be varied within a wide range, but is preferably 1 to 20% by volume. Although it is economical to use air as the molecular oxygen source, air or the like enriched with pure oxygen can be used if necessary.
- the molar ratio (volume ratio) between the reaction raw material and oxygen in the raw material gas is preferably in the range of 1: 0.5 to 1: 3.
- the raw material gas preferably contains water in addition to the reaction raw material and molecular oxygen, and is preferably diluted with an inert gas such as nitrogen or carbon dioxide.
- the water concentration in the raw material gas is preferably 1 to 45% by volume.
- the reaction pressure is preferably from normal pressure to several hundred kPa.
- the reaction temperature can usually be selected in the range of 200 to 450 ° C., but the range of 250 to 400 ° C. is particularly preferable.
- the contact time is preferably 1.5 to 15 seconds.
- the apparatus (C) used in the step (3) may be an apparatus capable of obtaining methacrolein and methacrylic acid by dehydrating and oxidizing t-butanol.
- step (3) In the reaction product obtained by dehydrating and oxidizing t-butanol in step (3), most of t-butanol is converted to methacrolein, and a part thereof is converted to methacrylic acid.
- the conversion of both may be adjusted as appropriate depending on the reaction conditions and the type of catalyst.
- the entire production process can be simplified.
- linear butenes other than isobutylene hardly react and are present in the product gas, which adversely affects the subsequent process. Therefore, for example, there is a method in which a step of purifying before the methacrolein catalytic vapor phase oxidation reaction (second stage oxidation) is added to return a part of the unreacted butenes to the raw material gas.
- Methacrolein is useful as a raw material for methacrylic acid.
- methacrylic acid can be obtained by subjecting a gas (such as air) containing methacrolein and molecular oxygen to a catalytic gas phase oxidation reaction (second stage oxidation).
- a gas such as air
- methacrolein and molecular oxygen can be obtained by subjecting a gas (such as air) containing methacrolein and molecular oxygen to a catalytic gas phase oxidation reaction (second stage oxidation).
- the methyl methacrylate which is one of the methacrylic resin raw materials is obtained by esterification reaction of methacrylic acid and methanol.
- a methacrylic resin can be obtained by polymerizing this methyl methacrylate.
- Step (1) Dehydration of isobutanol
- silica alumina N632HN 5 mm ⁇ ⁇ 5 mm, manufactured by JGC Catalysts and Chemicals
- the mixed gas was fed at a space velocity of 45 s-1 and reacted to obtain a butene mixed gas (butenes).
- Step (3) Dehydration and oxidation of t-butanol
- dehydration and oxidation were performed as follows to obtain methacrolein and methacrylic acid.
- the temperature is maintained at 160 ° C., and consists of a t-butanol concentration of 10 vol% and water vapor of 90 vol%.
- the mixed gas was reacted at a contact time of 3 seconds.
- the conversion of t-butanol was 91.2%, and isobutylene was obtained at a high purity of 97.1%.
- An oxidation catalyst 10 g was filled in a stainless steel reaction tube having an inner diameter of 15 mm. Then, a raw material gas comprising 5% by volume of high-purity isobutylene obtained by the above dehydration reaction, 12% by volume of molecular oxygen, 10% by volume of water vapor, and balance gas nitrogen is supplied, and the contact time is 3.0 seconds under normal pressure. Isobutylene was vapor-phase contact oxidized with molecular oxygen at a reaction temperature of 340 ° C. Table 1 shows the ratio of unreacted butenes and the reaction products in the obtained reaction gas.
- the oxidation catalyst used in the above step is specifically a catalyst prepared by the following method.
- Liquid A was prepared by dissolving and mixing 500 parts of ammonium paramolybdate, 6.2 parts of ammonium paratungstate, and 27.6 parts of cesium nitrate in 1000 parts of pure water at 60 ° C. Then, when 27.5 parts of bismuth trioxide was added, a white precipitate was formed in the liquid A. Separately, 100.2 parts of ferric nitrate, 78.9 parts of nickel nitrate, 14.0 parts of zinc nitrate, and 357.1 parts of cobalt nitrate were sequentially added and dissolved in 1000 parts of pure water. It was set as B liquid.
- the B liquid was added to the A liquid in which the white precipitate was generated to obtain a slurry C liquid.
- 24.1 parts of antimony trioxide was added to solution C to obtain solution D.
- most of the water was evaporated.
- the obtained cake-like substance A was heat-treated at 120 ° C. for 16 hours and further at 300 ° C. for 1 hour in an air atmosphere, and then pulverized.
- the pressure-molded product was crushed, and among the crushed particles, a particle that passed through a sieve having an aperture of 2.36 mm and not passed through a sieve having an aperture of 0.71 mm was obtained.
- the particles of a specific size thus classified were again heat-treated at 500 ° C. for 6 hours in an air atmosphere to obtain a catalyst.
- the catalyst composition other than oxygen of the obtained catalyst was Mo 12 W 0.1 Bi 0.5 Fe 2.1 Ni 2.3 Co 5.2 Zn 0.2 Sb 0.7 Cs 0.6 .
- the isobutylene was vapor-phase contact oxidized with molecular oxygen in the same manner as in Example 1 except that the above raw material gas was used.
- Table 1 shows the ratio of unreacted butenes and the reaction products in the obtained reaction gas.
- Example 1 is a method for producing methacrolein and methacrylic acid from isobutanol via steps (1) to (3). The ratio was high, but the residual ratio of butenes was low, and 1-butene, cis-2-butene, and trans-2-butene were not contained.
- Comparative Example 1 is a method similar to the case where the butene mixed gas generated by dehydration of isobutanol is used as it is as a raw material for the gas phase catalytic oxidation reaction, so the ratio of methacrolein and methacrylic acid in the obtained reaction gas is The residual ratio of butenes was low, and a large amount of 1-butene, cis-2-butene, and trans-2-butene, which had an adverse effect on the subsequent steps, were contained.
- the present invention is useful as a method for efficiently producing t-butanol, methacrolein and methacrylic acid, which are raw materials for methacrylic resins.
- methacrylic resin is excellent in characteristics such as transparency and weather resistance, it can be suitably used for many applications such as signboards, covers for lighting fixtures, aquarium tanks, and recently LED light guide plates for LED liquid crystal televisions. it can.
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Abstract
Description
イソブタノールを脱水してブテン類を得る工程(1)、
工程(1)で得たブテン類を水和してt-ブタノールを得る工程(2)
を有することを特徴とするt-ブタノールを製造する方法である。
上記方法により得たt-ブタノールを脱水及び酸化してメタクロレイン及びメタクリル酸を得る工程(3)
を有することを特徴とするメタクロレイン及びメタクリル酸を製造する方法である。
イソブタノールを脱水してブテン類を得る装置(A)
装置(A)で得たブテン類を水和してt-ブタノールを得る装置(B)
を有することを特徴とするt-ブタノールを製造する装置である。
を有することを特徴とするメタクロレイン及びメタクリル酸を製造する装置である。
(式中、Mo、Bi、Fe、Si及びOはそれぞれモリブデン、ビスマス、鉄、ケイ素及び酸素を示す。Mはコバルト及びニッケルから選ばれる少なくとも1種の元素を示す。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選ばれる少なくとも1種の元素を示す。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選ばれる少なくとも1種の元素を示す。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選ばれる少なくとも1種の元素を示す。a、b、c、d、e、f、g、h及びiは各元素の原子比率を表し、a=12のときb=0.01~3、c=0.01~5、d=1~12、e=0~8、f=0~5、g=0.001~2及びh=0~20であり、iは前記各成分の原子価を満足するのに必要な酸素原子比率である。)
原料及び生成物の分析はガスクロマトグラフィーを用いて行った。原料(イソブタノール、イソブチレン及びt-ブタノール)の転化率、生成する各成分の選択率はそれぞれ以下のように定義される。
原料の転化率(%)=(反応した原料のモル数/供給した原料のモル数)×100
各成分の選択率(%)=(生成した各成分のモル数/ガスクロマトグラフィーで検出した成分の総モル数)×100
(工程(1):イソブタノールの脱水)
脱水触媒として市販のシリカアルミナ(N632HN・5mmφ×5mm・日揮触媒化成製)を充填した固定床反応器を用いて340℃に保ち、イソブタノール5容量%、窒素45容量%および水蒸気50容量%からなる混合ガスを空間速度45s-1で送入し反応させ、ブテン混合ガス(ブテン類)を得た。その結果、イソブタノール転化率は90.3%で、ブテン混合ガスにおけるイソブチレン選択率は82.3%、1-ブテン選択率は5.8%、cis-2-ブテン選択率は3.7%、trans-2-ブテン選択率は5.8%、イソブタン選択率は2.3%であった。
工程(1)で得たブテン混合ガス1.0部と水0.4部をオートクレーブに入れ、イオン交換樹脂(ダウケミカル製アンバーリスト15JWET)5.0部を加え、60℃、1.5MPaで6時間反応を行なった。その結果、イソブチレン転化率92%でt-ブタノール1.04部を得た。副生物のsec-ブタノールは500ppm未満であった。
工程(2)で得たt-ブタノールを用いて、以下の通り脱水及び酸化を行ない、メタクロレイン及びメタクリル酸を得た。
本比較例では、イソブチレンを分子状酸素により気相接触酸化する際の原料として、イソブチレン5容量%、1-ブテン0.4容量%、cis-2-ブテン0.5容量%、トランス-2-ブテン0.4容量%、分子状酸素12容量%、水蒸気10容量%及び窒素71.7容積%からなる原料ガスを用いた。
表1に示す通り、実施例1は、工程(1)~(3)を経由してイソブタノールからメタクロレイン及びメタクリル酸を製造する方法なので、得られた反応ガス中のメタクロレイン及びメタクリル酸の比率が高く、ブテン類の残存比率は低く、1-ブテン、cis-2-ブテン、トランス-2-ブテンは含まれていなかった。
Claims (11)
- イソブタノールからt-ブタノールを製造する方法において、
イソブタノールを脱水してブテン類を得る工程(1)、
工程(1)で得たブテン類を水和してt-ブタノールを得る工程(2)
を有することを特徴とするt-ブタノールを製造する方法。 - イソブタノールからメタクロレイン及びメタクリル酸を製造する方法において、
請求項1記載の方法により得たt-ブタノールを脱水及び酸化してメタクロレイン及びメタクリル酸を得る工程(3)
を有することを特徴とするメタクロレイン及びメタクリル酸を製造する方法。 - 工程(1)において、酸触媒を脱水触媒として用いる請求項1記載の方法。
- 酸触媒が、アルミナ、シリカアルミナ、固体リン酸、チタニア又はジルコニアを含む酸触媒である請求項3記載の方法。
- 工程(2)において、酸触媒を水和触媒として用いる請求項1記載の方法。
- 酸触媒が、イオン交換樹脂又はヘテロポリ酸を含む酸触媒である請求項5記載の方法。
- 工程(3)において、少なくともモリブデン、ビスマス及び鉄を含む酸化物を酸化触媒として用いる請求項2記載の方法。
- 工程(1)において、イソブタノールとしてバイオマス由来のイソブタノールを用いる請求項1記載の方法。
- イソブタノールからt-ブタノールを製造する装置において、
イソブタノールを脱水してブテン類を得る装置(A)
装置(A)で得たブテン類を水和してt-ブタノールを得る装置(B)
を有することを特徴とするt-ブタノールを製造する装置。 - 請求項9記載の装置により得たt-ブタノールを脱水及び酸化してメタクロレイン及びメタクリル酸を得る装置(C)
を有することを特徴とするメタクロレイン及びメタクリル酸を製造する装置。 - メタノールと、請求項2記載の方法により得たメタクリル酸とからメタクリル酸メチルを合成する方法。
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CN201280054318.7A CN103917508A (zh) | 2011-11-07 | 2012-11-06 | 由异丁醇制造叔丁醇的方法、由异丁醇制造异丁烯醛和甲基丙烯酸的方法以及这些方法的制造装置 |
US14/356,168 US9346735B2 (en) | 2011-11-07 | 2012-11-06 | Method for producing t-butanol from isobutanol, method for producing methacrolein and methacrylic acid from isobutanol, and apparatus for producing them |
JP2012552183A JP6107139B2 (ja) | 2011-11-07 | 2012-11-06 | イソブタノールからメタクロレイン及びメタクリル酸を製造する方法、並びにその製造装置 |
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JP2015182032A (ja) * | 2014-03-25 | 2015-10-22 | Jx日鉱日石エネルギー株式会社 | 脱水触媒、及び共役ジエンの製造方法 |
JP2015182031A (ja) * | 2014-03-25 | 2015-10-22 | Jx日鉱日石エネルギー株式会社 | 脱水触媒、及び共役ジエンの製造方法 |
CN106470963A (zh) * | 2014-07-02 | 2017-03-01 | 三菱丽阳株式会社 | 异丁烯的制造方法、甲基丙烯酸的制造方法和甲基丙烯酸甲酯的制造方法 |
CN115135624A (zh) * | 2020-03-31 | 2022-09-30 | 三菱化学株式会社 | 异丁烯的制造方法、甲基丙烯酸的制造方法和甲基丙烯酸甲酯的制造方法 |
WO2023157870A1 (ja) * | 2022-02-17 | 2023-08-24 | 三菱ケミカル株式会社 | メタクロレイン及び/又はメタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法 |
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CN111004116A (zh) * | 2019-12-19 | 2020-04-14 | 湖北美和科技有限公司 | 一种用于制备结焦抑制剂组份的甲基丙烯酸酯单体 |
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JP2015182032A (ja) * | 2014-03-25 | 2015-10-22 | Jx日鉱日石エネルギー株式会社 | 脱水触媒、及び共役ジエンの製造方法 |
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CN106470963A (zh) * | 2014-07-02 | 2017-03-01 | 三菱丽阳株式会社 | 异丁烯的制造方法、甲基丙烯酸的制造方法和甲基丙烯酸甲酯的制造方法 |
CN106470963B (zh) * | 2014-07-02 | 2020-04-21 | 三菱化学株式会社 | 异丁烯的制造方法、甲基丙烯酸的制造方法和甲基丙烯酸甲酯的制造方法 |
CN115135624A (zh) * | 2020-03-31 | 2022-09-30 | 三菱化学株式会社 | 异丁烯的制造方法、甲基丙烯酸的制造方法和甲基丙烯酸甲酯的制造方法 |
WO2023157870A1 (ja) * | 2022-02-17 | 2023-08-24 | 三菱ケミカル株式会社 | メタクロレイン及び/又はメタクリル酸の製造方法、並びにメタクリル酸エステルの製造方法 |
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US20140357890A1 (en) | 2014-12-04 |
KR20140090650A (ko) | 2014-07-17 |
CN103917508A (zh) | 2014-07-09 |
MY167695A (en) | 2018-09-21 |
KR101979475B1 (ko) | 2019-05-16 |
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