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WO2025041647A1 - Procédé de production d'oléfine et dispositif de réaction pour la production d'oléfine - Google Patents

Procédé de production d'oléfine et dispositif de réaction pour la production d'oléfine Download PDF

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WO2025041647A1
WO2025041647A1 PCT/JP2024/028640 JP2024028640W WO2025041647A1 WO 2025041647 A1 WO2025041647 A1 WO 2025041647A1 JP 2024028640 W JP2024028640 W JP 2024028640W WO 2025041647 A1 WO2025041647 A1 WO 2025041647A1
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alcohol
metal oxide
reaction
sulfuric acid
oxide
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Japanese (ja)
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孝平 山下
滉諒 中村
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Moresco Corp
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Moresco Corp
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • 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 producing olefins and a reaction apparatus for producing olefins.
  • Patent Document 1 JP 2013-203705 A discloses a method for producing an internal olefin having a double bond inside the alkyl chain using a long-chain aliphatic primary alcohol as a raw material.
  • Patent Document 1 discloses the use of a complex oxide containing titanium oxide and silicon oxide and/or zirconium oxide as a catalyst, with the titanium oxide content being 20 to 95 mol %.
  • Patent Document 2 JP Patent Publication 2014-224107A discloses a method for producing olefins, in which two or more types of alcohols with different carbon numbers are used as raw materials to carry out olefination.
  • Patent Document 2 discloses the use of a solid acid catalyst, in which an aluminum oxide carrier supports an acid such as sulfuric acid, as a catalyst. Specifically, it discloses a solid acid catalyst that is a sintered body obtained by impregnating gamma-alumina with water-diluted sulfuric acid and calcining it at 500°C for three hours.
  • Patent document 3 JP Patent Publication 2008-538206 discloses a method for producing olefins from alcohols using trifluoromethanesulfonic acid as a catalyst.
  • the examples in patent document 3 describe an example in which dodecanol, tetradecanol, or other alcohols and trifluoromethanesulfonic acid are introduced into a distillation apparatus and heated at 240°C for several hours.
  • Patent Documents 1 and 2 state that the reaction temperature in the production of olefins from alcohols can be set to approximately 200°C to 300°C. In practice, however, reaction temperatures of 260°C or higher are often used, and reactions carried out at temperatures below this tend to require a long reaction time or a large amount of catalyst. On the other hand, from the perspective of energy consumption, it is preferable to be able to produce olefins at a low temperature in a short time. Therefore, one of the objects of the present invention is to provide a method for producing olefins that can be carried out at a low temperature and in a short time compared to conventional techniques.
  • the method for producing olefins according to the present disclosure involves reacting an alcohol having 6 to 36 carbon atoms in the presence of a metal oxide and sulfuric acid not supported on a metal oxide in a liquid phase at 150°C or higher.
  • the above-mentioned production method provides a method for producing olefins that can be carried out at a lower temperature and in a shorter time than conventional techniques.
  • FIG. 1 is a schematic diagram showing an overview of a reaction apparatus used in the production method according to the present disclosure.
  • the method for producing olefins according to the present disclosure involves reacting an alcohol having 6 to 36 carbon atoms in the presence of a metal oxide and sulfuric acid not supported on a metal oxide in a liquid phase at 150°C or higher.
  • Patent Document 1 proposes a method for efficiently producing internal olefins that have a double bond inside the alkyl chain.
  • Patent Document 2 proposes a method for suppressing olefin polymerization and producing olefins in high yields.
  • Patent Document 3 proposes a method for producing hydrocarbons that can be carried out under mild conditions and causes almost no side reactions.
  • due to demands for energy reduction, etc. there is a need for a method that can efficiently produce olefins from alcohols at a lower temperature and in a shorter time than before.
  • the prior art also states that the conversion reaction from alcohol to olefins can be carried out at temperatures of about 200°C or higher.
  • the reaction is carried out at temperatures of about 235 to 260°C, the reaction occurs but takes a long time, the reaction rate is insufficient, a large amount of catalyst is required, and so on, and satisfactory results are not necessarily obtained.
  • a method was investigated for producing olefins from alcohol in high yields through a reaction at a lower temperature and in a shorter time than before.
  • the mass ratio of the sulfuric acid to the metal oxide may be 3% or more and 23% or less. If the mass ratio is within this range, the effects of the present disclosure can be reliably obtained.
  • the alcohol may be a linear or branched primary or secondary alcohol having 8 to 24 carbon atoms.
  • the effects of the present disclosure are more pronounced.
  • the metal oxide may be one or more selected from the group consisting of oxides of elements selected from Groups 3 to 6 and Groups 12 to 13 of the Periodic Table.
  • the effects of the present disclosure are more pronounced.
  • the metal oxide may be one or more selected from the group consisting of zirconium oxide, titanium oxide, aluminum oxide, silica alumina, tungsten oxide, scandium oxide, yttrium oxide, hafnium oxide, vanadium oxide, and niobium oxide.
  • zirconium oxide titanium oxide, aluminum oxide, silica alumina, tungsten oxide, scandium oxide, yttrium oxide, hafnium oxide, vanadium oxide, and niobium oxide.
  • the ratio of the total mass of the metal oxide and sulfuric acid to the alcohol may be 0.5% or more.
  • the effects of the present disclosure can be clearly obtained while suppressing the cost of the olefin production method.
  • the reaction apparatus is an apparatus for the olefin production method, and includes a reaction tank capable of stirring alcohol, metal oxide, and sulfuric acid while heating them, a collection section for cooling and collecting the olefin produced, and a moisture adsorption section for accommodating a moisture adsorbent between the reaction tank and the collection section.
  • a reaction tank capable of stirring alcohol, metal oxide, and sulfuric acid while heating them
  • a collection section for cooling and collecting the olefin produced
  • a moisture adsorption section for accommodating a moisture adsorbent between the reaction tank and the collection section.
  • the production method disclosed herein is a method for obtaining olefins from alcohols using the above-mentioned reaction apparatus. This production method makes it easier to recover olefins, and can efficiently obtain olefins while reducing energy consumption.
  • the metal oxide examples include oxides of elements in Groups 1 to 14 of the periodic table. Among these, oxides of elements selected from Groups 3 to 6 and Groups 12 to 13 of the periodic table are preferred. More preferably, the metal oxide has a valence of 3 or 4. Examples include zirconium oxide, titanium oxide, calcium oxide, yttrium oxide, aluminum oxide (alumina), silica alumina (silicon oxide/aluminum oxide), zeolite, tungsten oxide, scandium oxide, yttrium oxide, hafnium oxide, vanadium oxide, and niobium oxide.
  • the metal oxide is preferably one or more selected from the group consisting of zirconium oxide, titanium oxide, aluminum oxide, and silica alumina. More preferably, the metal oxide is zirconium oxide.
  • the metal oxide may be a so-called composite metal oxide.
  • a plurality of types of metal oxides may be used in combination.
  • the metal oxide preferably includes zirconium oxide. The content of zirconium oxide relative to the total amount of metal oxides is preferably 50 wt% or more, and more preferably 80 wt% or more.
  • the crystal structure and shape of the metal oxide used in the manufacturing method according to the present disclosure are not particularly limited.
  • the shape of the metal oxide may be a powder or particle, or may be a pellet or tablet-shaped molding.
  • the particle size D50 of the metal oxide is, for example, 0.01 ⁇ m or more and 100 ⁇ m or less, and preferably 0.02 ⁇ m or more and 10 ⁇ m or less.
  • the specific surface area is also not particularly limited, but for example, the BET specific surface area may be 1 m 2 /g or more and 300 m 2 /g or less, and may be 20 m 2 /g or more and 300 m 2 /g or less, and preferably 20 m 2 /g or more and 150 m 2 /g or less.
  • the mass ratio of the metal oxide to the alcohol raw material is not limited as long as the effect of the present disclosure can be obtained, but it should be 0.4% or more relative to the alcohol, preferably 1% or more, and more preferably 2% or more. If it is 0.4% or more, the catalytic effect can be exerted. There is no particular upper limit to the mass ratio of the metal oxide to the alcohol raw material, but adding an excess does not increase the reaction efficiency, so in order to obtain olefins at reasonable cost, it is at most 25% or less, preferably 10% or less, and more preferably 5% or less.
  • Sulfuric acid generally used in industry can be used. Sulfuric acid may be used in an undiluted state, or may be used in a state diluted with, for example, water, methanol, ethanol, propanol, or other alcohol having 5 or less carbon atoms, or fuming sulfuric acid may be used.
  • the mass ratio of sulfuric acid to the alcohol raw material is not limited as long as the effect of the present disclosure can be obtained, but it is sufficient if it is 0.05% or more relative to the alcohol, preferably 0.1% or more, more preferably 0.14% or more, and even more preferably 0.2% or more.
  • the mass ratio of sulfuric acid to metal oxide is not limited as long as the effects of the present disclosure are obtained, but is preferably 3% or more, more preferably 4% or more, and even more preferably 10% or more.
  • the mass ratio of sulfuric acid to metal oxide is preferably 23% or less, more preferably 20% or less, and even more preferably 15% or less. If the ratio of sulfuric acid to metal oxide is 3% or more and 23% or less, olefins can be produced efficiently.
  • the mass ratio of the catalyst (total amount of metal oxide and sulfuric acid) to the raw material alcohol is not limited as long as the effect of the present disclosure can be obtained, but is 0.5% or more, and preferably 1% or more. There is no particular upper limit to the mass ratio of the catalyst to the alcohol, but from the viewpoint of reasonable cost, it is 26% or less, and preferably 6% or less.
  • the mass ratio of the catalyst added to the alcohol may be referred to as the catalyst amount (%).
  • a metal oxide and sulfuric acid are used as catalysts, but the sulfuric acid is present in a state not supported by the metal oxide.
  • a state in which sulfuric acid is supported by a metal oxide is a so-called solid acid catalyst.
  • a solid acid catalyst means a complex in which a metal oxide supports sulfuric acid.
  • a solid acid catalyst is generally a complex obtained by baking a metal oxide impregnated with an acid, so that the metal oxide and the acid are added together.
  • the ratio of sulfuric acid to the metal oxide is easier to adjust to an appropriate range when sulfuric acid is in a liquid state, and the catalytic activity is high, it is preferable to add the metal oxide and the liquid sulfuric acid separately.
  • the metal oxide may be a metal oxide supporting an acid (solid acid catalyst), or a combination of a metal oxide and a solid acid catalyst may be used.
  • the reaction is carried out in the presence of a metal oxide and sulfuric acid not supported by a metal oxide.
  • the sulfuric acid and the metal oxide may be used as materials to be added separately.
  • “added separately” does not necessarily mean that the metal oxide and sulfuric acid are added separately when the catalyst is added to the reaction tank, but also includes cases where the sulfuric acid and metal oxide are mixed together in advance and added to the reaction tank, or where the solid acid catalyst as the metal oxide and sulfuric acid are added to the reaction tank.
  • the alcohol used in the production method according to the present disclosure is an alcohol having 6 to 36 carbon atoms, and is not limited as long as the effects according to the present disclosure can be obtained, but is typically a linear or branched primary or secondary alcohol having 8 to 30 or 8 to 24 carbon atoms.
  • the alcohol is preferably a monohydric alcohol.
  • the alcohol may also contain a cyclic hydrocarbon group such as a saturated alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • alcohols include 1-hexanol, 1-octanol, 2-octanol, 2-methylheptanol, 6-methylheptanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 2-decyltetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 1-tricosanol, 1-tetracosanol, 2-cyclohexylethanol, and 2-phenylethanol.
  • 1-hexanol, 1-octanol, 2-octanol, 1-decanol, 2-decanol, 1-dodecanol, 1-tetradecanol, 1-octadecanol, and 2-decyltetradecanol which are alcohols not containing a cyclic hydrocarbon group, is preferred because the effect of efficiently obtaining olefins at low temperatures in a short period of time is particularly clear. Only one type of alcohol may be used as the raw material, or two or more types may be used in combination.
  • the alcohol used in the manufacturing method of the present disclosure has a boiling point of 150°C or higher and 450°C or lower.
  • the reaction is carried out with the alcohol in a liquid phase.
  • alcohol with a boiling point of 150°C or higher and 450°C or lower is used as a raw material, it is easy to maintain the alcohol in a liquid state in the reaction system, and the reaction can be carried out at normal or reduced pressure.
  • the alcohol used in the manufacturing method of the present disclosure has a melting point of 150°C or lower.
  • a solvent may not be used.
  • a solvent particularly an organic solvent, may be used as necessary.
  • the organic solvent is not particularly limited as long as it is liquid at the reaction temperature and does not inhibit the reaction.
  • a hydrocarbon-based organic solvent such as a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, or an aromatic hydrocarbon may be used as the organic solvent.
  • an organic solvent it is preferable that the organic solvent can be separated from the product after the reaction, for example, by using the boiling point difference.
  • Saturated aliphatic hydrocarbons include, for example, compounds having 10 to 35 carbon atoms, such as tridecane, hexadecane, octadecane, eicosane, docosane, triacontane, and squalane.
  • mixtures of liquid paraffin, naphthenic hydrocarbons, and isoparaffinic hydrocarbons may also be used as saturated aliphatic hydrocarbons.
  • Examples of unsaturated aliphatic hydrocarbons include eicosene, henicosene, docosene, tricosene, and squalene.
  • the unsaturated aliphatic hydrocarbons may be a mixture.
  • Examples of aromatic hydrocarbons include alkylbenzenes and alkylnaphthalenes such as n-dodecylbenzene, n-tridecylbenzene, n-tetradecylbenzene, n-pentadecylbenzene, n-hexadecylbenzene, and diisopropylnaphthalene.
  • the production method according to the present disclosure is a method for producing an olefin, which comprises reacting an alcohol having 6 to 36 carbon atoms in a liquid phase state at 150° C. or higher in the presence of a metal oxide and sulfuric acid not supported on a metal oxide, and specifically includes, for example, a first step of preparing an alcohol having 6 to 36 carbon atoms, a metal oxide, and sulfuric acid not supported on a metal oxide, and a second step of charging the alcohol, the metal oxide prepared in the first step, and sulfuric acid into a reaction tank and holding the alcohol in the presence of the metal oxide and sulfuric acid not supported on a metal oxide at 150° C. or higher and under conditions in which the alcohol is in a liquid state.
  • the first step is a preparation step.
  • an alcohol as a raw material, a metal oxide as a catalyst, and sulfuric acid not supported on a metal oxide are prepared.
  • the manufacturing method according to the present disclosure may also use an organic solvent, a dehydrating agent, water, etc., as necessary.
  • the second step is a reaction step for olefination.
  • the reaction is carried out in the liquid phase in the presence of a metal oxide and sulfuric acid not supported on the metal oxide.
  • An alcohol, a metal oxide, and sulfuric acid are charged into a reaction vessel.
  • the metal oxide and sulfuric acid may be charged separately, or may be charged as a premix.
  • the metal oxide may be charged in the form of a solid acid catalyst. The temperature is then raised to a predetermined temperature, and the reaction is carried out.
  • the reaction temperature can be below the boiling point of the raw alcohol.
  • the reaction can be carried out under pressure to maintain the raw alcohol in a liquid state.
  • the specific reaction temperature can be selected depending on the type of raw alcohol, but may be 150°C or higher, preferably 170°C or higher, and more preferably 200°C or higher. From the viewpoint of energy efficiency and equipment load, the reaction temperature may be 300°C or lower, preferably 270°C or lower, and more preferably 240°C or lower. From the viewpoint of energy saving, a lower reaction temperature is preferable, but a reaction temperature in the range of 210°C to 250°C is suitable because it has high reaction efficiency. In the production method disclosed herein, by using the above-mentioned catalyst, olefins can be obtained in a short time even at about 230°C.
  • the pressure during the reaction may be normal pressure, or may be reduced or increased pressure as necessary.
  • the pressure may be, for example, 0.001 MPa or more and 0.09 MPa or less.
  • the pressure may also be changed during the second step. It is also preferable to distill and separate the product olefin from the raw material alcohol by controlling the pressure.
  • the inside of the reaction apparatus may be an inert gas atmosphere.
  • the inert gas that can be used include nitrogen gas, argon gas, etc.
  • the reaction time can be selected depending on the reaction temperature, the type of catalyst, the amount used, etc., but is, for example, from 0.5 hours to 10 hours, preferably from 1 hour to 7 hours, and more preferably from 2 hours to 5 hours. According to the production method disclosed herein, it has been confirmed that olefination proceeds even in a reaction time of 2.5 hours at a temperature of about 230°C.
  • the alcohol conversion rate is 25% or more, preferably 30% or more, more preferably 60% or more, and even more preferably 90% or more.
  • the alcohol conversion rate (%) is 100 - (the ratio of the amount of alcohol present in the liquid after the reaction).
  • the ratio of olefins present is 5% or more, preferably 15% or more, more preferably 30% or more, even more preferably 50% or more, and most preferably 75% or more.
  • the olefins obtained by the manufacturing method disclosed herein typically contain 1-15% alpha olefins and 85-99% internal olefins.
  • the olefins also contain 1-15% branched olefins. Because the olefins obtained by the manufacturing method of the present invention contain a large amount of internal olefins, the obtained olefins can be suitably used as raw materials or intermediate raw materials for lubricants, surfactants, etc.
  • the reaction it is preferable to carry out the reaction while separating the olefin from the alcohol, taking advantage of the difference in boiling points between the alcohol and the olefin produced from the alcohol.
  • Distillation can be used as a method of separation.
  • a moisture adsorbent can be used to adsorb the water.
  • FIG. 1 shows an example of a reaction apparatus used in the production method according to the present disclosure.
  • the reaction apparatus has a distillation column at the top of the reaction vessel.
  • the reaction vessel 1 is charged with alcohol as a raw material, metal oxide as a catalyst, and sulfuric acid not supported on the metal oxide.
  • the reaction vessel 1 is equipped with a stirrer 10.
  • a thermometer 11 is inserted into the reaction vessel 1, and the temperature inside the reaction vessel can be detected.
  • the reaction vessel 1 is heated using a heating device (not shown).
  • a tube portion 2 is provided as a moisture adsorption portion that accommodates a moisture adsorbent 6.
  • the tube portion 2 has a side pipe 12.
  • the moisture adsorbent 6 for example, a known moisture adsorbent such as molecular sieve (crystalline zeolite) can be used.
  • the water generated in the reaction vessel 1 due to the dehydration reaction which is the conversion of alcohol to olefin, becomes water vapor and diffuses upward from the reaction vessel 1 because the temperature inside the reaction vessel 1 is equal to or higher than the boiling point of water.
  • the water vapor is cooled in the cooling section 3 and the cooling section 9, turns into water, and flows back to the tube section 2, where it is adsorbed by the moisture adsorbent 6. In this manner, moisture is separated from within the reaction vessel 1.
  • Cooling section 3 and cooling section 9 are provided at the top of tube section 2. In the example of FIG. 1, two stages of cooling section 3 and cooling section 9 are provided, but a single cooling section or multiple stages of cooling sections may be provided as necessary.
  • Cooling section 4 branches off between cooling section 3 and cooling section 9.
  • Collection vessel 5 is provided at the end of cooling section 4.
  • Pump 13 is provided between cooling section 4 and collection vessel 5 via branch pipe 8. Using pump 13, the pressure inside the reaction system can be increased or decreased as necessary.
  • the olefins produced in the reaction have a lower boiling point than the raw material alcohol. This difference in boiling point can be used to recover the olefins by distillation. Specifically, the gaseous olefins can be cooled in the cooling section 4, and the olefins can be collected as a liquid in the collection vessel 5. The cooling section 4 and the collection vessel 5 make up the olefin collection section.
  • the reactor shown in Figure 1 allows the olefins produced to be separated by distillation while the water produced during the dehydration of alcohol is quickly removed from the reactor, preventing water from refluxing into the reactor. This makes it possible to recover olefins with high purity, makes temperature control easier, and reduces the energy consumption required for the reaction.
  • a reactor may also be used in which a tubular vessel is filled with metal oxide, and alcohol to which sulfuric acid has been added is caused to flow through the tubular vessel filled with metal oxide to react the alcohol, and then the olefins are recovered by distillation. From the standpoint of energy efficiency and reaction efficiency, it is preferable to use a reactor having a distillation column above the reaction vessel.
  • Vaporization chamber temperature 350°C
  • Injection method total injection method
  • Carrier gas nitrogen (column flow rate: 1.48 mL/min)
  • Temperature conditions 50°C to 350°C, heated at 12.5°C/min, and then held at 350°C for 15 minutes. Based on the areas of the peaks indicating olefins, the peaks indicating alcohols, and the peaks indicating polymers and ethers, which are by-products, in the obtained GC chart, the abundance ratios of olefins and alcohols and the conversion rate of alcohols were calculated.
  • the peaks in the obtained GC chart were compared with the GC peaks of dithiolated olefins of known structure to identify the position of the double bond in the olefins obtained by the production method of the present invention.
  • the abundance ratio of each olefin produced was calculated based on the respective peak areas. The measurements were performed under the same conditions as in (i) and (ii).
  • Example 1 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 6 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.3 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230° C. for 2.5 hours under a nitrogen atmosphere.
  • Example 2 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 6 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.43 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230° C. for 0.5 hours under a nitrogen atmosphere. The components cooled in the cooling section 3 were refluxed.
  • Example 3 The reaction and evaluation were carried out in the same manner as in Example 2, except that the amount of sulfuric acid was changed to 0.53 g. 159 g of a colorless transparent liquid was recovered by distillation, and 43.81 g of a liquid remained in the flask was obtained. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 2. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 4 The reaction and evaluation were carried out in the same manner as in Example 2, except that the amount of sulfuric acid was changed to 0.6 g. 166 g of a colorless transparent liquid was recovered by distillation, and 44 g of a liquid remained in the flask was obtained. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 2. The production of a monoolefin having a carbon number of 12 was confirmed by GC. The produced olefin was reacted with dimethyl disulfide, and the produced olefin was identified by GC.
  • the olefins produced were 2.1% 1-dodecene, 12.9% trans-2-dodecene, 6.6% cis-2-dodecene, 13.8% trans-3-dodecene, 4.7% cis-3-dodecene, 15.6% trans-4-dodecene, 26.9% cis-4-dodecene and trans-5-dodecene, 7.2% cis-5-dodecene and 6-dodecene, and 10.2% branch-dodecene.
  • Example 5 The reaction and evaluation were carried out in the same manner as in Example 2, except that the amount of sulfuric acid was changed to 1.2 g. 113 g of a colorless transparent liquid was recovered by distillation, and 104 g of a liquid remained in the flask was obtained. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 2. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 2 The same composition as in Example 4 was used except that zirconium oxide was not added, and the mixture was stirred for 2.5 hours at 230° C. Water was supplied to the cooling section 3, but there was no reflux and distillation was not possible, so 294 g of liquid was recovered from the flask and the component ratios in the recovered product and the conversion rate of alcohol were evaluated by GC measurement.
  • Examples 1 to 5 zirconium oxide and sulfuric acid were used as catalysts, and olefins were obtained at a reaction temperature of 230°C for a reaction time of 2.5 hours.
  • examples 2 to 5 in which the mass ratio of sulfuric acid to the metal oxide was 6% or more and 20% or less, olefins were obtained in high yields.
  • Comparative Example 1 in which only zirconium oxide was used as the catalyst, the reaction did not proceed even when heated for 5 hours at 250°C, a reaction temperature higher than Examples 1 to 5.
  • Comparative Example 2 in which only sulfuric acid was used as the catalyst, some conversion of alcohol occurred at 230°C, but no olefins were produced and only by-products were obtained.
  • Example 6 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 3 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.6 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230° C. for 2.5 hours under a nitrogen atmosphere.
  • Example 7 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 4.5 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.63 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230 ° C. for 1 hour under a nitrogen atmosphere. The components cooled by the cooling section 3 were refluxed.
  • Example 8 The reaction and evaluation were carried out in the same manner as in Example 7, except that the amount of zirconium oxide was changed to 5.24 g. 184 g of a colorless transparent liquid was recovered by distillation, and 46 g of a liquid remained in the flask. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 7. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 9 The reaction and evaluation were carried out in the same manner as in Example 7, except that the amount of zirconium oxide was changed to 12 g. 115 g of a colorless transparent liquid was recovered by distillation, and 115.5 g of a liquid remained in the flask was obtained. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 7. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 10 The reaction and evaluation were carried out in the same manner as in Example 7, except that the amount of zirconium oxide was changed to 15 g. 94 g of a colorless transparent liquid was recovered by distillation, and 124 g of a liquid remained in the flask. The component ratios relative to the total recovered material and the alcohol conversion rate were calculated in the same manner as in Example 7. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 11 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 3 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.3 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230° C. for 2.5 hours under a nitrogen atmosphere. The components cooled by the cooling section 3 were refluxed.
  • reaction solution could not be distilled even when the supply of water to the cooling section 3 was stopped, so 276 g of liquid in the flask was recovered, and the component ratio in the recovered material and the conversion rate of alcohol were evaluated by GC.
  • the production of monoolefin with 12 carbon atoms was confirmed by GC.
  • Example 12 The reaction and evaluation were carried out in the same manner as in Example 2, except that the amount of zirconium oxide was changed to 9 g and the amount of sulfuric acid was changed to 0.9 g. 160 g of a colorless and transparent liquid was recovered by distillation, and 54.5 g of a liquid remained in the flask was obtained. The product recovered by distillation and the remaining liquid were each measured by GC, and the component ratio relative to the total recovered material and the conversion rate of alcohol were calculated by the above formula. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 13 498 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 10 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 1 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 1000 mL four-neck flask and stirred at 210° C. for 2.5 hours under a nitrogen atmosphere. The components cooled by the cooling section 3 were refluxed.
  • the reaction solution could not be distilled even when the supply of water to the cooling section 3 was stopped, so 460 g of the liquid in the flask was recovered, and the component ratio in the recovered material and the conversion rate of alcohol were evaluated by GC.
  • the production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 11 zirconium oxide and sulfuric acid were used as catalysts, and olefins were obtained at a reaction temperature of 230°C and a reaction time of 2.5 hours.
  • Example 13 zirconium oxide and sulfuric acid were used as catalysts, and olefins were obtained at a reaction temperature of 210°C and a reaction time of 2.5 hours.
  • Example 14 The reaction was carried out using the apparatus outlined in FIG. 1. 300 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 6 g of ⁇ -alumina (STREM CHEMICALS, INC.), and 0.6 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230° C. for 2.5 hours under a nitrogen atmosphere.
  • 1-dodecanol Kao Corporation, Kalcol (registered trademark) 2098
  • 6 g of ⁇ -alumina STREM CHEMICALS, INC.
  • sulfuric acid FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent
  • Example 3 Except for not adding sulfuric acid, the reaction was carried out and evaluated under the same conditions as in Example 14. As in Example 14, the reaction solution could not be refluxed or distilled, so 299 g of a cloudy white liquid in the flask was recovered, and the component ratios in the recovered product and the conversion rate of the alcohol were evaluated by GC.
  • Example 15 The reaction was carried out under the same conditions as in Example 14, except that ⁇ -alumina was replaced with titanium oxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and evaluation was performed. As in Example 14, the reaction solution could not be refluxed or distilled, so 291.5 g of a brown, turbid liquid in the flask was recovered, and the component ratios in the recovered material and the alcohol conversion rate were evaluated by GC. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 4 Except for not adding sulfuric acid, the reaction was carried out and evaluated under the same conditions as in Example 15. As in Example 14, the reaction solution could not be refluxed or distilled, so 300 g of a gray turbid liquid in the flask was recovered, and the component ratios in the recovered product and the conversion rate of the alcohol were evaluated by GC.
  • Example 16 The reaction was carried out and evaluated under the same conditions as in Example 14, except that ⁇ -alumina was changed to silica alumina (Neobead SA, manufactured by Mizusawa Industrial Chemicals, Ltd.). As in Example 14, the reaction solution could not be refluxed or distilled, so 297 g of a turbid brown liquid in the flask was recovered, and the component ratios in the recovered product and the alcohol conversion rate were evaluated by GC. The production of a monoolefin having a carbon number of 12 was confirmed by GC.
  • Example 5 Except for not adding sulfuric acid, the reaction was carried out and evaluated under the same conditions as in Example 16. As in Example 16, the reaction solution could not be refluxed or distilled, so 295 g of a cloudy white liquid in the flask was recovered, and the component ratios in the recovered product and the conversion rate of the alcohol were evaluated by GC.
  • Comparative Example 7 in which a solid acid catalyst of zirconium oxide supporting sulfuric acid was used, the conversion of alcohol occurred after a reaction for 5 hours at 250°C, which is a higher reaction temperature than in the Examples, but only a small amount of olefin was produced. This is thought to be because the sulfuric acid supported on zirconium oxide had lower catalytic activity than sulfuric acid in a liquid state. Comparative Example 6 showed that sulfuric acid is a good acid to combine with a metal oxide as a catalyst. Comparative Example 7 showed that the use of a metal oxide and liquid sulfuric acid is more effective in producing olefins than the use of sulfuric acid supported on a metal oxide.
  • Example 17 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 1-octanol (Kao Corporation, Kalcol (registered trademark) 0898), 6 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd. RC-100), and 0.6 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 200° C. for 1 hour under a nitrogen atmosphere. The components cooled in the cooling section 3 were refluxed. Thereafter, the supply of water to the cooling section 3 was stopped, and the product was recovered by distillation by stirring for 2 hours.
  • 1-octanol Kao Corporation, Kalcol (registered trademark) 0898
  • 6 g of zirconium oxide Diaiichi Kigenso Kagaku Kogyo Co., Ltd. RC-100
  • sulfuric acid FEZIFIL
  • the produced olefins were 10.8% 1-octene, 26.9% trans-2-octene, 18.8% cis-2-octene, 19.0% trans-3-octene, 16.2% cis-3-octene, 3.8% 4-octene, and 4.5% branch-octene.
  • Example 18 The reaction was carried out using the apparatus shown in FIG. 1. 158 g of 2-octanol (manufactured by Kokura Synthetic Industries Co., Ltd.), 3.2 g of zirconium oxide (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 0.3 g of sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd., special grade reagent) were added to a 200 mL four-neck flask and stirred at 170 ° C. for 2 hours under a nitrogen atmosphere. The components cooled in the cooling section 3 were refluxed.
  • 2-octanol manufactured by Kokura Synthetic Industries Co., Ltd.
  • zirconium oxide manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100
  • sulfuric acid manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd., special grade rea
  • the produced olefin was reacted with dimethyl disulfide, and the produced olefin was identified by GC.
  • the produced olefins were 9.0% 1-octene, 25.1% trans-2-octene, 55.2% cis-2-octene, 4.6% trans-3-octene, 3.8% cis-3-octene, 0.8% 4-octene, and 1.5% branch-octene.
  • Example 19 The reaction was carried out using the apparatus shown in FIG. 1. 3040 g of 1-dodecanol (Kao Corporation, Kalcol (registered trademark) 2098), 61 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., RC-100), and 6 g of sulfuric acid (FUJIFILM Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 5000 mL four-neck flask and stirred at 230° C. for 1.5 hours under a nitrogen atmosphere. The components cooled in the cooling section 3 were refluxed.
  • Example 20 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of octadecanol (Kao Corporation, Kalcol (registered trademark) 8098), 6 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd. RC-100), and 0.6 g of sulfuric acid (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) were added to a 500 mL four-neck flask and stirred at 230 ° C. and 90 kPa for 1 hour. Thereafter, the supply of water to the cooling section 3 was stopped, the pressure was further reduced to 1 kPa, and the mixture was stirred at 230 ° C.
  • octadecanol Kao Corporation, Kalcol (registered trademark) 8098
  • 6 g of zirconium oxide Diaiichi Kigenso Kagaku Kogyo Co., Ltd. RC-100
  • sulfuric acid
  • Example 21 The reaction was carried out using the apparatus shown in FIG. 1. 300 g of 2-decyltetradecanol (NJC, NJCOL (registered trademark) 240A, manufactured by New Japan Chemical Co., Ltd.), 6 g of zirconium oxide (RC-100, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.), and 0.6 g of sulfuric acid (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to a 500 mL four-neck flask and stirred at 230 ° C. for 1 hour under a nitrogen atmosphere. The pressure was then reduced to 1 kPa and the mixture was stirred for 4.5 hours.
  • NJC 2-decyltetradecanol
  • NJCOL registered trademark
  • RC-100 zirconium oxide
  • sulfuric acid special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.
  • the catalyst configurations, reaction conditions, and analysis results of the recovered products after the reactions in Examples 17 to 21 are summarized in Table 5.
  • the catalyst amount (%) indicates the mass ratio of the catalyst to the raw material alcohol (the total mass ratio of the metal oxide and sulfuric acid).
  • Examples 17 to 21 a primary or secondary alcohol having 8 to 24 carbon atoms was used as the raw material alcohol.
  • zirconium oxide and sulfuric acid were used as catalysts, and the reaction was carried out at a temperature of 230°C or less, producing olefins in high yields.

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Abstract

L'invention concerne un procédé de production d'oléfine qui comprend la réaction d'un alcool à 150°C ou plus, dans un état en phase liquide, et en présence d'un oxyde métallique et d'acide sulfurique qui n'est pas supporté sur l'oxyde métallique, l'alcool ayant de 6 à 36 atomes de carbone. Le rapport de la masse de l'acide sulfurique à la masse de l'oxyde métallique est de préférence de 3 à 23%. Le procédé de production peut être mis en œuvre à l'aide d'un dispositif comprenant : un réservoir de réaction dans lequel l'alcool, l'oxyde métallique et l'acide sulfurique peuvent être agités pendant le chauffage ; et une unité de collecte qui refroidit et collecte l'oléfine générée, le dispositif comprenant également, entre le réservoir de réaction et l'unité de collecte, une section d'adsorption d'humidité qui reçoit un adsorbant d'humidité.
PCT/JP2024/028640 2023-08-24 2024-08-09 Procédé de production d'oléfine et dispositif de réaction pour la production d'oléfine Pending WO2025041647A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110098519A1 (en) * 2007-08-13 2011-04-28 Kanaparthi Ramesh Modified catalyst composition for conversion of alcohol to alkene
WO2011052732A1 (fr) * 2009-10-30 2011-05-05 花王株式会社 Procédé de fabrication d'oléfines
JP2013535484A (ja) * 2010-12-01 2013-09-12 エルジー・ケム・リミテッド αメチルスチレンの製造方法
JP2013203705A (ja) * 2012-03-28 2013-10-07 Kao Corp オレフィンの製造方法
JP2014224107A (ja) * 2013-04-23 2014-12-04 花王株式会社 オレフィンの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110098519A1 (en) * 2007-08-13 2011-04-28 Kanaparthi Ramesh Modified catalyst composition for conversion of alcohol to alkene
WO2011052732A1 (fr) * 2009-10-30 2011-05-05 花王株式会社 Procédé de fabrication d'oléfines
JP2013535484A (ja) * 2010-12-01 2013-09-12 エルジー・ケム・リミテッド αメチルスチレンの製造方法
JP2013203705A (ja) * 2012-03-28 2013-10-07 Kao Corp オレフィンの製造方法
JP2014224107A (ja) * 2013-04-23 2014-12-04 花王株式会社 オレフィンの製造方法

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