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WO2016111203A1 - Procédé de production de 1,3-butadiène - Google Patents

Procédé de production de 1,3-butadiène Download PDF

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Publication number
WO2016111203A1
WO2016111203A1 PCT/JP2015/086235 JP2015086235W WO2016111203A1 WO 2016111203 A1 WO2016111203 A1 WO 2016111203A1 JP 2015086235 W JP2015086235 W JP 2015086235W WO 2016111203 A1 WO2016111203 A1 WO 2016111203A1
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WIPO (PCT)
Prior art keywords
ethanol
stage
acetaldehyde
butadiene
supplied
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Ceased
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PCT/JP2015/086235
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English (en)
Japanese (ja)
Inventor
海野　洋
広樹 松山
千津 稲木
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JGC Corp
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JGC Corp
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    • 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
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene

Definitions

  • It relates to a method for producing 1,3-butadiene from ethanol.
  • Butadiene production from ethanol is an industrially proven technology in the past, but lost its competitiveness with the completion of butadiene extractive distillation technology for C4 fraction obtained from naphtha crackers.
  • ETB ethanol
  • C4 fraction obtained from naphtha crackers C4 fraction obtained from naphtha crackers.
  • An object of the present invention is to provide a production method for improving 1,3-butadiene selectivity.
  • ethanol was dehydrogenated in the first stage to synthesize acetaldehyde, and then in the second stage, 1,3- When synthesizing butadiene, A method for producing 1,3-butadiene, characterized in that, in the total amount of ethanol and acetaldehyde supplied to the second-stage reactor, the ethanol supply ratio is in the range of 60 to 90 mol%.
  • [5] Either [1] or [2], wherein the ethanol raw material is supplied to the first and second stage reactors, and the separated ethanol is supplied to the first stage reactor.
  • [6] Either [1] or [2], wherein the ethanol raw material is supplied to the first and second stage reactors, and the separated ethanol is supplied to the second stage reactor.
  • [7] The method for producing 1,3-butadiene according to any one of [2] to [6], wherein the content of acetaldehyde in ethanol to be recycled is 10 mol% or less.
  • [8] The 1,3-butadiene according to any one of [1] to [7], wherein no component separation is performed between the first-stage and second-stage reactors in the process described above. Production method.
  • the supply of recycled acetaldehyde to the second-stage reactor avoids the suppression of the conversion rate of the first-stage reactor, and ethanol and acetaldehyde to be supplied to the second-stage reactor.
  • the yield of 1,3-butadiene can be improved.
  • ethanol and acetaldehyde which are the raw materials, are separated when recycled, and ethanol is supplied to the first stage reactor and acetaldehyde is supplied to the second stage reactor. It is also possible to optimize the ratio of ethanol and acetaldehyde supplied to the second-stage reactor.
  • the construction cost is reduced by not separating the components between the reactors. It is also possible to reduce the manufacturing cost.
  • FIG. 1 is an explanatory diagram showing the flow of the method for producing 1,3-butadiene according to the present invention.
  • the 1,3-butadiene production apparatus 10 of this embodiment includes a first-stage reactor 11, a second-stage reactor 12, and a separation and purification apparatus 13.
  • the mixture of ethanol and acetaldehyde is sent to the second stage reactor 12 to synthesize 1,3-butadiene from ethanol and acetaldehyde.
  • Separation and purification unit 13 separates and purifies the reactor outlet gas containing 1,3-butadiene obtained in the second-stage reactor 12 and purifies the C4 fraction, light gas, heavy component, water, ethanol, acetaldehyde, etc. Isolate. Of these, unreacted ethanol and acetaldehyde are preferably recycled separately, and ethanol is sent to the first-stage reactor 11 or the second-stage reactor 12, and acetaldehyde is sent to the second-stage reactor 12.
  • First stage reactor 11 In the first stage reactor, a reaction represented by the following formula is performed, and acetaldehyde is synthesized from ethanol.
  • the ethanol raw material is not particularly limited, and examples thereof include biomass-derived ethanol such as sugar cane and corn, petroleum or natural gas, and coal-derived ethanol. In addition, if ethanol derived from biomass is used, it can contribute to greenhouse gas reduction.
  • a known copper catalyst or silver catalyst disclosed in JP-A-2005-342675, JP-A-2011-532, or the like is used.
  • Cu-based materials, metals of group 8 of the periodic table of elements such as Ni, Pd, and Pt can be suitably used, and those containing Cu are more preferable.
  • Cu alone or a material containing a two-component metal obtained by adding a transition metal element such as Cr, Co, Ni, Fe, or Mn to this can be used, and a material containing Cu and Ni is preferably used.
  • those containing a metal having three or more components are also preferably used.
  • those in which these are further supported on silicon dioxide, aluminum oxide, titanium oxide, zeolite or the like can be used.
  • CuO, ZnO, CuO / ZnO, etc. can also be used as a catalyst.
  • the reaction conditions are not particularly limited, and the reaction is usually carried out in the range of about 200 to 300 ° C. under the conditions of 0.1 to 1.0 MPa.
  • Examples of the method for bringing the raw material into contact with the catalyst include a suspension bed system, a fluidized bed system, and a fixed bed system. Further, the present invention may be either a gas phase method or a liquid phase method, but it is preferable to use the gas phase method.
  • the raw material gas for example, ethanol gas
  • the raw material gas is diluted. It may be supplied to the reactor without being diluted, or may be appropriately diluted with an inert gas such as nitrogen or water vapor and supplied to the reactor.
  • the ethanol raw material can be supplied to one or both of the first stage reactor and the second stage reactor.
  • the unreacted ethanol recovered in the first stage reactor is supplied, an embodiment in which the ethanol raw material is not supplied to the first stage reactor is also possible.
  • ethanol recovered from the reactor outlet gas containing 1,3-butadiene obtained in the second stage reactor 12 it is preferable to supply ethanol recovered from the reactor outlet gas containing 1,3-butadiene obtained in the second stage reactor 12 to the first stage reactor. You may supply.
  • the first-stage reactor a part of ethanol is converted to acetaldehyde, and this reaction has an equilibrium conversion rate. Therefore, when supplying the unreacted ethanol collected in the first stage, the conversion efficiency to acetaldehyde can be increased by separating the contained acetaldehyde and supplying only ethanol.
  • the content of acetaldehyde in the ethanol to be recycled is preferably 10 mol% or less from the viewpoint of ethanol conversion.
  • Second stage reactor 12 In the second-stage reactor, a reaction represented by the following formula is performed from a mixture of acetaldehyde and ethanol synthesized in the first-stage reactor to synthesize 1,3-butadiene.
  • the ratio of ethanol is 60 to 90 mol%, more preferably 70 to 80 mol%, out of the total of ethanol and acetaldehyde (total when added) supplied to the second stage reactor.
  • the amount of acetaldehyde necessary for the second-stage reaction can be secured, and the synthesis efficiency of 1,3-butadiene can be increased.
  • an ethanol raw material may be added to the second-stage reactor. In this way, it is possible to optimize the ethanol: acetaldehyde mol ratio supplied to the second-stage reactor.
  • the second stage reactor for example, ZrO 2 / SiO 2 , HfO 2 / SiO 2 , Ta 2 O 5 disclosed in Non-Patent Document Industrial and Engineering Chemistry, vol. 42, p.359-372 (1950), etc. / SiO 2 , MgO-SiO 2 disclosed in Non-Patent Document Bulletin of the Chemical Society of Japan, vol. 45, p.655-659 (1972), Non-patent Document Industrial and Engineering Chemistry Process Design and Development, ZnO—Al 2 O 3 and the like disclosed in vol.2, p.45-51 (1963) are used as the catalyst, but the type of the catalyst is not particularly limited.
  • the shape of the catalyst is not particularly limited, and it can be used even if it is granular, columnar, cylindrical or honeycomb.
  • the same method as the first-stage reactor can be adopted, and examples thereof include a suspension bed method, a fluidized bed method, and a fixed bed method.
  • the present invention may be either a gas phase method or a liquid phase method, but it is preferable to use a gas phase method.
  • the raw material gas for example, ethanol gas, preferably a mixture of ethanol gas and acetaldehyde gas
  • the solution may be appropriately diluted by the above and supplied to the reactor.
  • the contact time between the raw material and the catalyst can be controlled by adjusting the feed rate of the raw material, and the weight space velocity (WHSV) is 1.0 to 40 g-(EtOH + AcH ) as the total value of the raw material ethanol and the raw material acetaldehyde. ) ⁇ G ⁇ cat ⁇ 1 ⁇ h ⁇ 1 , preferably 1.0 to 5.0 g ⁇ (EtOH + AcH) ⁇ g ⁇ cat ⁇ 1 ⁇ h ⁇ 1 . If WHSV is too low, the 1,3-butadiene selectivity decreases. On the other hand, if WHSV is too high, the butadiene yield decreases.
  • WHSV weight space velocity
  • the reaction temperature is, for example, about 300 to 400 ° C., preferably 330 to 360 ° C.
  • the reaction pressure can be appropriately set within a wide range from normal pressure to high pressure. From the viewpoint of production efficiency and apparatus configuration, it is preferable to set the pressure to 0.1 to 1.0 MPa.
  • Separation and purification unit 13 After completion of the reaction, the reaction product is sent to the separation / purification device 13, for example, by a separation means such as distillation, extraction, absorption, etc., or a separation means that combines these, light gas, C4 fraction, heavy fraction, water, It can be separated into ethanol, acetaldehyde and the like.
  • FIG. 2 is an explanatory diagram showing an ethanol supply mode in the flow of the method for producing 1,3-butadiene of the present invention.
  • Various side reaction products are generated depending on the catalyst used in the first stage reactor 11 and the reaction conditions.
  • Various side reaction products are generated depending on the catalyst used in the second-stage reactor 12 and the reaction conditions.
  • the accompanying side reaction product is converted into acetaldehyde or ethanol in the first-stage reactor 11, as shown in FIG. 2 (a)
  • the ethanol raw material is supplied in the first-stage and second-stage reactions. It is preferable to supply the ethanol separated and separated to the first-stage reactor 11.
  • the accompanying side reaction product contributes to the decrease in the catalytic activity of the first-stage reactor 11, as shown in FIG.
  • the separated ethanol is preferably supplied to the second-stage reactor 12.
  • the ethanol: acetaldehyde molar (EtOH: AcH) ratio is 1: 9, 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, 8:
  • Example 2 Ethanol / acetaldehyde ratio supplied to the second stage reactor Of the total ethanol and acetaldehyde supplied to the second stage reactor, ZrO 2 / SiO 2 (1.0 wt% ) 0.63 g of catalyst was charged into a fixed bed flow type reactor, and an experiment was conducted under the following reaction conditions.
  • the 1,3-butadiene selectivity was high when the ethanol supply ratio was in the range of 60 to 90 mol%. Further, higher results were obtained in the range of 70 to 80 mol%.
  • the higher the acetaldehyde ratio the smaller the amount of ethylene and diethyl ether produced, resulting in C5-C8 carbonization. As a result, the amount of hydrogen produced increased.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un procédé de production qui améliore la sélectivité du 1,3-butadiène au cours d'un procédé en deux étapes (procédé américain). Ledit procédé de production du 1,3-butadiène à l'aide d'un réacteur à deux étapes est caractérisé en ce que, lorsque l'acétaldéhyde est synthétisé par déshydrogénation de l'éthanol au cours de la première étape et ensuite le 1,3-butadiène est synthétisé à partir de l'éthanol et de l'acétaldéhyde au cours de la seconde étape tel que représenté par les formules réactionnelles ci-dessous, la proportion d'alimentation en éthanol dans le total d'éthanol et d'acétaldéhyde à introduire dans le réacteur de la seconde étape est fixée à une valeur située dans la plage allant de 60 à 90 % en moles. CH3CH2OH → CH3CHO + H2 (Première étape) CH3CH2OH + CH3CHO → CH2=CH-CH=CH2 + 2H2O (Seconde étape)
PCT/JP2015/086235 2015-01-05 2015-12-25 Procédé de production de 1,3-butadiène Ceased WO2016111203A1 (fr)

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JP2015-000155 2015-01-05
JP2015000155 2015-01-05

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WO2016111203A1 true WO2016111203A1 (fr) 2016-07-14

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021006250A1 (fr) * 2019-07-05 2021-01-14 積水化学工業株式会社 Procédé de production de 1,3-butadiène
WO2021006252A1 (fr) * 2019-07-05 2021-01-14 積水化学工業株式会社 Procédé de production de 1,3-butadiène
WO2021193457A1 (fr) * 2020-03-23 2021-09-30 積水化学工業株式会社 Procédé de production de 1,3-butadiène et dispositif de production de 1,3-butadiène
JP2021195304A (ja) * 2020-06-09 2021-12-27 横浜ゴム株式会社 ブタジエンの製造方法およびブタジエンの製造装置
JP2023031584A (ja) * 2021-08-25 2023-03-09 積水化学工業株式会社 １，３－ブタジエンの製造方法及び１，３－ブタジエンの製造装置
JP2024546685A (ja) * 2021-12-08 2024-12-26 ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー 使用済みタイヤからのブタジエン生成

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2012153654A (ja) * 2011-01-26 2012-08-16 Sumitomo Rubber Ind Ltd 合成システム、タイヤ用ゴム薬品、タイヤ用合成ゴム及び空気入りタイヤ
WO2013125389A1 (fr) * 2012-02-20 2013-08-29 株式会社ダイセル Procédé de production de 1,3-butadiène
JP2013535465A (ja) * 2010-07-29 2013-09-12 オブシュチェスティヴォ エス オグラニチェノイ オトヴェツヴェノスユ “ユニジット” ブタジエンを製造する１ステップ法
JP2014210755A (ja) * 2013-04-22 2014-11-13 昭和電工株式会社 ブタジエンの製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2013535465A (ja) * 2010-07-29 2013-09-12 オブシュチェスティヴォ エス オグラニチェノイ オトヴェツヴェノスユ “ユニジット” ブタジエンを製造する１ステップ法
JP2012153654A (ja) * 2011-01-26 2012-08-16 Sumitomo Rubber Ind Ltd 合成システム、タイヤ用ゴム薬品、タイヤ用合成ゴム及び空気入りタイヤ
WO2013125389A1 (fr) * 2012-02-20 2013-08-29 株式会社ダイセル Procédé de production de 1,3-butadiène
JP2014210755A (ja) * 2013-04-22 2014-11-13 昭和電工株式会社 ブタジエンの製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021006250A1 (fr) * 2019-07-05 2021-01-14 積水化学工業株式会社 Procédé de production de 1,3-butadiène
WO2021006252A1 (fr) * 2019-07-05 2021-01-14 積水化学工業株式会社 Procédé de production de 1,3-butadiène
JPWO2021006250A1 (ja) * 2019-07-05 2021-09-13 積水化学工業株式会社 １，３−ブタジエンの製造方法
JPWO2021006252A1 (ja) * 2019-07-05 2021-09-13 積水化学工業株式会社 １，３−ブタジエンの製造方法
CN114364649A (zh) * 2019-07-05 2022-04-15 积水化学工业株式会社 1,3-丁二烯的制造方法
US11472753B2 (en) 2019-07-05 2022-10-18 Sekisui Chemical Co., Ltd. Method for producing 1,3-butadiene
US11479518B2 (en) 2019-07-05 2022-10-25 Sekisui Chemical Co., Ltd. Method for producing 1,3-butadiene
WO2021193457A1 (fr) * 2020-03-23 2021-09-30 積水化学工業株式会社 Procédé de production de 1,3-butadiène et dispositif de production de 1,3-butadiène
JP2021195304A (ja) * 2020-06-09 2021-12-27 横浜ゴム株式会社 ブタジエンの製造方法およびブタジエンの製造装置
JP7546245B2 (ja) 2020-06-09 2024-09-06 横浜ゴム株式会社 ブタジエンの製造方法およびブタジエンの製造装置
JP2023031584A (ja) * 2021-08-25 2023-03-09 積水化学工業株式会社 １，３－ブタジエンの製造方法及び１，３－ブタジエンの製造装置
JP2024546685A (ja) * 2021-12-08 2024-12-26 ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー 使用済みタイヤからのブタジエン生成

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