WO2014129248A1 - Procédé de production sélective de buta-1,3-diène à partir d'éthanol - Google Patents

Procédé de production sélective de buta-1,3-diène à partir d'éthanol Download PDF

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Publication number
WO2014129248A1
WO2014129248A1 PCT/JP2014/051094 JP2014051094W WO2014129248A1 WO 2014129248 A1 WO2014129248 A1 WO 2014129248A1 JP 2014051094 W JP2014051094 W JP 2014051094W WO 2014129248 A1 WO2014129248 A1 WO 2014129248A1
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catalyst
butadiene
producing
ethanol
weight
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PCT/JP2014/051094
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English (en)
Japanese (ja)
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中谷哲
馬場俊秀
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株式会社ダイセル
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Priority to JP2015501364A priority Critical patent/JPWO2014129248A1/ja
Publication of WO2014129248A1 publication Critical patent/WO2014129248A1/fr

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J35/613—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • C07C2521/08—Silica
    • 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
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead

Definitions

  • the present invention relates to a novel 1,3-butadiene production method for producing 1,3-butadiene, which is a raw material for synthetic rubber, which is important in many industrial fields including the automotive industry field and the electronic material field, from ethanol in one pass.
  • This application claims the priority of Japanese Patent Application No. 2013-031930 for which it applied to Japan on February 21, 2013, and uses the content here.
  • 1,3-butadiene has been produced mainly by refining the C4 fraction produced as a by-product during the synthesis of ethylene from petroleum.
  • biomass-derived raw materials instead of petroleum-derived chemical industrial raw materials, attempts to derive chemical industrial raw materials from biomass-derived raw materials have attracted attention.
  • bioethanol derived from biomass such as sugar cane and corn is 1,3-
  • the technology to convert to butadiene is eagerly desired.
  • Patent Document 1 As a method for obtaining 1,3-butadiene using alcohol as a raw material, a method using MgO as a catalyst (Patent Document 1), a method using a mixture of Al 2 O 3 and ZnO (mixing ratio: 60/40) (non-patent document) Patent Document 1) and the like are known.
  • the manufacturing technology is not as delicate and established as compared to naphtha cracking, the catalyst is easily deteriorated by heat and difficult to recycle, resulting in high costs, low alcohol conversion efficiency, and yield of 1,3-butadiene.
  • an object of the present invention is to provide a method for producing 1,3-butadiene which obtains 1,3-butadiene from ethanol by a simple and industrially advantageous method.
  • the present invention is a method for producing 1,3-butadiene that obtains 1,3-butadiene from ethanol, and is characterized in that ethanol is brought into contact with a catalyst containing germanium oxide and magnesium oxide under heating.
  • a method for producing 1,3-butadiene is provided.
  • content of each component in a catalyst is in the following range.
  • Germanium oxide content 0.1-90% by weight
  • Magnesium oxide content 10-90% by weight
  • the weight ratio of magnesium oxide / germanium oxide in the catalyst is preferably 0.1 to 200.
  • the catalyst containing germanium oxide and magnesium oxide preferably further contains an inorganic oxide other than the above having a specific surface area of 10 m 2 / g or more.
  • content of each component in a catalyst is in the following range.
  • Germanium oxide content 0.1-30% by weight
  • Magnesium oxide content 10-90% by weight
  • the inorganic oxide other than germanium oxide and magnesium oxide is preferably silicon dioxide.
  • the raw material is brought into contact with the catalyst under hydrogen conditions.
  • the method for producing 1,3-butadiene of the present invention preferably uses a fixed bed type gas phase continuous flow reactor.
  • the present invention relates to the following.
  • the catalyst containing germanium oxide and magnesium oxide is a catalyst further containing an inorganic oxide other than the above having a specific surface area of 10 m 2 / g or more.
  • the method for producing 1,3-butadiene according to (5), wherein the content of each component in the catalyst (100% by weight) is as follows.
  • Germanium oxide content 0.1-30% by weight
  • Magnesium oxide content 10-90% by weight
  • Manufacturing method (8) The method for producing 1,3-butadiene according to any one of (5) to (7), wherein the inorganic oxide other than germanium oxide and magnesium oxide is silicon dioxide.
  • the catalyst is prepared by mixing germanium oxide, a magnesium compound and an inorganic oxide other than the above, suspending in a solvent, kneading using an auto mill, drying, and firing (heat treatment)
  • the contact time between ethanol and the catalyst is 1 to 50 seconds, and the ethanol gas space velocity is in the range of 50 to 5000 hr ⁇ 1.
  • the selectivity of 1,3-butadiene 75 minutes after the start of the reaction at the reaction temperature of 400 ° C. and the space velocity of 360 hr ⁇ 1 is 55% or more, and the reaction temperature is 400 ° C. and the space velocity.
  • 1,3-butadiene can be selectively produced from ethanol by a simple method.
  • the catalyst used in the present invention is hardly deteriorated by heat and can be used repeatedly. Therefore, the method for producing 1,3-butadiene according to the present invention is preferably used in a method for industrially producing 1,3-butadiene, which is an important raw material for synthetic rubber in many industrial fields, from ethanol. Can do.
  • the method for producing 1,3-butadiene according to the present invention is characterized in that ethanol is brought into contact with a catalyst containing germanium oxide and magnesium oxide under heating.
  • the catalyst of the present invention is characterized by containing germanium oxide and magnesium oxide, and is preferably a joined catalyst.
  • Magnesium oxide is an active species in the catalytic reaction for obtaining 1,3-butadiene from ethanol.
  • Germanium oxide acts as a co-catalyst and exhibits the effect of improving the selectivity of 1,3-butadiene.
  • a specific surface area of a catalyst it is 10 m ⁇ 2 > / g or more, for example, Preferably it is 80 m ⁇ 2 > / g or more, More preferably, it is 100 m ⁇ 2 > / g or more, More preferably, it is 120 m ⁇ 2 > / g or more.
  • an upper limit does not have a restriction
  • the catalyst of this application may contain the inorganic oxide whose specific surface areas other than a germanium oxide and a magnesium oxide are 10 m ⁇ 2 > / g or more. In order to improve the surface area, it is preferable to use a catalyst in which the inorganic oxide is used as a carrier or a binder and germanium oxide and magnesium oxide are joined.
  • silicon dioxide can be preferably used as the inorganic oxide other than germanium oxide and magnesium oxide.
  • the specific surface area (BET specific surface area) of the inorganic oxide is, for example, about 10 to 1000 m 2 / g, preferably 50 to 1000 m 2 / g, more preferably 100 to 1000 m 2 / g. If the specific surface area of the inorganic oxide is out of the above range, it tends to be difficult to stabilize fine particles of the mixed oxide of germanium oxide and magnesium oxide which are active species. For example, if the specific surface area of the inorganic oxide exceeds the above range, the pore diameter becomes extremely small, so that pore clogging due to carbon deposition is liable to occur and the diffusion of the substrate to the active site is inhibited. There is a tendency to increase speed.
  • the shape of the inorganic oxide is not particularly limited, and various shapes such as a granular material, a lump, a layer, a porous shape, a so-called honeycomb structure can be used.
  • inorganic oxide examples include colloidal silica (silica sol), silica gel, fumed silica, diatomaceous earth, mica, mesoporous silica (MCM-41), zeolite, and silicoaluminophosphate. These can be used alone or in admixture of two or more.
  • the inorganic oxide for example, trade name “Snowtex 30” (silicon dioxide content ratio: 30 wt%, specific surface area: 300 ⁇ 100 m 2 / g, manufactured by Nissan Chemical Industries, Ltd.), product Name “Snowtex XS” (silicon dioxide content: 20% by weight, specific surface area: 800 ⁇ 200 m 2 / g, manufactured by Nissan Chemical Industries, Ltd.), trade name “AEROSIL380PE” (silicon dioxide content: 99.9% by weight) %, Specific surface area: 380 ⁇ 30 m 2 / g, manufactured by Nippon Aerosil Co., Ltd.) and the like may be used.
  • the catalyst of the present invention is preferably a catalyst obtained by joining germanium oxide and magnesium oxide, or a catalyst obtained by further joining the above catalyst to an inorganic oxide other than the above.
  • Germanium oxide content for example 0.1 to 90% by weight, preferably 5 to 80% by weight, particularly preferably 30 to 70% by weight
  • Magnesium oxide content for example 10 to 90% by weight, preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight
  • the weight ratio of magnesium oxide / germanium oxide in the catalyst is, for example, 0.1 to 200, preferably 0.3 to 20, and more preferably 0.5 to 5.
  • the content of each component in the catalyst (100% by weight) is preferably in the following range.
  • Germanium oxide content for example 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 5 to 10% by weight
  • Magnesium oxide content for example, 10 to 90% by weight, preferably 65 to 87% by weight, particularly preferably 70 to 85% by weight
  • Inorganic oxide content other than the above for example, 0.1 to 89.9% by weight, preferably 3 to 25% by weight, particularly preferably 5 to 20% by weight
  • the weight ratio of magnesium oxide / germanium oxide in the catalyst is, for example, 0.1 to 200, preferably 1 to 170, and more preferably 6 to 18.
  • germanium oxide content in the catalyst is below the above range, the effect of improving the 1,3-butadiene selectivity tends to be difficult to obtain.
  • germanium oxide content exceeds the above range, the catalyst activity is not easily dispersed on the catalyst, but rather the catalytic activity tends to be reduced by blocking the active sites.
  • magnesium oxide content in the catalyst is below the above range, the active sites are reduced, and the butadiene yield tends to be greatly reduced.
  • the magnesium oxide content exceeds the above range, the basicity of the catalyst tends to increase and the n-butanol selectivity tends to increase.
  • Examples of the method for preparing the catalyst include a kneading method, an impregnation method, a vapor deposition method, and a supported complex decomposition method.
  • a kneading method it is preferable to employ a kneading method because a catalyst capable of producing 1,3-butadiene with an excellent selectivity can be prepared.
  • germanium oxide and a magnesium compound for example, magnesium hydroxide, magnesium nitrate, magnesium oxalate, etc.
  • an inorganic oxide other than the above for example, silicon dioxide
  • a solvent for example, water, Suspended in acetone, alcohol, or a mixture thereof, etc., kneaded using an auto mill, etc., dried and baked (heat treatment), and germanium oxide and magnesium oxide are bonded with a binder containing the inorganic oxide.
  • Prepared catalysts can be prepared.
  • the method for producing 1,3-butadiene according to the present invention is a method for producing 1,3-butadiene, which obtains 1,3-butadiene from ethanol, wherein ethanol is converted into the above catalyst (germanium oxide and magnesium oxide under heating). A catalyst obtained by bonding, or a catalyst obtained by bonding the catalyst to an inorganic oxide other than the above is contacted.
  • the raw material ethanol is not particularly limited, and examples thereof include bioethanol derived from biomass such as sugar cane and corn, and synthetic ethanol derived from petroleum or natural gas.
  • biomass-derived bioethanol 1,3-butadiene useful as a raw material for synthetic rubber is industrially produced from bioethanol in place of conventional petroleum-derived chemical industrial materials. It is preferable in that it can greatly contribute to the reduction of greenhouse gases.
  • the method for producing 1,3-butadiene of the present invention can be performed by a conventional method such as a batch method, a semi-batch method, or a continuous method.
  • a conventional method such as a batch method, a semi-batch method, or a continuous method.
  • the usage rate of the raw material ethanol can be made extremely high.
  • the method for producing 1,3-butadiene according to the present invention uses the above catalyst, raw ethanol can be converted at a higher conversion rate than in the past even if a continuous method is adopted, and unreacted raw material can be converted.
  • the usage rate of the raw material ethanol can be improved to an extremely high level. Therefore, a continuous system capable of separating and recovering 1,3-butadiene simply and efficiently can be suitably employed.
  • examples of the method of bringing ethanol into contact with the catalyst 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.
  • the catalyst layer is formed by filling the above-mentioned catalyst into a reaction tube, particularly in that mass synthesis is possible, operation workload is low, and catalyst recovery and regeneration treatment is simple. It is preferable to use a fixed bed type gas phase continuous flow reaction apparatus in which a gas is circulated and reacted in the gas phase.
  • the raw ethanol gas may be supplied to the reactor without dilution, and is appropriately determined depending on the inert gas such as nitrogen, helium, argon, carbon dioxide, or hydrogen partially involved in the reaction. It may be diluted and fed to the reactor.
  • the inert gas such as nitrogen, helium, argon, carbon dioxide, or hydrogen partially involved in the reaction. It may be diluted and fed to the reactor.
  • contacting the raw material with a catalyst in the presence of hydrogen promotes a selective hydrogenation reaction of crotonaldehyde to crotyl alcohol in the reaction step, Since condensation and decomposition of crotonaldehyde are suppressed, it is preferable in that the selectivity of 1,3 butadiene can be improved.
  • the molar ratio of the raw material to be brought into contact with the catalyst and hydrogen is, for example, about 10/90 to 90/10, preferably 20/80 to 80/20, and particularly preferably 40/60 to 60/40. .
  • the reaction temperature is, for example, about 300 to 500 ° C., preferably 350 to 450 ° C. If the reaction temperature is lower than the above range, sufficient catalytic activity may not be obtained, the reaction rate may be reduced, and the production efficiency may be reduced. On the other hand, when the reaction temperature exceeds the above range, the catalytic activity may be deteriorated.
  • the reaction pressure can be appropriately set within a wide range from normal pressure to high pressure. In addition, it is preferable to set to 1 Mpa or less from viewpoints of manufacturing efficiency, apparatus configuration, and the like.
  • the contact time between the raw ethanol and the catalyst is, for example, about 1 to 50 seconds, preferably 5 to 30 seconds. If the contact time is too short, ethanol does not convert to butadiene, and unreacted ethanol and acetaldehyde, crotonaldehyde, and the like as intermediates tend to increase at the reactor outlet. On the other hand, if the contact time with the catalyst becomes too long, condensation or polymerization of acetaldehyde, butadiene or the like proceeds and a large amount of high-boiling components tend to be generated.
  • Contact time between feedstock ethanol and the catalyst can be controlled by adjusting the feed rate of the raw material ethanol, for example, ethanol gas space velocity 50 ⁇ 5000 hr -1 (preferably 100 ⁇ 1000 hr -1, particularly preferably It is preferable to adjust within the range of 200 to 500 hr ⁇ 1 ).
  • reaction product After completion of the reaction, the reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, etc., or a separation means combining these.
  • separation means such as filtration, concentration, distillation, extraction, etc., or a separation means combining these.
  • the catalyst of the present invention has a structure in which magnesium oxide and germanium oxide, which are catalytic active components, are joined, the catalytic active component is difficult to elute in the reaction solution even in an organic synthesis reaction. It can be easily recovered by a physical separation technique such as separation. Moreover, unreacted raw material ethanol may be recovered and reused.
  • air is circulated in the reactor under heating at, for example, about 350 to 500 ° C., preferably 450 to 500 ° C., for example, for 1 to 24 hours, preferably 2 to 4 hours.
  • the catalyst activity is recovered to 90% or more with respect to the unused catalyst, and can be reused in the reaction as it is.
  • ethanol is brought into contact with the catalyst under heating, so that 1,3-butadiene is produced with excellent ethanol conversion and excellent selectivity. Can do.
  • the method for producing 1,3-butadiene according to the present invention can selectively produce 1,3-butadiene, for example, after the start of the reaction when the reaction is carried out under conditions of a reaction temperature of 400 ° C. and a space velocity of 360 hr ⁇ 1.
  • the selectivity for 1,3-butadiene after 75 minutes is, for example, 55% or more, preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more.
  • the method for producing 1,3-butadiene of the present invention is excellent in the conversion rate of ethanol.
  • the rate is, for example, 40% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the 1,3-butadiene production method of the present invention has a very high selectivity for 1,3-butadiene as described above, the ethanol usage rate is improved by reusing unreacted ethanol in the reaction system. 1,3-butadiene can be produced industrially efficiently.
  • Example 1 used the catalyst obtained in Preparation Example 1, Example 2 used in Preparation Example 2, and Comparative Example 1 used in Preparation Example 3.
  • Example 3 used the catalyst obtained in Preparation Example 4
  • Example 4 used the preparation obtained in Preparation Example 2
  • Examples 5 to 7 used the catalysts obtained in Preparation Examples 5 to 7, respectively.
  • 1,3-butadiene can be selectively produced from ethanol by a simple method.
  • the catalyst used in the present invention is hardly deteriorated by heat and can be used repeatedly. Therefore, the method for producing 1,3-butadiene according to the present invention is preferably used in a method for industrially producing 1,3-butadiene, which is an important raw material for synthetic rubber in many industrial fields, from ethanol. Can do.

Abstract

L'invention porte sur un procédé de production sélective de buta-1,3-diène à partir d'éthanol, qui utilise un processus simple et industriellement avantageux. Ce procédé est caractérisé en ce qu'une matière première, telle que mentionnée ci-dessous, est mise en contact avec un catalyseur, tel que mentionné ci-dessous, pendant le chauffage. La matière première contient de l'éthanol. Le catalyseur comprend de l'oxyde de germanium et de l'oxyde de magnésium.
PCT/JP2014/051094 2013-02-21 2014-01-21 Procédé de production sélective de buta-1,3-diène à partir d'éthanol WO2014129248A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015501364A JPWO2014129248A1 (ja) 2013-02-21 2014-01-21 エタノールから１，３−ブタジエンを選択的に製造する方法

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Application Number Priority Date Filing Date Title
JP2013-031930 2013-02-21
JP2013031930 2013-02-21

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WO2014129248A1 true WO2014129248A1 (fr) 2014-08-28

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018147934A1 (fr) * 2017-02-07 2018-08-16 Battelle Memorial Institute Conversion en une étape d'éthanol en butadiène
WO2019065924A1 (fr) 2017-09-27 2019-04-04 積水化学工業株式会社 Catalyseur, dispositif de fabrication de diène conjugué et procédé de fabrication de diène conjugué
JPWO2019098208A1 (ja) * 2017-11-17 2020-04-02 三井化学株式会社 半導体素子中間体、金属含有膜形成用組成物、半導体素子中間体の製造方法、半導体素子の製造方法
US11446635B2 (en) 2017-12-27 2022-09-20 Sekisui Chemical Co., Ltd. Catalyst and method for producing same, and method for producing diene compound using said catalyst
US11465128B2 (en) 2018-01-12 2022-10-11 Sekisui Chemical Co., Ltd. Catalyst, method for producing same, and method for producing diene compound using said catalyst

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5859928A (ja) * 1981-10-02 1983-04-09 Takeda Chem Ind Ltd ブタジエンの製造法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5859928A (ja) * 1981-10-02 1983-04-09 Takeda Chem Ind Ltd ブタジエンの製造法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
E.V. MAKSHINA ET AL.: "Catalytic study of the conversion of ethanol into 1,3-butadiene", CATALYSIS TODAY, vol. 198, 2012, pages 338 - 344, XP028958465, DOI: doi:10.1016/j.cattod.2012.05.031 *
S. K. BHATTACHARYYA ET AL.: "Catalytic production of butadiene from ethyl alcohol by single-step process in fixed bed", JOURNAL OF SCIENTIFIC & INDUSTRIAL RESEARCH, vol. 19 B, 1960, pages 33 - 34 *
YOSHIE KITAYAMA ET AL.: "Preparation of large surface area nickel magnesium silicate and its catalytic activity for conversion", CATALYSIS LETTERS, vol. 36, 1996, pages 95 - 97 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018147934A1 (fr) * 2017-02-07 2018-08-16 Battelle Memorial Institute Conversion en une étape d'éthanol en butadiène
US10647625B2 (en) 2017-02-07 2020-05-12 Battelle Memorial Institute Single step conversion of ethanol to butadiene
WO2019065924A1 (fr) 2017-09-27 2019-04-04 積水化学工業株式会社 Catalyseur, dispositif de fabrication de diène conjugué et procédé de fabrication de diène conjugué
US11352307B2 (en) 2017-09-27 2022-06-07 Sekisui Chemical Co., Ltd. Catalyst, device for manufacturing conjugated diene, and method for manufacturing conjugated diene
JPWO2019098208A1 (ja) * 2017-11-17 2020-04-02 三井化学株式会社 半導体素子中間体、金属含有膜形成用組成物、半導体素子中間体の製造方法、半導体素子の製造方法
JP7070935B2 (ja) 2017-11-17 2022-05-18 三井化学株式会社 半導体素子中間体、金属含有膜形成用組成物、半導体素子中間体の製造方法、半導体素子の製造方法
US11446635B2 (en) 2017-12-27 2022-09-20 Sekisui Chemical Co., Ltd. Catalyst and method for producing same, and method for producing diene compound using said catalyst
US11465128B2 (en) 2018-01-12 2022-10-11 Sekisui Chemical Co., Ltd. Catalyst, method for producing same, and method for producing diene compound using said catalyst

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