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WO2016125578A1 - Procédé de production de 1,3-butadiène - Google Patents

Procédé de production de 1,3-butadiène Download PDF

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Publication number
WO2016125578A1
WO2016125578A1 PCT/JP2016/051387 JP2016051387W WO2016125578A1 WO 2016125578 A1 WO2016125578 A1 WO 2016125578A1 JP 2016051387 W JP2016051387 W JP 2016051387W WO 2016125578 A1 WO2016125578 A1 WO 2016125578A1
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WO
WIPO (PCT)
Prior art keywords
butadiene
catalyst
ethanol
producing
fraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/051387
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English (en)
Japanese (ja)
Inventor
一規 本田
千津 稲木
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JGC Corp
Original Assignee
JGC Corp
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Filing date
Publication date
Application filed by JGC Corp filed Critical JGC Corp
Publication of WO2016125578A1 publication Critical patent/WO2016125578A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • It relates to a method for producing 1,3-butadiene from ethanol.
  • Butadiene production from ethanol is a technology with an industrial track record in the past, but lost its competitiveness with the completion of butadiene extractive distillation technology from C4 fraction obtained from naphtha crackers. Currently not used except. However, in recent years, there are concerns about the expansion of the global butadiene supply-demand gap accompanying the growth in the number of automobiles, especially in Asia, and the lighter cracker raw materials, and there is an increasing interest in the ETB process that can produce butadiene alone.
  • an MgO—SiO 2 catalyst to which a metal such as Ag, Cu, Ni, Zn or the like is added for the purpose of imparting ethanol dehydrogenation ability Patent Document 5, Non-Patent Documents 3 to 6
  • An MgO—SiO 2 catalyst (Patent Document 5) to which an element such as tantalum is added has been developed for the purpose of improving selectivity.
  • Ta 2 O 5 / SiO 2 (Patent Document 6, Non-Patent Document 6) and ZrO 2 / SiO 2 (Patent Document 7, Non-Patent Document 6) are known as catalysts for producing butadiene from ethanol and acetaldehyde. .
  • Patent Document 8 Ag—ZrO 2 —SiO 2 in which ethanol dehydrogenation ability is imparted to these catalysts has been reported.
  • ZnO—Al 2 O 3 Non-patent Documents 7 and 8
  • Sepiolite Non-patent Document 9
  • Patent Documents 9 to 11 technologies related to ethanol and acetaldehyde recycling (Patent Documents 9 to 11) have also been proposed.
  • none of the prior art has been devised to improve the 1,3-butadiene concentration in the C4 fraction, and the C4 fraction (crude butadiene) produced through the ETB process is obtained from a conventional cracker. It was thought to be purified through a butadiene extraction unit in the same manner as a C4 fraction containing about several tens of percent of butenes and butanes.
  • the type, loading, and reaction conditions of the catalyst having a butadiene selectivity of 98 mol% or more in the C4 fraction that does not require purification in the butadiene extraction unit of the C4 fraction obtained from the ETB process are as follows. It is intended to provide.
  • the catalyst is composed of Group 4 and Group 5 elements (A) and metal oxide (B) in the periodic table, and the ratio of (A) is in the range of 0.2 wt% to 30 wt% as an oxide.
  • the method for producing 1,3-butadiene as described in [4], wherein [6] The method for producing 1,3-butadiene according to [5], wherein the metal oxide (B) is a substance containing silicon dioxide.
  • the 1,3-butadiene concentration in the C4 fraction increases, so that the number of butadiene extraction units can be reduced. Therefore, it is possible to reduce construction costs and butadiene production costs.
  • the ratio of 1,3-butadiene in the C4 fraction comprising butanes, butenes and butadienes in the product is set to 98 mol% or more. , 3-butadiene production method.
  • the raw material used in the present invention contains at least ethanol.
  • the ethanol is not particularly limited, and examples include ethanol derived from biomass such as sugar cane and corn, ethanol derived from petroleum, coal, or natural gas. In addition, if ethanol derived from biomass is used, it can contribute to greenhouse gas reduction.
  • the raw material of the present invention may be ethanol alone or may contain acetaldehyde together with ethanol.
  • the molar ratio of ethanol to acetaldehyde is in the range of 95: 5 to 40:60, preferably 90:10 to 50:50, more preferably 85:15 to 60:40. is there.
  • acetaldehyde one produced by ethanol dehydrogenation can be used.
  • a known copper catalyst or silver catalyst disclosed in JP-A Nos. 2005-342675 and 2011-532 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.
  • the reaction conditions are not particularly limited, and the reaction is usually carried out in the range of about 200 to 300 ° C. under conditions that produce a predetermined amount of acetaldehyde.
  • the catalyst used in the present invention contains Group 4 and Group 5 elements (A) in the periodic table.
  • the element (A) examples include titanium, zirconium, hafnium, vanadium, niobium, tantalum and the like.
  • the element ( A) is preferably any of zirconium, hafnium and tantalum, more preferably zirconium or tantalum.
  • These elements (A) are fixed to the metal oxide (B) in the state of metal, oxide, hydroxide, salt or the like.
  • the proportion of element (A) in the catalyst is selected so that the proportion of 1,3-butadiene in the C4 fraction is 98 mol% or more.
  • the range of 0.2 to 10% by weight is preferable when the element (A) is zirconium as an oxide, and the range of 0.2 to 30% by weight is preferable when tantalum is used.
  • the element (A) is more preferably in the range of 0.5 to 8.0% by weight, still more preferably 1.0 to 5.0% by weight.
  • the 1,3-butadiene ratio in the C4 fraction is high, and the butadiene yield can be increased. If the content of the element (A) is too large, the butenes formation reaction, which is a side reaction, is promoted, so that the 1,3-butadiene ratio in the C4 fraction decreases. On the other hand, if the content of element (A) is too small, the number of active sites is so small that the butadiene yield decreases.
  • metal oxide (B) examples include silicon dioxide, magnesium oxide, aluminum oxide, zirconium oxide, titanium oxide, and zeolite (aluminosilicate). These can be used alone or in admixture of two or more. Of these, those containing silicon dioxide are preferred.
  • Examples of those containing silicon dioxide include amorphous silica, silica sol, silica gel, and colloidal silica. Further, mesoporous silica such as MCM-41, FSM-16, SBA-15, and zeolite can also be used.
  • Such a catalyst is prepared by, for example, dissolving a chloride salt, nitrate, sulfate, phosphate, or alkoxide containing the element (A) in water or an organic solvent, impregnating the metal oxide (B), and then heating. It can be prepared by drying and baking.
  • the impregnation method a known method can be adopted, and examples thereof include a spray method, a coating method, a pore filling method, and a selective adsorption method.
  • after mixing the precursor of an element (A) and a metal oxide (B) it can also prepare by performing processes, such as heating, concentration, and hydrothermal synthesis, and drying and baking.
  • Examples of the precursor of the element (A) and the metal oxide (B) include alkoxides, chloride salts, nitrates, sulfates, phosphates, metal oxide sols, and the like. You may add the organic compound used as a structure directing agent to what mixed the precursor of an element (A) and a metal oxide (B).
  • the shape of the catalyst is not particularly limited, and a known shape such as a granular shape, a columnar shape, a cylindrical shape, or a honeycomb shape can be used.
  • Method for producing 1,3-butadiene The method for producing 1,3-butadiene of the present invention is characterized in that the raw material is brought into contact with the catalyst under heating.
  • a known method such as a batch method, a semi-batch method, or a continuous method can be adopted.
  • the continuous method is adopted, large-scale synthesis is possible, the operation workload is light, and the unreacted raw material can be reused in the reaction system to improve the raw material ethanol usage rate to an extremely high level. For this reason, it is preferable to employ a continuous system that can separate and recover 1,3-butadiene simply and efficiently.
  • Examples of the method for bringing the raw material 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, 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 raw material gas may be supplied to the reactor without dilution, such as nitrogen, helium, argon, water vapor, etc. It may be appropriately diluted with an inert gas and supplied to the reactor.
  • acetaldehyde may be added to a raw material containing ethanol, and the molar ratio (EtOH: AcH) of ethanol and acetaldehyde (total amount after addition) may be set to the above ratio.
  • the reaction temperature is appropriately selected so that the proportion of 1,3-butadiene in the C4 fraction is 98 mol% or more. For example, it is in the range of about 260 to 450 ° C., preferably 300 to 400 ° C. If the temperature is too high, the proportion of 1,3-butadiene in the C4 fraction will decrease. On the other hand, if the temperature is too low, the butadiene yield decreases.
  • the reaction pressure can be appropriately set in a wide range from normal pressure to high pressure, but is preferably set to 1.0 MPa or less from the viewpoints of production efficiency and apparatus configuration.
  • 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) per unit catalyst is 1.0 to 40 g-(EtOH + AcH) ⁇ g -cat -1 ⁇ h -1 , preferably in the range of 2.0 to 20 g-(EtOH + AcH) ⁇ g -cat -1 ⁇ h -1 .
  • WHSV weight space velocity
  • reaction product is separated and purified into light gas, C4 fraction, heavy fraction, water, ethanol, acetaldehyde, etc., by separation means such as distillation, extraction, etc., or a separation means combining these. Can do.
  • the present invention by bringing a raw material containing ethanol and acetaldehyde into contact with a specific catalyst under predetermined conditions, 1,3-butadiene in a C4 fraction comprising butanes, butenes and butadienes in the product is obtained. Is 98 mol% or more. For this reason, the C4 fraction can be used as a raw material for synthetic rubber or the like without purification by a butadiene extraction unit, leading to a reduction in construction cost and manufacturing cost of the butadiene extraction unit. The availability is high.
  • Preparation Example 3 0.22 g of zirconium oxynitrate dihydrate was dissolved in 5.0 ml of ion-exchanged water, and supported on 5.0 g of Carrêtct G-6 (manufactured by Fuji Silysia Chemical Co., Ltd.) by the pore filling method. After drying at 120 ° C., the catalyst was calcined at 500 ° C. under air flow to obtain a ZrO 2 / SiO 2 (supported amount 2.0% by weight) catalyst.
  • the ratio of 1,3-butadiene in the C4 fraction of MgO—SiO 2 which is a general ETB catalyst, is lower than 98%, whereas ZrO 2 / SiO 2 (1.0 wt%), Ta Examples 1 and 2 using 2 O 5 / SiO 2 (1.6 wt%) are 98% or more.
  • Ta 2 O 5 / is Ta 2 O 5 amount of SiO 2 is 1,3-butadiene fraction in the C4 fraction in the range of 0.2 to 30% by weight was 98% or more, Ta 2 When the amount of O 5 was 40% by weight, the 1,3-butadiene ratio in the C4 fraction was lower than 98%. The smaller the amount of Ta 2 O 5 in Ta 2 O 5 / SiO 2, the lower the 1,3-butadiene yield.
  • the temperature was raised to 300 ° C. while flowing nitrogen into the reactor, and ethanol, acetaldehyde and nitrogen were mixed as raw material gases at the flow rates shown in Table 6 and supplied to the reactor.
  • the gas composition at the outlet of the reactor 6 to 15 minutes after the start of the reaction was determined by gas chromatography.
  • the temperature was raised to 300 ° C. while flowing nitrogen into the reactor, and ethanol, acetaldehyde and nitrogen were mixed as raw material gases at the flow rates shown in Table 7 and supplied to the reactor.
  • the gas composition at the outlet of the reactor 6 to 15 minutes after the start of the reaction was determined by gas chromatography.

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

Abstract

Cette invention concerne un procédé de production favorisant la sélectivité envers le butadiène dans une fraction C4 obtenue par un procédé ETB de 98 % en moles ou plus, ce qui permet d'éviter la nécessaire purification de la fraction C4 par une unité d'extraction de butadiène. L'invention est caractérisée en ce que la proportion de 1,3-butadiène dans la fraction C4 comprenant des butanes, des butènes, et des butadiènes dans le produit est portée à 98 % en moles ou plus par mise en contact d'un matériau brut contenant de l'éthanol avec un catalyseur. La température de fonctionnement ci-dessus est de 260 à 450°C, et la WHSV de 1,0 à 40g-(EtOH+AcH)⋅g-cat -1⋅h-1. Le catalyseur contient des éléments du Groupe 4 et du Groupe 5 du Tableau périodique des éléments.
PCT/JP2016/051387 2015-02-04 2016-01-19 Procédé de production de 1,3-butadiène Ceased WO2016125578A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-020280 2015-02-04
JP2015020280 2015-02-04

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WO2016125578A1 true WO2016125578A1 (fr) 2016-08-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018171587A (ja) * 2017-03-31 2018-11-08 日揮株式会社 エタノールからの１，３−ブタジエン製造触媒およびプロセス
JP2022547817A (ja) * 2019-09-16 2022-11-16 シントス ドボリ ７ スプウカ ズ オグラニザツィーノン オトゥポビエジャルノシチョン スプウカ ヤフナ １，３－ブタジエン製造用の担持タンタル触媒

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421361A (en) * 1942-09-29 1947-05-27 Carbide & Carbon Chem Corp Process for making diolefins
US2524848A (en) * 1946-07-13 1950-10-10 Koppers Co Inc Process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421361A (en) * 1942-09-29 1947-05-27 Carbide & Carbon Chem Corp Process for making diolefins
US2524848A (en) * 1946-07-13 1950-10-10 Koppers Co Inc Process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAE-WAN KIM ET AL.: "Butadiene production from bioethanol and acetaldehyde over tantalum oxide-supported spherical silica catalysts for circulating fluidized bed", CHEMICAL ENGINEERING JOURNAL, vol. 278, 16 October 2014 (2014-10-16), pages 217 - 223 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018171587A (ja) * 2017-03-31 2018-11-08 日揮株式会社 エタノールからの１，３−ブタジエン製造触媒およびプロセス
JP2022547817A (ja) * 2019-09-16 2022-11-16 シントス ドボリ ７ スプウカ ズ オグラニザツィーノン オトゥポビエジャルノシチョン スプウカ ヤフナ １，３－ブタジエン製造用の担持タンタル触媒
JP7758660B2 (ja) 2019-09-16 2025-10-22 シントス ドボリ ７ スプウカ ズ オグラニザツィーノン オトゥポビエジャルノシチョン １，３－ブタジエン製造用の担持タンタル触媒

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