WO2013012048A1 - Procédé de production de 1,4-butanediol - Google Patents

Procédé de production de 1,4-butanediol Download PDF

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Publication number
WO2013012048A1
WO2013012048A1 PCT/JP2012/068381 JP2012068381W WO2013012048A1 WO 2013012048 A1 WO2013012048 A1 WO 2013012048A1 JP 2012068381 W JP2012068381 W JP 2012068381W WO 2013012048 A1 WO2013012048 A1 WO 2013012048A1
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Prior art keywords
butanediol
solid catalyst
butyrolactone
gamma
crude
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PCT/JP2012/068381
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English (en)
Japanese (ja)
Inventor
雄輔 井澤
宇都宮　賢
範和 小西
幸太 田中
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三菱化学株式会社
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Publication of WO2013012048A1 publication Critical patent/WO2013012048A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only

Definitions

  • the present invention relates to a process for producing 1,4-butanediol which obtains high-purity 1,4-butanediol by hydrogenating gamma-butyrolactone in crude 1,4-butanediol and converting it to 1,4-butanediol. .
  • 1,4-butanediol (hereinafter sometimes abbreviated as “1,4BG”) is an extremely useful substance used as a raw material for various solvents and derivatives.
  • 1,4BG-containing composition by catalytic hydrogenation of 1,4-butynediol obtained by reacting acetylene with formaldehyde
  • Patent Document 1 a method of using maleic acid, succinic acid, maleic anhydride and / or fumaric acid as raw materials and hydrogenating them to obtain a 1,4BG-containing composition
  • Patent Document 2 a method of using maleic acid, succinic acid, maleic anhydride and / or fumaric acid as raw materials and hydrogenating them to obtain a 1,4BG-containing composition
  • the 1,4BG-containing composition obtained by the method contains by-products such as gamma-butyrolactone in addition to 1,4BG.
  • Patent Document 3 as a distillation method for obtaining high-purity 1,4BG from such a 1,4BG-containing composition, a crude 1,4-butanediol product is distilled using three distillation columns. Thus, a method is described in which gamma-butyrolactone is separated to obtain high purity 1,4BG. Although some separation of gamma butyrolactone is possible by this method, complete separation is not easy, and a small amount of gamma butyrolactone may be mixed into the product 1,4-butanediol.
  • a method for producing 1,4BG and tetrahydrofuran (hereinafter sometimes abbreviated as “THF”) by catalytic hydrogenation of gammabutyrolactone in the gas phase (Patent Document 4), or containing ruthenium as an essential component, and nickel, cobalt From a C4 hydrocarbon containing oxygen atoms consisting of maleic anhydride, maleic acid, succinic anhydride, gamma butyrolactone, and mixtures of two or more thereof, using a mixed metal oxygenation catalyst comprising -A method for producing butanediol and tetrahydrofuran (Patent Document 5) There is.
  • THF 1,4BG and tetrahydrofuran
  • Patent Document 4 is a hydrogenation reaction under gas-phase conditions, and requires a large amount of heat for vaporizing the hydrogenation raw material.
  • Patent Document 5 uses ruthenium, a noble metal, as an essential catalyst component, the catalyst cost may increase.
  • An object of the present invention is to provide a method for producing high-purity 1,4BG by purifying gamma-butyrolactone in crude 1,4-butanediol by hydrogenation and conversion to 1,4BG.
  • the present inventors have determined that if the content of gamma-butyrolactone is crude 1,4-butanediol having a content of 0.01 to 10% by weight, this is expressed as magnesium and a periodic table.
  • a metal element belonging to Group 10 of the present invention By contacting a metal element belonging to Group 10 of the present invention with a solid catalyst supported on a carrier, the formation of high-boiling by-products is suppressed, and hydrogenation of gamma-butyrolactone in crude 1,4-butanediol is efficiently performed. Found that it is possible to do.
  • the present invention has been achieved on the basis of such knowledge, and the gist thereof is as follows.
  • crude 1,4-butanediol can be purified by efficiently converting gammabutyrolactone in crude 1,4-butanediol containing gammabutyrolactone to 1,4-butanediol.
  • the present invention for example, by bringing crude 1,4-butanediol into contact with a solid catalyst by a method such as passing through a packed bed filled with the solid catalyst, the formation of high-boiling by-products is suppressed.
  • gamma-butyrolactone in the crude 1,4-butanediol can be converted to 1,4-butanediol with high conversion and high selectivity by industrially advantageous hydrogenation.
  • the method for producing 1,4-butanediol of the present invention obtains high-purity 1,4-butanediol by hydrogenating gammabutyrolactone in crude 1,4-butanediol and converting it to 1,4-butanediol.
  • This method is characterized in that the following conditions (1) and (2) are satisfied.
  • the content of gamma-butyrolactone in the crude 1,4-butanediol is 0.01 to 10% by weight
  • a hydrogenation solid catalyst it is generally known to use a catalyst containing a Lewis acid or Bronsted acid as a catalyst component, and when such a solid catalyst is used, In some cases, 4-butanediol or 1,4-butanediol present in the reaction system was converted to a high-boiling by-product and disappeared.
  • a solid catalyst in which magnesium and a Group 10 metal element are supported on a carrier is used, and for example, gamma-butyrolactone in crude 1,4-butanediol is distributed through a packed bed filled with the solid catalyst.
  • gamma-butyrolactone in crude 1,4-butanediol is distributed through a packed bed filled with the solid catalyst.
  • the group 10 metal element in the solid catalyst is excellent in catalytic activity and that the magnesium component neutralizes the acidic content on the catalyst and suppresses side reactions.
  • the contact efficiency with the catalyst is increased for gamma-butyrolactone and the hydrogenation is activated, while multimerization is performed for 1,4-butanediol. It is considered that this reaction is suppressed and hydrogenation can be performed more efficiently.
  • the concentration of gamma butyrolactone in the crude 1,4-butanediol subjected to hydrogenation in the present invention is 0.01% by weight or more, preferably 0.1% by weight or more, and particularly preferably 1.0% by weight. That's it.
  • concentration of gamma-butyrolactone in the crude 1,4-butanediol increases, the effect of the present invention increases and the separation load of gamma-butyrolactone in the 1,4-butanediol production process tends to be reduced.
  • the concentration of gamma-butyrolactone in crude 1,4-butanediol is 10% by weight or less, preferably 7% by weight or less, and particularly preferably 5% by weight or less.
  • loads such as pressure, amount of catalyst and reaction temperature in the hydrogenation reaction of the present invention tend to be reduced.
  • the crude 1,4-butanediol having a gamma-butyrolactone concentration in the above range may be prepared by mixing gamma-butyrolactone with commercially available 1,4-butanediol, but obtained by reacting acetylene with formaldehyde.
  • the 1,4BG-containing composition obtained by catalytic hydrogenation of 1,4-butynediol usually, gamma-butyrolactone in the above concentration range is present. Therefore, this 1,4BG-containing composition is crude 1,4 -It may be used as it is as butanediol.
  • this 1,4BG-containing composition may be purified by a method such as distillation to separate components other than gamma butyrolactone and 1,4BG, and may be used after adjusting to a gamma butyrolactone concentration.
  • gamma-butyrolactone within the above-mentioned concentration range usually also exists in 1,4BG-containing compositions obtained by hydrogenating maleic acid, succinic acid, maleic anhydride and / or fumaric acid as raw materials.
  • the 1,4BG-containing composition may be used as crude 1,4-butanediol as it is. Further, this 1,4BG-containing composition may be purified by a method such as distillation to separate components other than gammabutyrolactone and 1,4BG, and may be used after adjusting to a gammabutyrolactone concentration.
  • gamma-butyrolactone may be distilled off from the 1,4BG-containing composition in these production methods, and the amount of gamma-butyrolactone in the crude 1,4-butanediol is determined by the degree of distillation separation.
  • gamma-butyrolactone obtained by hydrogenation of maleic anhydride, hydrogenation of maleic acid, hydrogenation of succinic anhydride, hydrogenation of succinic acid, dehydrogenation of 1,4-butanediol, etc. may be used. .
  • the amount of these other components other than 1,4-butanediol is preferably 5% by weight or less, more preferably 2% by weight or less, and particularly preferably 1% by weight as the concentration in the crude 1,4-butanediol. % Or less.
  • the solid catalyst in the present invention is one in which one or more of magnesium and a group 10 metal element, that is, nickel (Ni), palladium (Pd), and platinum (Pt) are supported on a carrier.
  • a group 10 metal element that is, nickel (Ni), palladium (Pd), and platinum (Pt) are supported on a carrier.
  • nickel is most preferable in terms of catalyst cost and catalyst activity.
  • the form of the group 10 metal element such as nickel in the solid catalyst may be a single metal, an oxide such as nickel oxide, a hydroxide, or other various salts.
  • the ratio of oxide or the like to the metal simple substance is high, it is possible to perform the conversion to the metal simple substance by performing reduction activation treatment in advance with hydrogen gas before starting the reaction. However, the reaction can be started as it is. That is, since hydrogen gas is introduced into the hydrogenation reaction system, these oxides and the like are reduced into active metal elements during the reaction.
  • Magnesium may be contained in the form of a metal element itself, or may be contained in the form of an oxide, hydroxide, or other various salts.
  • silica or diatomaceous earth can be preferably used, and silica is particularly preferable.
  • the content of group 10 metal element component in solid catalyst is the metal oxide when the group 10 metal element is in the form of a metal oxide or the like. Is preferably 5% by weight or more and 80% by weight or less, more preferably 15% by weight or more and 80% by weight or less, and particularly preferably 50% by weight or more and 80% by weight or less. It is.
  • the content of magnesium in the solid catalyst (here, the content of magnesium in the solid catalyst is the content as an oxide or the like when magnesium is in the form of an oxide or the like), It is preferably 0.1% by weight or more and 20% by weight or less, more preferably 0.5% by weight or more and 15% by weight or less, and particularly preferably 1% by weight or more and 10% by weight or less.
  • the content of the support in the solid catalyst is preferably 5% by weight or more and 95% by weight or less, more preferably 7% by weight or more and 80% by weight or less, and particularly preferably 10% by weight or more and 60% by weight. % Or less.
  • the solid catalyst in the present invention may contain other metal elements as long as it contains magnesium and a group 10 metal element. However, the solid catalyst used in the present invention does not contain ruthenium.
  • metal elements examples include chromium, manganese, zinc, sodium, rhenium, calcium, and the like, and it is particularly preferable to contain sodium. These metal elements may also be contained in the form of metal elements themselves, oxides, hydroxides, and other various salts.
  • the solid catalyst in the present invention contains a group 10 metal element such as sodium and a metal element component other than magnesium (excluding ruthenium), the content thereof (here, the group 10 metal element and magnesium)
  • the content of the metal element component other than is the content as the metal oxide or the like when the other metal element is in the form of a metal oxide or the like. % By weight or less is preferable, more preferably 0.5% by weight or more and 15% by weight or less, and particularly preferably 1% by weight or more and 10% by weight or less.
  • the shape and size of the solid catalyst are not particularly limited, and may be a molded product such as powder, granule, granule, or pellet.
  • the size of the solid catalyst is also arbitrary. For example, in the case of a solid catalyst formed into a pellet, it is preferable that the diameter is 1 to 20 mm and the thickness is 1 to 20 mm.
  • Such a solid catalyst can be produced by a method in which a carrier is immersed in an aqueous solution of a Group 10 metal salt and a magnesium salt to carry the metal salt, and then calcined and molded as necessary.
  • reaction method contact method with a solid catalyst
  • crude 1,4-butanediol is brought into contact with a solid catalyst to convert gamma butyrolactone into 1,4-butanediol
  • the catalyst From the viewpoint of contact efficiency with the catalyst, it is preferable to adopt a catalyst packed bed circulation system in which crude 1,4-butanediol is passed through a packed bed filled with a solid catalyst.
  • all of the general packed bed type hydrogenation reactors with various solid catalysts such as fixed bed, trickle bed or multi-tube type can be used, but preferably fixed bed reaction. Or trickle bed reactor.
  • One reactor or a plurality of reactors can be used.
  • the reaction temperature for carrying out the hydrogenation in the present invention is preferably in the range of 0 to 200 ° C, more preferably 30 to 150 ° C, still more preferably 40 to 120 ° C.
  • the reaction temperature is too high, catalyst deterioration is promoted. Furthermore, the amount of high boiling by-products increases. If the reaction temperature is too low, the reaction hardly proceeds.
  • the hydrogen gas pressure in hydrogenation is preferably in the range of 0.1 to 100 MPa, more preferably 0.5 to 10 MPa, and still more preferably 1 to 6 MPa in terms of gauge pressure. If the hydrogen gas pressure is too low, the reaction rate is slow and productivity is lowered. If the hydrogen gas pressure is too high, the pressure resistance load of the reactor and the compressor load increase, resulting in a significant increase in construction costs.
  • the residence time of the reaction liquid on an empty column basis is preferably 5 minutes or more, more preferably 10 minutes or more, and particularly preferably 30 minutes or more. Moreover, 100 hours or less are preferable, More preferably, it is 50 hours or less, Especially preferably, it is 10 hours or less. If the residence time is too short, the hydrogenation reaction hardly proceeds. On the other hand, when the residence time is too long, the catalyst packed bed becomes long, and the economic efficiency is greatly deteriorated due to the increase in the equipment cost of the reactor and the increase in the amount of catalyst.
  • the catalyst filling amount is preferably 5 times or more, more preferably 10 times or more, particularly preferably 30 times the flow rate of the introduced liquid per minute.
  • the capacity is doubled. Further, it is preferably 6000 volume times or less, more preferably 3000 volume times or less, and particularly preferably 600 volume times or less. If the catalyst loading is too small, the reaction hardly proceeds. Moreover, when there is too much catalyst filling amount, catalyst cost will increase and economical efficiency will deteriorate significantly.
  • reaction products were analyzed by gas chromatography using an internal standard method. At that time, n-dodecane was used as an internal standard.
  • GC-14A column: DB-WAX
  • Shimadzu Corporation was used for the gas chromatography.
  • the solid catalysts I to VI used in the following examples and comparative examples, the solid catalysts I to V all have a metal element component supported on a carrier and are pelletized (diameter 1 to 5 mm, Table 1 shows the type of the carrier, the type of the carrier, and the content in the solid catalyst.
  • the solid catalyst VI is Raney nickel as shown in Table 1.
  • the solid catalyst is provided with a SUS filter, a glass bead layer, a solid catalyst layer, a glass bead layer, and a SUS filter in this order in the reactor of the flow reactor. Filled with.
  • Example 1 Using a flow reactor with a reactor capacity of 120 cc, this reactor was charged with 50 cc of solid catalyst I, and crude 1,4-butanediol containing 1.7% by weight of gamma butyrolactone was hydrogenated.
  • the hydrogenation reaction conditions were a temperature of 100 ° C. and a hydrogen gas pressure of 2.0 MPaG.
  • the flow rate of crude 1,4-butanediol was 50 cc / h.
  • the conversion rate of gamma butyrolactone to 1,4-butanediol was 20.0 mol%, and the concentration of high boiling by-products in the reaction product solution was 0.04 wt%.
  • Example 2 The reaction was performed in the same manner as in Example 1 except that the solid catalyst II was used as the solid catalyst. As a result, the conversion rate of gamma butyrolactone to 1,4-butanediol was 7.0 mol%, and the concentration of high boiling by-products in the reaction product solution was 0.23% by weight.
  • Example 3 The reaction was performed in the same manner as in Example 1 except that the solid catalyst V was used as the solid catalyst. As a result, the conversion rate of gamma butyrolactone to 1,4-butanediol was 5.3 mol%, and the concentration of high boiling by-products in the reaction product solution was 0.19 wt%.
  • Example 4 The reaction was performed in the same manner as in Example 1 except that the solid catalyst V was used as the solid catalyst and the reaction temperature was 130 ° C. As a result, the conversion rate of gamma butyrolactone to 1,4-butanediol was 11.3 mol%, and the concentration of high boiling by-products in the reaction product solution was 0.30 wt%.
  • Example 5 The reaction was performed in the same manner as in Example 1 except that the hydrogen gas pressure was 3.5 MPaG and the flow rate of crude 1,4-butanediol was 17 cc / h. As a result, the conversion rate of gamma butyrolactone to 1,4-butanediol was 24.8 mol%, and the concentration of high boiling by-products in the reaction product solution was 0.39 wt%.
  • Comparative Examples 4 and 5 When comparing Comparative Examples 4 and 5 in which hydrogenation was carried out batchwise using the same solid catalyst as in Examples 1 and 2, Comparative Examples 4 and 5 were both in crude 1,4-butanediol. It was found that the concentration of gamma butyrolactone was high, and the conversion rate of gamma butyrolactone and the amount of high boiling by-products produced were inferior to those of Examples 1 and 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Cette invention concerne un procédé de production de 1,4-butanediol qui permet d'obtenir un 1,4-butanediol très pur par mise en contact d'un 1,4-butanediol brut contenant 0,01 à 10 % en poids de gamma butyrolactone avec un catalyseur solide qui supporte un élément métallique appartenant au Groupe 10 de la Classification périodique des éléments et du magnésium sur un support, pour convertir ainsi la gamma butyrolactone en 1,4-butanediol.
PCT/JP2012/068381 2011-07-20 2012-07-19 Procédé de production de 1,4-butanediol WO2013012048A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106458948A (zh) * 2014-04-11 2017-02-22 Cj第制糖株式会社 用于处理基于高丝氨酸的化合物的方法
US9873652B2 (en) 2013-03-15 2018-01-23 Genomatica, Inc. Process and systems for obtaining 1,4-butanediol from fermentation broths

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY184283A (en) 2015-06-30 2021-03-30 Takeda Pharmaceuticals Co Method for producing pyrrole compound

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JPS61197534A (ja) * 1985-02-27 1986-09-01 Mitsubishi Chem Ind Ltd 粗１，４−ブタンジオ−ルの精製方法
JPH06172235A (ja) * 1992-12-10 1994-06-21 Mitsubishi Kasei Corp １，４−ブタンジオールの精製方法
JPH06239778A (ja) * 1993-02-17 1994-08-30 Mitsubishi Kasei Corp １，４−ブタンジオールの製造方法
JP2001048819A (ja) * 1999-08-04 2001-02-20 Tonen Chem Corp ジカルボン酸類の二段階水素化法

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US4797382A (en) * 1987-11-27 1989-01-10 Gaf Corporation Hydrogenation catalyst and process for preparing the catalyst
TW366335B (en) * 1996-03-29 1999-08-11 Kvaerner Process Tech Ltd Process for the purification of butane-1,4-diol
GB0421928D0 (en) * 2004-10-01 2004-11-03 Davy Process Techn Ltd Process

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Publication number Priority date Publication date Assignee Title
JPS61197534A (ja) * 1985-02-27 1986-09-01 Mitsubishi Chem Ind Ltd 粗１，４−ブタンジオ−ルの精製方法
JPH06172235A (ja) * 1992-12-10 1994-06-21 Mitsubishi Kasei Corp １，４−ブタンジオールの精製方法
JPH06239778A (ja) * 1993-02-17 1994-08-30 Mitsubishi Kasei Corp １，４−ブタンジオールの製造方法
JP2001048819A (ja) * 1999-08-04 2001-02-20 Tonen Chem Corp ジカルボン酸類の二段階水素化法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9873652B2 (en) 2013-03-15 2018-01-23 Genomatica, Inc. Process and systems for obtaining 1,4-butanediol from fermentation broths
CN106458948A (zh) * 2014-04-11 2017-02-22 Cj第制糖株式会社 用于处理基于高丝氨酸的化合物的方法

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JP2013040169A (ja) 2013-02-28

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