WO2004013183A1 - Procede pour la production d'un oligomere butenique - Google Patents

Procede pour la production d'un oligomere butenique Download PDF

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Publication number
WO2004013183A1
WO2004013183A1 PCT/JP2003/009605 JP0309605W WO2004013183A1 WO 2004013183 A1 WO2004013183 A1 WO 2004013183A1 JP 0309605 W JP0309605 W JP 0309605W WO 2004013183 A1 WO2004013183 A1 WO 2004013183A1
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WO
WIPO (PCT)
Prior art keywords
fraction
butene
acid catalyst
polymer
polymerization reaction
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Ceased
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PCT/JP2003/009605
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English (en)
Japanese (ja)
Inventor
Tetsuya Saruwatari
Hideki Yamane
Kenichi Wakui
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Idemitsu Petrochemical Co Ltd
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Idemitsu Petrochemical Co Ltd
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Publication date
Application filed by Idemitsu Petrochemical Co Ltd filed Critical Idemitsu Petrochemical Co Ltd
Publication of WO2004013183A1 publication Critical patent/WO2004013183A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/10—Catalytic processes with metal oxides
    • 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
    • C07C2521/12—Silica and alumina

Definitions

  • the present invention relates to an improvement in a method for producing a pteno oligomer. More specifically, in the present invention, when producing a pentene oligomer by polymerizing a pentene in the presence of an acid hornworm medium, a specific boiling point range (for example, 20 ° C. to 28 ° C. or higher) The present invention relates to a method for producing a butenoligomer that selectively increases the yield of butedan oligomers (below ° C).
  • a specific boiling point range for example, 20 ° C. to 28 ° C. or higher
  • Butene origoma is generally obtained by polymerizing the remaining fraction obtained by extracting butadiene from the C 4 fraction produced by naphtha cracking (butane-butene mixed fraction) and having an average molecular weight of 1 It is a liquid polymer of about 50 to 2500.
  • This ptene oligomer has excellent electrical properties, stability, mixed solubility, water resistance, and gas and water vapor permeation resistance4.
  • a liquid slurry in which a raw material comprising a butane-peptene fraction is suspended in a Friedel craft catalyst such as anhydrous aluminum chloride See, for example, Japanese Patent Application Laid-Open No. 60-0 1 2 4 60 2) or a method of contacting a solid catalyst made of dry chlorinated alumina (for example, And a method of contacting with a solid catalyst such as fluorinated alumina, alumina boron, silica anoremina, solid phosphoric acid, chromium oxide, zinc oxide (see, for example, Japanese Patent Laid-Open No. Sho 7-7-8 23 25) 5 6-4 0 6 1 8) are known. Industrially, the standard method process and the Cosden process have been put to practical use.
  • a specific boiling point range for example, 20.00 to less than 28.0. It is an object of the present invention to provide a method for selectively increasing the yield of butene oligomers.
  • the present inventors have found that the results of intensive studies to achieve the above object, the total amount or part of the remaining polymer was separated 0 4 fractions unreacted polymer of butene down, another For example, a fraction having a boiling point of 160 ° C. or lower in the polymerized product is allowed to have a boiling point of 20 ° C. or higher and lower than 28 ° C. As a result, the inventors have found that it is possible to selectively convert to a distillate fraction.
  • the present invention 1.
  • the step of polymerizing butene in the presence of an acid catalyst (first polymerization reaction)
  • the step of separating unreacted C 4 fraction from the polymer by distillation and (3) Unreacted
  • a step of further polymerizing the whole or a part of the remaining polymer separated from the C 4 fraction in the presence of an acid catalyst in a separate polymerization reactor (second polymerization reaction).
  • step (3) The total amount or a part of the polymer obtained in step (3) is combined with the total amount or a part of the remaining polymer obtained by separating the four unreacted fractions obtained in step (2) ( The method for producing a butene oligomer as described in 1 above, further comprising the step of supplying to (3),
  • step (3) a solid acid catalyst is used as the acid catalyst, the sulfur concentration in the raw material fed to the polymerization reactor is 2 ppm or less, and the reaction temperature is 130 ° C.
  • FIG. 1 is a diagram showing an example of a device configuration for realizing the butene oligomer production method of the present invention.
  • the method for producing a butene oligomer of the present invention comprises the following steps: (1) a step of polymerizing butene in the presence of an acid catalyst (first polymerization reaction), (2) polymer power, etc.
  • the remaining fraction obtained by extracting butadiene from the C 4 fraction produced by naphtha decomposition which is generally used in the industry, is the so-called Spend.
  • B-B fraction butane-butene mixed fraction
  • the acid catalyst for the butene polymerization reaction is not particularly limited, and may be appropriately selected from conventionally known catalysts that can be used as a butene polymerization catalyst. You can.
  • Examples of such an acid catalyst include a Friedel-Craft catalyst and a solid acid catalyst.
  • Examples of the above-mentioned Friedel-Craft catalyst include aluminum chloride, aluminum bromide, Examples thereof include Lewis acids such as ferric chloride, boron trifluoride, ferric chloride, and zinc chloride, and strong protonic acids such as sulfuric acid and hydrofluoric acid. This Friedel-Craft catalyst may be used alone or in combination of two or more, but aluminum chloride is particularly preferred.
  • the acid catalyst used in the polymerization reaction is preferably a solid acid catalyst.
  • solid acid catalysts include, for example, silica alumina, silica magnesium, silica, aluminum, chlorinated alumina, fluorinated alumina, silica / lea aluminum nagel. Hydrochloric acid, sulfuric acid, phosphoric acid,
  • Examples include cation exchange resin, synthetic zeolite, and clay minerals such as acid clay, bentonite, kaolin, and montmorillonite with BF 3 attached. These solid acid hornworm media may be used singly or in combination of two or more, and among these, silica alumina is particularly preferable.
  • the liquid polymerization method is generally employed, and the reaction temperature is usually 0. Is selected in the range of ⁇ 1500 ° C, preferably 1100 ⁇ 130 ° C, and the reaction pressure is usually 0.0 ⁇ 2.8 MPa a G, preferably 1.5 ⁇ 2. It is selected within the range of 8 MP a 'G.
  • the polymerization mode may be either a batch type or a continuous type.
  • the reaction temperature is usually selected in the range of 20 to 200 ° C, preferably 60 to 1995 ° C
  • the reaction pressure is It is usually selected from the range of atmospheric pressure to l OMP a 'G, preferably the pressure that can maintain the liquid phase (approximately l to 6 MP a' G).
  • the LHSV liquid hourly space velocity
  • the polymerization mode a continuous flow system in which the raw material is supplied to the catalyst packed tower can be adopted.
  • step (2) is removed by a ⁇ 4 fractions unreacted distilled from the resulting polymer in the above step (1).
  • This process is a conventionally known method. Can be used.
  • step (3) the first polymerization reaction in step (1) above was carried out using all or part of the remaining polymer obtained by removing the unreacted ⁇ 4 fraction from the polymer in the first polymerization reaction.
  • the second polymerization reaction is carried out in the presence of an acid catalyst in a separate polymerization reaction vessel (hereinafter referred to as the second polymerization reactor).
  • the second polymer for carrying out the second polymerization reaction as it is is used.
  • the second polymerization reaction may be performed by supplying the polymerization reactor.
  • the separation method for fractional distillation is arbitrary, but as an example, the fraction with a boiling point of less than 160 ° C (1 0 16), 160 ° C or more and less than 200 ° C Method of dividing into a fraction (1 6 2 0), a fraction above 2 200 ° C and below 2 80 ° C (2 0 2 8) and a fraction above 2 80 ° C (2 8 +) Can be mentioned.
  • a fraction containing at least a fraction below 160 ° C. (10 16) is preferred, and a fraction below 160 ° C. It is particularly preferable that the total amount or a part of (1 0 1 6).
  • the shallow polymer is supplied to the second polymerization reactor and further polymerized with the same acid catalyst and reaction conditions as the first polymerization reaction.
  • the reaction pressure may be sufficient to maintain the liquid phase, and may be 1 M Pa ⁇ ⁇ 3 ”or less.
  • fraction (2 0 2 8) of the ptenoligomer of more than C and less than 2 80 ° C The yield is selectively increased.
  • the concentration of sulfur in the raw material supplied to step (3) be 2 ppm or less.
  • the sulfur concentration in the raw material exceeds 2 ppm, the catalytic activity is significantly reduced, and the volume of the second polymerization reactor needs to be increased in order to compensate for the decreased angular ⁇ medium activity.
  • the butane-butene mixed fraction fed to the first polymerization reaction step is preliminarily desulfurized. There is a way to pass.
  • the desulfurizing agent a commonly used one can be used. Examples include molecular sieves 13 X, physical adsorbents such as activated carbon, and chemical adsorbents carrying copper, zinc, nickel, and the like.
  • the reactor volume is small. It is possible to construct an economical polymerization process with a high selectivity for the target fraction.
  • the reaction efficiency is high, and in order to increase the selectivity of the target fraction, the ratio of diisoptylene in the feed material to the second polymerization reactor is increased. It is preferable to increase as much as possible.
  • the components contained in the feed material to the second polymerization reactor The most reactive one is diisoptylene, and by increasing the yield of diisoptylene in the first polymerization reaction, the second polymerization reaction proceeds efficiently and the selectivity of the target fraction is high. You can get a ptenoligomer.
  • diisoptylene produced in the first polymerization reaction in step (1) is highly reactive and the diisoptylene concentration is already lowered at the outlet of the first polymerization reactor. Therefore, in performing the first polymerization reaction in step (1), diisobutylene can be obtained in a high yield by reducing the conversion of isobutylene in the 4 fractions to 95% or less.
  • the whole or a part of the polymer obtained in the second polymerization reaction in the step (3) is used as the unreacted C 4 fraction obtained in the step (2). Together with the whole or a part of the remaining polymer separated from the polymer, it can be supplied (recycled) to the second polymerization reactor in the step (3). This makes it possible to further selectively increase the butene oligomer yield of a fraction having a boiling point of 20 ° C. or higher and lower than 2 80 ° C. (20 28 8).
  • FIG. 1 shows an example of an apparatus configuration for realizing the method of the present invention including the above step (4).
  • Butanpute emissions mixtures force Ranaru material (A) is fed to the first polymerization reactor (1), after the butene down component is polymerized, the polymerization reaction solution is fed to the unreacted C 4 distillation column (2) Unreacted C 4 fraction (F) is distilled out of the system by distillation. Unreacted C 4 distillation column
  • the bottom solution from (2) is supplied to the oligomer distillation column (3a), and the fraction (1 0 16) with a boiling point of less than 160 ° C is taken out of the system as the top fraction. At least a part of it is supplied to the second polymerization reactor (4), and the rest becomes the product (P1).
  • the fraction (2 0 28) with a boiling point of 20 ° C or higher and lower than 2800 ° C is withdrawn out of the system as the top fraction, and the product (P 3) It becomes.
  • the bottom liquid of the oligomer distilling column (3c) is a fraction (28+) with a boiling point of 2880 ° C or higher, and is taken out as a product (P4).
  • the fraction (1 0 16) having a boiling point of less than 160 ° C. fed to the second polymerization reactor (4) is made heavy in the second polymerization reactor (4), and the boiling point 2 Converted selectively to fractions above 0 0 ° C and below 2 80 ° C.
  • the polymer obtained in the second polymerization reaction is supplied to the oligomer distillation column (3a).
  • a SUS tubular reactor having an inner diameter of 10 mm and a length of 500 mm was charged with 1 g (1.7 ml) of commercially available silica alumina (manufactured by JGC Chemical Co., Ltd., N 6 33 HN).
  • a raw material corresponding to the polymer supplied to the second polymerization reactor
  • a polymerization reaction was carried out for 3 hours at a reaction temperature of 120 ° C., LHSV 3 hr — 1 and a reaction pressure of 0.5 MPa ⁇ G.
  • the ratio of each fraction in the polymerization reaction product is shown in Table 1 below. Concentration (mass%)
  • the reaction pressure is 5.MPa
  • the reaction temperature is 2 0 2 8 (boiling point 2 0 0-2 at 1 0 0 ° C and 1 3 0 ° C.
  • the reaction temperature is 130 ° C or less, especially 10 ° C or less.
  • the selectivity of 20 28 is high.
  • SUS pipe reactor with inner diameter of 21 mm and length of 50 O mm is filled with 20 ml of silica alumina catalyst (manufactured by Ryuga Chemical Co., Ltd., N 6 3 3 HN). 9%, n—includes butene 4 1%.
  • Four fractions were fed at a rate of 200 ml / hr.
  • the reaction pressure was 5.6 MPa and the reaction temperature was 75 ° C.
  • Table 4 shows the conversion rate of dibutylene and the yield of dibutylene. Table 4
  • a butene oligomer having a specific boiling range (for example, 200 ° C. or more and less than 28 ° C.) is used in producing a ptenene oligomer by polymerizing putene in the presence of an acid catalyst. It is possible to provide a method for selectively increasing the yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé servant à produire un oligomère buténique et comprenant les étapes suivantes : 1) polymérisation de butène en présence d'un catalyseur acide (première réaction de polymérisation), 2) séparation entre fractions C4 n'ayant pas réagi et polymère par distillation et 3) nouvelle polymérisation de la quantité totale ou d'une partie du polymère restant après la séparation des fractions C4 n'ayant pas réagi, en présence d'un catalyseur acide dans un autre polymérisateur (deuxième réaction de polymérisation). Le procédé selon l'invention est caractérisé en ce que la production d'oligomère buténique dans une étendue de points d'ébullition donnée (par exemple, 200 °C à moins de 280 °C) peut être augmentée sélectivement lorsqu'un oligomère buténique est produit par polymérisation de butène en présence d'un catalyseur acide.
PCT/JP2003/009605 2002-08-01 2003-07-29 Procede pour la production d'un oligomere butenique Ceased WO2004013183A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002224655 2002-08-01
JP2002-224655 2002-08-01
JP2003-068120 2003-03-13
JP2003068120A JP3929916B2 (ja) 2002-08-01 2003-03-13 ブテンオリゴマーの製造方法

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WO2004013183A1 true WO2004013183A1 (fr) 2004-02-12

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PCT/JP2003/009605 Ceased WO2004013183A1 (fr) 2002-08-01 2003-07-29 Procede pour la production d'un oligomere butenique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1630178A1 (fr) * 2004-08-10 2006-03-01 Innovene Manufacturing Belgium NV Procédé de polymèrisation
US8067655B2 (en) * 2008-05-29 2011-11-29 Lyondell Chemical Technology, L.P. Diisobutylene process

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01225695A (ja) * 1988-03-04 1989-09-08 Res Assoc Util Of Light Oil オレフィンの低重合物の製造方法
JPH01284587A (ja) * 1988-03-21 1989-11-15 Shell Internatl Res Maatschappij Bv 液体炭化水素の製造方法
JPH08505888A (ja) * 1992-12-30 1996-06-25 ネステ・オイ Ｃ▲下４▼オレフィンを線状α−オレフィンとともにオリゴマー化する方法
JP2000159832A (ja) * 1998-11-30 2000-06-13 Bp Amoco Corp オリゴマ―化方法
WO2001030868A1 (fr) * 1999-10-28 2001-05-03 Basf Aktiengesellschaft Procede pour la production de polyisobutenes hautement reactifs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01225695A (ja) * 1988-03-04 1989-09-08 Res Assoc Util Of Light Oil オレフィンの低重合物の製造方法
JPH01284587A (ja) * 1988-03-21 1989-11-15 Shell Internatl Res Maatschappij Bv 液体炭化水素の製造方法
JPH08505888A (ja) * 1992-12-30 1996-06-25 ネステ・オイ Ｃ▲下４▼オレフィンを線状α−オレフィンとともにオリゴマー化する方法
JP2000159832A (ja) * 1998-11-30 2000-06-13 Bp Amoco Corp オリゴマ―化方法
WO2001030868A1 (fr) * 1999-10-28 2001-05-03 Basf Aktiengesellschaft Procede pour la production de polyisobutenes hautement reactifs

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JP3929916B2 (ja) 2007-06-13
JP2004124046A (ja) 2004-04-22

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