WO2011027755A1 - Procédé de production d'un hydrindane et d'un solvant - Google Patents

Procédé de production d'un hydrindane et d'un solvant Download PDF

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Publication number
WO2011027755A1
WO2011027755A1 PCT/JP2010/064870 JP2010064870W WO2011027755A1 WO 2011027755 A1 WO2011027755 A1 WO 2011027755A1 JP 2010064870 W JP2010064870 W JP 2010064870W WO 2011027755 A1 WO2011027755 A1 WO 2011027755A1
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Prior art keywords
hydrindane
reaction
tetrahydroindene
producing
solvent
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PCT/JP2010/064870
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English (en)
Japanese (ja)
Inventor
真一朗 柳川
秀怜 近藤
彰 松尾
朝子 柳瀬
毅 山口
貴 鈴木
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Ｊｘ日鉱日石エネルギー株式会社
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Publication of WO2011027755A1 publication Critical patent/WO2011027755A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • C11D7/245—Hydrocarbons cyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
    • C07C13/465—Indenes; Completely or partially hydrogenated indenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane

Definitions

  • the present invention relates to a method for producing hydrindane and a solvent containing hydrindane obtained by the production method.
  • the hydrindan is important as a naphthenic solvent.
  • Hydrindan is a naphthenic hydrocarbon having 9 carbon atoms represented by the following formula, and exhibits excellent performance as a paint solvent or cleaning agent due to its excellent solubility. It is known that hydrindan is obtained by completely hydrogenating indene (Non-patent Document 1, Non-patent Document 2). Further, it is well known that the indene is contained in a fraction having 9 carbon atoms obtained by thermal decomposition of a tar content or a petroleum fraction obtained during coal dry distillation. However, the tar fraction obtained from coal coal distillation or the fraction having 9 carbon atoms obtained by pyrolysis of petroleum fraction is a mixture of many hydrocarbons having boiling points close to indene.
  • Indene In order to obtain the indene with high purity, it was necessary to carry out a multistage distillation, which was difficult. Indene has low thermal stability, and has various problems such as thermal polymerization in the course of distillation to reduce the recovery rate and fouling of distillation equipment. Furthermore, in order to perform complete hydrogenation of indene, nuclear hydrogenation of the benzene ring is necessary, and it is necessary to react at a high temperature and high pressure using a hydrogenation catalyst. There is also a problem. Therefore, there is a need for an inexpensive and efficient method for producing hydrindane.
  • An object of the present invention is to provide a method for producing hydrindane that is easy to procure raw materials, is inexpensive and efficient.
  • a method for producing hydrindane including the following steps (1) to (3) is provided.
  • Step (1) for producing The reaction mixture obtained in step (1) is distilled to separate 3a, 4,7,7a-tetrahydroindene (2), Step (3) for producing hydrindane by hydrogenating 3a, 4,7,7a-tetrahydroindene obtained in Step (2) in the presence of a hydrogenation catalyst.
  • the method for producing hydrindane wherein the purity of 3a, 4,7,7a-tetrahydroindene obtained in step (2) is 97% by mass or more. Furthermore, according to the present invention, there is provided the method for producing hydrindane, wherein the hydrogenation catalyst contains at least one metal selected from nickel, palladium, rhodium and ruthenium. Furthermore, according to the present invention, there is provided a solvent containing hydrindane obtained by any one of the production methods described above.
  • the production method of the present invention employs a method of hydrogenating tetrahydroindene obtained by reacting cyclopentadiene and butadiene with Diels Alder reaction, the procurement of raw materials is easier than the conventional method of hydrogenating indene, Hydrindan can be produced efficiently at low cost.
  • the obtained hydrindane is useful as a solvent for cleaning agents, metal working oil, lubricating oil, cutting oil, rolling oil, press oil, ink solvent, paint solvent, cleaning solvent and the like.
  • the production method of the present invention includes a step (1) of producing a reaction mixture containing 3a, 4,7,7a-tetrahydroindene by subjecting cyclopentadiene and 1,3-butadiene to Diels-Alder reaction.
  • the Diels-Alder reaction of cyclopentadiene and butadiene is well known as a method for producing vinyl norbornene, which is an intermediate for producing ethylidene norbornene.
  • cyclopentadiene acts as a diolefin compound and butadiene acts as a dienophile compound.
  • step (1) of the present invention when tetrahydroindene is produced from cyclopentadiene and butadiene in step (1) of the present invention, cyclopentadiene acts as a dienophile compound and butadiene acts as a diolefin compound.
  • Diels-Alder reaction of cyclopentadiene and butadiene the formation of tetrahydroindene and vinyl norbornene occur simultaneously. Therefore, in step (1), it is important to select reaction conditions that favorably produce tetrahydroindene.
  • the molar ratio of butadiene to cyclopentadiene is usually in the range of 0.2 to 10, preferably 0.5 to 5.
  • the yield of tetrahydroindene based on cyclopentadiene may decrease due to the formation of dicyclopentadiene or the formation of a high polymer by Diels-Alder reaction of cyclopentadiene alone.
  • the molar ratio exceeds this range, the formation of dicyclopentadiene or the formation of a high polymer can be suppressed.
  • the yield of the standard tetrahydroindene may be reduced.
  • cyclopentadiene it is also possible to use the precursor dicyclopentadiene. In such a case, 1 mol of dicyclopentadiene corresponds to 2 mol of cyclopentadiene.
  • butadiene and cyclopentadiene may be reacted in the absence of a solvent, but can also be reacted in the presence of a solvent.
  • a solvent is preferable because the formation of a high polymer is suppressed and the formation of a dimer is also suppressed.
  • the solvent for example, inert solvents such as n-heptane, benzene and toluene, alcohols such as methanol and ethanol, and organic halogen compounds such as chlorobenzene and dichloroethane are preferably used.
  • the reaction temperature of the above reaction is usually appropriately selected from the range of 100 to 250 ° C.
  • a polymerization reaction of cyclopentadiene or butadiene, particularly cyclopentadiene, which is a reaction raw material easily occurs, and a high polymer may be formed and the yield of tetrahydroindene may be reduced.
  • blockage of equipment such as reactors and heat exchangers, poor heat transfer due to adhesion of polymer to the inner wall surface of the apparatus, and other obstacles may occur.
  • reverse reactions such as product cleavage by reverse Diels-Alder reaction become dominant, and the equilibrium yield may be reduced.
  • the reaction pressure of the above reaction is a pressure that maintains the liquid phase in the reactor at the adopted reaction temperature.
  • the presence of a gas phase portion in the reactor is not preferable because the polymer is easily deposited on the inner wall surface of the gas phase portion.
  • the reaction time of the above reaction is appropriately set depending on the reaction temperature or the raw material composition, but is preferably 30 minutes to 4 hours. More preferably, it is 1 to 3 hours.
  • a stirring tank type continuous reaction apparatus or a tube type continuous flow reactor is used, a liquid space velocity capable of realizing a residence time corresponding to the above reaction time can be employed.
  • the cyclopentadiene used in the step (1) is usually available as a dimer, that is, dicyclopentadiene. Therefore, in order to carry out the Diels-Alder reaction described above, dicyclopentadiene must be thermally decomposed to cyclopentadiene. This thermal decomposition reaction is usually carried out before the Diels Alder reaction, but depending on the Diels Alder reaction conditions employed, dicyclopentadiene is supplied to the Diels Alder reactor, and the thermal decomposition of the dicyclopentadiene and the cyclohexane produced thereby. It is also possible to carry out the Diels-Alder reaction of pentadiene and butadiene in parallel. Various methods for preventing contamination of the reactor and heat exchanger by preventing the formation of high polymer in the Diels-Alder reaction have been proposed. 121250, JP-A-55-153727).
  • the production method of the present invention includes a step (2) in which the reaction mixture obtained in the step (1) is distilled to separate 3a, 4,7,7a-tetrahydroindene.
  • the reaction mixture obtained by the Diels-Alder reaction in step (1) is then distilled to separate the desired tetrahydroindene.
  • the reaction mixture consists mainly of tetrahydroindene and vinylnorbornene which are Diels Alder reaction products of butadiene and cyclopentadiene, and vinyl cyclohexene, 1,5-cyclooctadiene and cyclopentadiene which are Diels Alder reaction products of butadiene alone.
  • Dicyclopentadiene which is a Diels-Alder reaction product, and a heavy product composed of unreacted butadiene and cyclopentadiene and mainly a polymer of cyclopentadiene.
  • the boiling points at normal pressure of the reaction mixture by these Diels-Alder reactions are as shown in Table 1, and can be appropriately separated by combining distillation steps.
  • a continuous distillation method in which the residence time in the high temperature part is short is preferable.
  • the purity of tetrahydroindene recovered by distillation is appropriately set, but is preferably 97% by mass or more. If it is less than 97% by mass, the purity of the hydrindane obtained in the hydrogenation reaction in the next step is lowered, and as a result, the odor becomes strong, which is not preferable. In order to improve the odor, further distillation must be performed, which increases the cost. Further, hydrogen is consumed in the hydrogenation reaction of components other than tetrahydroindene, which is not preferable because of high costs. Thus, in order to increase the purity of tetrahydroindene, it is preferable to select the conditions appropriately from the ranges of the above reaction conditions and distillation conditions.
  • the production method of the present invention includes a step (3) of producing hydrindane by hydrogenating 3a, 4,7,7a-tetrahydroindene obtained in step (2) in the presence of a hydrogenation catalyst.
  • the hydrogenation reaction is usually performed under pressure using a hydrogenation catalyst.
  • the hydrogenation catalyst is not particularly limited as long as it is a catalyst capable of hydrogenation reaction.
  • the metal oxide support include alumina, silica, silica-alumina, crystalline aluminosilicate, zeolite, and diatomaceous earth.
  • activated carbon is preferably used as the support.
  • the Group VIII metal is, for example, selected from the group consisting of nickel, cobalt, platinum, rhodium, ruthenium, palladium and mixtures thereof. Among these, nickel, palladium, rhodium, and ruthenium are preferably used, and nickel is particularly preferable from the viewpoint of hydrogenation activity and cost.
  • the reaction mode of the hydrogenation reaction is a general mode. That is, a method using a batch type reaction vessel equipped with a stirrer, or a stationary phase continuous flow type reaction system in which a cylindrical or multi-tubular reactor is filled with a catalyst and a reaction raw material is continuously circulated is used.
  • the hydrogenation temperature can be appropriately selected according to the reaction conditions other than the type of catalyst and the temperature, and is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. When the reaction temperature is lower than 100 ° C., the hydrogenation reaction proceeds slowly and hydrindane may not be efficiently generated.
  • the hydrogen pressure in the hydrogenation reaction is usually 2 to 6 MPa, preferably 3 to 5 MPa.
  • the hydrogen pressure falls below this range, not only the progress of the hydrogenation reaction becomes slow, but also the dehydrogenation reaction of the cyclohexene ring of tetrahydroindene occurs at the same time, and indane tends to be generated. Since indane has an aromatic ring, it is difficult to be hydrogenated. This also makes it difficult to produce hydrindane.
  • the reactor is required to have high pressure resistance, and the cost of the hydrogenation apparatus increases, which is not preferable.
  • the molar ratio of hydrogen to tetrahydroindene is such that, in the case of a batch reactor, the hydrogen pressure decreases as the reaction proceeds.
  • the molar ratio of hydrogen to tetrahydroindene is usually 10 to 100, preferably 40 to 70.
  • the reaction time in the case of a batch reactor can be appropriately determined by measuring the reaction rate of tetrahydroindene or the production rate of hydrindane in the reactor, and is usually 1 to 10 hours, preferably 3 to 7 hours.
  • a preferred liquid space velocity (LHSV (tetrahydroindene feed rate / catalyst layer volume: L-feed / L-cat / Hr)) is 0.1 to 5.
  • indane may be generated as an intermediate during the hydrogenation reaction. Since indane has an aromatic ring, it is preferable that a hydrogenation reaction does not proceed more easily than tetrahydroindene, is an unfavorable intermediate, and a catalyst in which indane is difficult to generate is selected and reaction conditions are selected. Indane is an unfavorable component in terms of odor, so it is preferable to completely hydrogenate it to convert it to hydrindan.
  • the content of indane remaining in the hydrindane obtained is preferably 0.5% by mass or less from the viewpoint of odor.
  • the obtained hydrogenation reaction product can be subjected to distillation if necessary to remove light and heavy components to obtain the desired hydrindane.
  • the hydrindane obtained by the method of the present invention is suitable for various uses such as cleaning solvents, metal working oils, lubricating oils, cutting oils, rolling oils, press oils, ink solvents, paint solvents, and cleaning solvents.
  • Example 1 Diels-Alder reaction of cyclopentadiene and butadiene
  • 250 g of a mixture of dicyclopentadiene and butadiene mixed at a molar ratio of 0.5: 1 (corresponding to a molar ratio of 1: 1 in terms of cyclopentadiene to butadiene) is placed in a stainless steel autoclave and reacted at 230 ° C. for 3 hours. It was. After completion of the reaction, the reaction mixture in the autoclave was analyzed by gas chromatography with a flame ion detector (FID-GC).
  • FID-GC flame ion detector
  • Step (2) Tetrahydroindene is separated and purified by distillation of the reaction mixture
  • the reaction mixture was distilled to obtain 57 g of tetrahydroindene having a purity of 98% by mass.
  • the recovery rate of tetrahydroindene in distillation was 60% by mass in terms of pure tetrahydroindene.
  • the distillation column used was a batch type, the number of theoretical plates was 37, the column top pressure was 100 mmHg, and the column top temperature was 95-100 ° C. when tetrahydroindene was distilled.
  • Step (3) Production of hydrindane by hydrogenating tetrahydroindene
  • 30 ml of tetrahydroindene prepared in step (2) and 0.84 g of “N112” (Ni content 50 mass%) manufactured by JGC Catalysts & Chemicals Co., Ltd. as a nickel-based hydrogenation catalyst are placed.
  • the temperature was raised to 200 ° C., and the reaction was continued for 5 hours after reaching 200 ° C.
  • hydrogen was introduced every 30 minutes until the pressure reached 4.0 MPa.
  • Example 2-4 The hydrogenation reaction was carried out under the same conditions as in Example 1 except that tetrahydroindene obtained under the same conditions as in Step (2) of Example 1 was used and the catalysts shown in Table 2 were used as the hydrogenation catalyst. The results are shown in Table 2. In any of the catalysts, almost no indane was observed, and hydrindane was obtained in a yield of nearly 100 mol%.
  • Example 5 Using tetrahydroindene obtained under the same conditions as in Step (2) of Example 1, an alumina-supported palladium catalyst (“F10H” (Pd content 0.05% by mass, manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a hydrogenation catalyst. The hydrogenation reaction was carried out under the same conditions as in Example 1 except that)) was used. Tetrahydroindene was 100% hydrogenated, and the yield of hydrindane relative to the charged tetrahydroindene was 67 mol%. The yield of indane was 31 mol%, and further hydrogenation was required to convert indane to hydrindan.
  • F10H alumina-supported palladium catalyst
  • Example 6 In addition to using tetrahydroindene obtained under the same conditions as in step (2) of Example 1, using a platinum catalyst supported by activated carbon (manufactured by N Chemcat Co., Ltd., 3% Pt-carbon powder) as the hydrogenation catalyst The hydrogenation reaction was carried out under the same conditions as in Example 1. Tetrahydroindene was 100% hydrogenated, and the yield of hydrindane relative to the charged tetrahydroindene was 73 mol%. The yield of indane was 23 mol%, and further hydrogenation was required to convert indane to hydrindan.
  • a platinum catalyst supported by activated carbon manufactured by N Chemcat Co., Ltd., 3% Pt-carbon powder
  • Comparative Example 1 Using indene as a raw material, the same catalyst as in Example 1 was used, and the hydrogenation reaction was performed under the same conditions.
  • the inden used is manufactured by Tokyo Chemical Industry Co., Ltd. and has a purity of 96% by mass.
  • the reaction rate of indene was 93.8%, while the selectivity for hydrindan was 0.1 mol%, while the selectivity for indane was 90.3 mol%. Since indene has an aromatic ring, indene is difficult to be hydrogenated, and it has become clear that it is not suitable for the production of hydrindane.
  • Example 7 and Comparative Examples 2 to 4 The properties of hydrindane obtained in Example 1 as a solvent were evaluated.
  • the physical properties of hydrindane produced in Example 1 were evaluated in comparison with various commercially available solvents by the following test methods. The results are shown in Table 3.
  • the aromatic content was calculated from the peak area ratio of olefin by 1 H-NMR.
  • the flash point was measured according to JIS K 2265.
  • the boiling point range was estimated from gas chromatography analysis or from the components of the solvent and the boiling points of the components.
  • the aniline point was measured according to JIS K 2256.
  • the hydrindane obtained by the production method of the present invention has the same physical properties as hydrindane obtained by nuclear hydrogenation of indane or indene, which is a conventional production method, and the production of the present invention. It has been found that the method can be replaced with a conventional manufacturing method without any problems and that hydrindane can be manufactured under milder manufacturing conditions than the conventional manufacturing conditions. Moreover, since hydrindane obtained by the production method of the present invention is almost a single component, the boiling point range is narrow, and the end point of the distillation test is particularly low. Therefore, it is excellent in drying property compared with other solvents having the same flash point. It can also be seen that the aniline point is low and the dissolving power is large.
  • the hydrindane according to the present invention has excellent characteristics as a solvent and is useful as a solvent for paints or inks. It is also useful as a cleaning agent in metalworking and machinery industries, and as a rubber extender. Furthermore, it can be used for plasticizers of synthetic resins such as vinyl chloride resin.
  • the production method of the present invention can produce high-purity hydrindan efficiently and inexpensively compared with the conventional method.
  • the hydrindane produced according to the present invention is useful as a cleaning agent or a solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé destiné à produire un hydrindane, de manière efficace, facile et peu coûteuse par rapport à des procédés conventionnels. L'invention concerne en outre un solvant naphténique peu coûteux et un solvant pour un détergent. Le procédé de production produit un hydrindane en hydrogénant un tétrahydroindène obtenu au moyen d'une réaction de Diels-Alder entre le butadiène et le cyclopentadiène. De plus, l'hydrindane obtenu par le biais de ce procédé peut être utilisé comme solvant ou comme détergent.
PCT/JP2010/064870 2009-09-03 2010-09-01 Procédé de production d'un hydrindane et d'un solvant WO2011027755A1 (fr)

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JP2009204106A JP2011051951A (ja) 2009-09-03 2009-09-03 ヒドリンダンの製造方法及び溶剤
JP2009-204106 2009-09-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022154048A1 (fr) * 2021-01-15 2022-07-21 Ｅｎｅｏｓ株式会社 Procédé de production d'indane et d'hydrindane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013133293A (ja) * 2011-12-26 2013-07-08 Waseda Univ インダンおよび／またはインデンの製造方法

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JPS53111048A (en) * 1977-03-08 1978-09-28 Japan Synthetic Rubber Co Ltd Preparation of vinylnorbornene and/or tetrahydroindene
JP2001220359A (ja) * 2000-02-04 2001-08-14 Adchemco Corp インダンの製造方法

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JP2587296B2 (ja) * 1989-09-08 1997-03-05 日本石油株式会社 潤滑油組成物
JP2807908B2 (ja) * 1989-11-13 1998-10-08 東燃株式会社 アリールブテン環状二量体およびその製造方法
JP3478350B2 (ja) * 1994-03-14 2003-12-15 日本ゼオン株式会社 開環重合体水素添加物の製造方法

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JPS53111048A (en) * 1977-03-08 1978-09-28 Japan Synthetic Rubber Co Ltd Preparation of vinylnorbornene and/or tetrahydroindene
JP2001220359A (ja) * 2000-02-04 2001-08-14 Adchemco Corp インダンの製造方法

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SHOICHI TSUCHIDA ET AL.: "Butadiene to Cyclopentadiene tono Diels-alder Hanno -3a,4,7,7a-Tetrahydroindene no Gosei", JOURNAL OF JAPAN PETROLEUM INSTITUTE, vol. 13, no. 12, 1970, pages 950 - 954 *
SPIELMANN W. ET AL: "Thermolyse des endo, exo-tetracyclo [ 6.1.0.02,4.05,7] nonans (trans-tris-sigma-homobenzols)", ANGEWANDTE CHEMIE, vol. 90, no. 6, 1978, pages 470 - 471 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022154048A1 (fr) * 2021-01-15 2022-07-21 Ｅｎｅｏｓ株式会社 Procédé de production d'indane et d'hydrindane

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