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Process for the Preparation of Cyclohexanedimethanol Verfahren Zur Herstellung Von Cyclohexandimethanol Procede De Preparation De Cyclohexanedimethanol

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Process for the Preparation of Cyclohexanedimethanol Verfahren Zur Herstellung Von Cyclohexandimethanol Procede De Preparation De Cyclohexanedimethanol Europäisches Patentamt *EP000922690B1* (19) European Patent Office Office européen des brevets (11) EP 0 922 690 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C07C 31/27, C07C 29/149, of the grant of the patent: C07C 69/608, C07C 67/303, 03.12.2003 Bulletin 2003/49 B01J 23/86, B01J 23/46, (21) Application number: 97928455.1 C07C 69/75 (22) Date of filing: 25.06.1997 (86) International application number: PCT/JP97/02188 (87) International publication number: WO 98/000383 (08.01.1998 Gazette 1998/01) (54) PROCESS FOR THE PREPARATION OF CYCLOHEXANEDIMETHANOL VERFAHREN ZUR HERSTELLUNG VON CYCLOHEXANDIMETHANOL PROCEDE DE PREPARATION DE CYCLOHEXANEDIMETHANOL (84) Designated Contracting States: • YOSHIDA, Yasuhisa BE CH DE ES FR GB IT LI LU NL PT Kyoto 611 (JP) • IWAMURA, Taiichiro (30) Priority: 28.06.1996 JP 18875996 Kyoto 610-01 (JP) 22.10.1996 JP 35937396 • NAKAZAWA, Mikio 24.12.1996 JP 35617696 Kyoto 611 (JP) 26.02.1997 JP 5993197 (74) Representative: Barz, Peter, Dr. et al (43) Date of publication of application: Patentanwalt 16.06.1999 Bulletin 1999/24 Kaiserplatz 2 80803 München (DE) (73) Proprietor: SK NJC Co., Ltd. Suwon-si, Kyungki-do (KR) (56) References cited: WO-A-94/29261 FR-A- 1 276 722 (72) Inventors: JP-A- 6 192 146 JP-A- 6 321 823 • ITOH, Hiroshi US-A- 3 334 149 Kyoto 619-02 (JP) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 922 690 B1 Printed by Jouve, 75001 PARIS (FR) EP 0 922 690 B1 Description Field of the Invention 5 [0001] The present invention relates to a process for preparing cyclohexanedimethanol (hereinafter referred to as "CHDM"). When used as the diol component of polyester resins, polyurethane resins, polycarbonate resins or the like, CHDM is effective in improving the heat resistance, transparency, weatherability and molding properties of these resins. Particularly 1,4-cyclohexanedimethanol is drawing attention as a compound useful for improving the properties of pol- yethylene terephthalate. 10 Background Art [0002] Conventional processes for preparing CHDM generally comprise ring hydrogenation of aromatic dicarboxylic acid dialkyl ester to give cyclohexanedicarboxylic acid dialkyl ester (first reaction) and hydrogenation of its ester groups 15 to give CHDM (second reaction). [0003] Among these catalysts used for the respective reactions, known as effective for the first reaction are palladium, nickel, ruthenium, rhodium and the like US-A-3,334,149, JP-A-163554/1979 and 192146/1994, US-A-5,286,898 and 5,399,742); and known as effective for the second reaction are copper-chromite, copper oxide/zinc oxide, copper oxide/ titanium oxide, copper oxide/iron oxide and catalysts prepared by modifying these copper-based catalysts with oxides 20 of barium, magnesium and zinc and reducing the modified catalysts for activation (US-A- 3,334,149, JP-A-192146/1994 and 196549/1995, US-A-5,334,779, 5,030,771 and 4,929,777). [0004] As the mode of reaction, a fixed-bed continuous reaction process is considered to be advantageous over a suspended catalyst reaction process in terms of productivity and yield. Herein, the fixed-bed continuous reaction proc- ess includes a reaction process (downflow-type process) wherein a preformed catalyst is placed into a pressure-re- 25 sistant reactor, into which hydrogen and a raw material are supplied to the top of the reactor at a predetermined tem- perature and hydrogen pressure, and the reaction product is withdrawn from the bottom of the reactor; and a reaction process (upflow-type process) wherein hydrogen and a raw material are supplied to the bottom of the reactor and the reaction product is removed from the top of the reactor. The suspended catalyst reaction process comprises suspending a catalyst powder in an aromatic dicarboxylic acid diester or a cyclohexanedicarboxylic acid diester and subjecting the 30 suspension to a reaction with heating while being pressurized with hydrogen. [0005] As the examples of fixed-bed continuous reaction process, reported are processes comprising ring hydro- genation of a terephthalic acid dialkyl ester in the presence of a preformed supported ruthenium catalyst to give 1,4-cy- clohexanedicarboxylic acid dialkyl ester in the first reaction (JP-A-163554/1979 and 192146/1994). [0006] Ruthenium catalysts are inexpensive compared with palladium catalysts, and exhibit a high activity even at 35 a low pressure and a low temperature, but have the disadvantage of being likely to cause undesirable reactions involving high exothermic heat, such as hydrogenolysis of ester groups to hydroxymethyl group(s) or methyl group(s), in addition to the hydrogenation of the aromatic ring. [0007] It is advantageous to use a cyclohexane-dicarboxylic acid diester as a reaction solvent in order to avoid adverse effect due to reaction heat. However, the cyclohexanedicarboxylic acid diester used may be consumed due 40 to the above-mentioned side reactions, not only resulting in a low yield but also, in extreme case, leading to a rapid generation of heat in a portion of the reactor which makes it difficult to continue the reaction. Therefore, JP-A- 192146/1994 proposes the provision of a perforated plate in the reactor to improve the dispersibility of gas and liquid. However, even in this case, the concentration of terephthalic acid dialkyl ester in the feed to the reactor actually must be limited to an extremely low range of 5 to 20 weight %, and a large amount of reaction product is subjected to reaction 45 by recycling, resulting in a low yield based on the terephthalic acid dialkyl ester used and leading to a low productivity. [0008] Examples of the fixed-bed continuous reaction process for the second reaction are those disclosed in JP-A- 196549/1995; 196560/1995; 196558/1995; 196559/1995; 188077/1995; 188078/1995 and 188079/1995. These pro- posed processes are characterized in that the reaction is conducted under gas phase conditions of relatively low hy- drogen pressure. However, the processes entail various disadvantages such as loss of thermal energy in vaporizing 50 the raw material and necessity for removal of generated reaction heat in a gas phase of low heat conductivity, resulting in a need for complicated equipments. Furthermore, high-boiling-point by-products are deposited on the surface of catalyst, thereby markedly reducing the catalyst activity and thus necessitating frequent catalyst replacement or catalyst regeneration treatment. [0009] On the other hand, US-A-3,334,149, 5,030,771 and 5,334,779 and JP-A-192146/1994 disclose a gas-liquid 55 mixed phase reaction. However, the disclosed processes include various problems. For example, the feed rate (F/V) of cyclohexanedicarboxylic acid dialkyl ester is as low as 1 /h or less, leading to a low productivity per reactor. Alter- natively, cyclohexanedicarboxylic acid dialkyl ester is fed as diluted with the reaction product, i.e. CHDM or the like to a concentration of about 16% by weight or less, consequently involving complicated equipment and cumbersome 2 EP 0 922 690 B1 operation relating to the reactor and resulting in increased by-products due to side reaction of CHDM. Disclosure of the Invention 5 [0010] An object of the present invention is to provide a process for preparing high-quality CHDM, which is capable of producing CHDM with safety in a high yield by a simplified procedure at a high productivity per reactor and capable of diminishing costs for equipment. [0011] The present inventors found that in producing cyclohexanedimethanol a high yield can be achieved using simplified equipment when cyclohexanedicarboxylic acid ester is hydrogenated under specific reaction conditions, and 10 completed the present invention. [0012] The present invention provides a process for preparing cyclohexanedimethanol represented by the formula (1) 15 20 which comprises the steps of a) continuously feeding an aromatic dicarboxylic acid dialkyl ester represented by formula (3) 25 30 35 wherein R is an alkyl group having 1 to 4 carbon atoms, and hydrogen to the top of a multi-tubular pressure- resistant reactor packed with a preformed supported ruthenium catalyst to effect hydrogenation under a gas-liquid mixed phase condition, and removing excess hydrogen and the obtained cyclohexanedicarboxylic acid dialkyl ester represented by formula (2) 40 45 wherein R is a defined above, 50 from the bottom of the reactor, wherein each tube of the multi-tubular reactor has an inner diameter of 2.5 to 10 cm and a length of 3 to 15 m, and (b) continuously feeding the cyclohexanedicarboxylic acid dialkyl ester obtained in step (a) above and hydrogen to the top of a multi-tubular pressure-resistant reactor packed with a preformed copper-containing catalyst to effect hydrogenation under a gas-liquid mixed phase condition, wherein the reaction temperature is 200 to 280°C, the 55 hydrogen pressure is 18.14 to 29.42 MPa (185 to 300 kgf/cm2) and the hydrogen gas feed rate is 1 to 40 cm/s in terms of superficial linear velocity, and removing excess hydrogen and the resulting cylcohexanedimethanol from the bottom of said reactor wherein each tube of the multi-tubular reactor has an inner diameter of 2.5 to 10 cm and a length of 3 to 15 m, wherein the number of tubes is 10 to 2000 in both of step (a) and step (b). 3 EP 0 922 690 B1 [0013] In the specification and claims, superficial linear velocity has a generally recognized meaning and is defined as a value obtained by dividing the hydrogen gas flow rate (cm3/s) by a cross-sectional area (cm2) of the tubular or columnar reactor in the case of a single-column reactor, or as a value obtained by dividing the hydrogen gas flow rate (cm3/s) by a total cross-sectional area (cm2) of a plurality of tubes in the case of a multitubular reactor.
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