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A Modified Raney Nickel Catalyst and a Process for Preparing Diols by Using the Same

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A Modified Raney Nickel Catalyst and a Process for Preparing Diols by Using the Same ~™ llll III II III I III IIIMII II 1 1 (19) J European Patent Office Office europeen des brevets (11) EP 0 807 464 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: (51) int. CI.6: B01 J 25/00, B01J 25/02, 19.11.1997 Bulletin 1997/47 C07C 29/141 , C07C 29/132 (21) Application number: 96303388.1 (22) Date of filing: 14.05.1996 (84) Designated Contracting States: • LIN, Fwu Shen AT BE CH DE DK ES Fl FR GB GR IE IT LI LU MC Kaohslung (TW) NL PT SE • Chou, Jiunn Yann Kaohslung (TW) (71) Applicant: . Huang, Chian Chong Dairen Chemical Corporation Kaohslung (TW) Taipei (TW) (74) Representative: (72) Inventors: Jones, Helen Marjorie Meredith • Chen, Shien Chang Gill Jennings & Every, Taipei (TW) Broadgate House, • Chu, Cheng Chang 7 Eldon Street Kaohslung (TW) London EC2M 7LH (GB) (54) A modified raney nickel catalyst and a process for preparing diols by using the same (57) The present invention relates to a modified Raney nickel catalyst which can serve as a hydrogena- tion catalyst for hydroxy aldehydes, such as 4-hydroxy- butanal, and 2-methyl-3-hydroxypropanal and hydroxy cyclic ethers such as 2-hydroxy-tetrahydrofuran. Fur- ther, a process for preparing diols by using the modified Raney nickel catalyst is provided. < CO r»- o CO o Q_ LU Printed by Rank Xerox (UK) Business Services 2.14.23/3.4 EP 0 807 464 A1 Description 1 . Field of the Invention 5 The present invention relates to a modified Raney nickel catalyst and a process for preparing diols by using the modified Raney nickel catalyst. 2. Background of the Invention 10 Conventionally, 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, and 2-methyl-3-hydroxypropanal are industrially prepared by hydroformylating allyl alcohol carbon monoxide, and hydrogen in the presence of rhodium as a catalyst. The reactions of the conventional processes are shown as follows: CH2CHCH2OH+CO+H2 - HCOCH2CH2CH2OH «* CH2-CH2 15 CH2 CH \ A O OH 20 CH2CHCH2OH+CO+H2 -+ HCOCHCH2OH CH3 25 4-hydroxy-butanal and 2-hydroxy-tetrahydrofuran can be used for producing 1,4-butanediol through hydrogenation while 2-methyl-3-hydroxypropanal can be used for producing 2-methyl-1 ,3-propanediol through hydrogenation. The reactions thereof are shown as follows: 30 HCOCH2CH2CH2OH+H2^CH2OHCH2CH2CH2OH CH,-CH? 35 | | CH2 CH + H2 - CH2OHCH2CH2CH2OH O OH 40 HCOCHCH,OH+H? - CH,OHCHCH,OH I I CH3 CH3 45 The hydrogenation of 4-hydroxy-butanal and 2-methyl-3-hydroxypropanal is subject to hydrogenation of the carbo- nyl group. Presently, the catalyst used in the process of hydrogenation of the carbonyl group is selected from precious metals including palladium, which is disclosed in Biochemistry Journal, 1943, Vol. 37, p. 726; platinum, which is dis- 50 closed in Journal of American Chemical Society, 1948, Vol. 70. p.664; ruthenium, which is disclosed in U.S. Patent No. 3,144,490; rhenium, which is disclosed in Journal of Organic Chemistry, 1959, Vol. 24, p. 1847; copper chromite, which is disclosed in Industrial and Engineering Chemistry, 1946, Vol. 38, p.251 ; copper, which is disclosed in British Patent No. 659,981 ; nickel, which is disclosed in Journal of Chemical Society, Japan, Industrial Chemistry Section, 1 943, Vol. 46, p.901; Raney nickel, which is disclosed in Journal of American Chemical Society, 1948, Vol. 70, p.695; Raney 55 cobalt, which is disclosed in Journal of Applied Chemistry, 1958, Vol. 8, p. 492; and so on. Through long-term experiments, it has been found by the inventors that the hydrogenations of 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, and 2-methyl-3-hydroxypropanal differ from those of other carbonyl groups. For instance, the use of palladium or zinc copper oxide as catalyst shows almost no reaction activity; and the use of ruthenium or cop- per chromite as catalyst shows only relatively low reaction activity to the hydrogenation, which provides little utilization 2 EP 0 807 464 A1 value. Only nickel and Raney nickel provide higher reaction activity to the hydrogenation. However, a drawback has sub- sequently been found to the use of nickel or Raney nickel as catalyst in the aforementioned hydrogenation process in that their reaction activities rapidly decay after repetitive use. More specifically, after batchwise repetitive use exceeding 33 batches or continuous use exceeding 30 hours, their reaction activity significantly decreases to a low level that can- 5 not practically be used further. Accordingly, the use of nickel or Raney nickel as catalyst in the hydrogenation process for producing 1 ,4-butanediol, 2-methyl-1,3-propanediol from 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, and 2- methyl-3-hydroxypropanal is still not a practical approach in the chemical industry. 3. Summary of the Invention 10 It is therefore a primary objective of the present invention to provide a modified Raney nickel catalyst which is of high and long-lasting reaction activity for the hydrogenation of 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, and 2- methyl-3-hydroxypropanal. It is another objective of the present invention to provide an improved process for preparing diols by using the mod- 15 ified Raney nickel catalyst. In accordance with the foregoing and other objectives of the present invention, there is provided a modified Raney nickel catalyst and a process for preparing diols by using the modified Raney nickel catalyst. It is found through exper- iments that Raney nickel modified by the addition of iron or iron and at least one metal selected from the group consist- ing of chromium, molybdenum, tungsten, cobalt, manganese, and titanium shows a relatively high reaction activity to 20 the process for preparing diols and allows long-term use thereof as the catalyst for the process for preparing diols. The provision of the catalyst according to the present invention thus enables the preparation of 1 ,4-butanediol and 2-methyl- 1 ,3-propanediol through hydrogenation of 4-hydroxy-butanal, 2-hydroxytetrahydrofuran, and 2-methyl-3-hydroxypro- panal to have high commercial value. 25 4. Detailed Description of the Invention The modified Raney nickel catalyst according to the present invention consists essentially of 40-98 wt% of nickel, 1 -50 wt% of aluminium, and 0.05-1 5 wt% of iron. If necessary, the modified Raney nickel catalyst can be further added with 0.05-10 wt% of at least one metal selected from the group consisting of chromium, molybdenum, tungsten, cobalt, 30 manganese, and titanium. The process for producing the modified Raney nickel catalyst according to the present invention is essentially sim- ilar to conventional ones for producing Raney nickel catalyst. Typically, predetermined amounts of nickel, aluminium, and iron are mixed first and, if necessary, at least one metal selected from the group consisting of chromium, molybde- num, tungsten, cobalt, manganese, and titanium may be added thereto. The mixture is then melted at a temperature of 35 1 200 to 2000°C to produce a precursor alloy. After being sat still and cooled, the precursor alloy is crushed into powder or granules with suitable size and then developed in a solution of alkali metal hydroxide. Finally, the thus-obtained prod- uct is washed with distilled or ion-exchanged water to obtain the modified Raney nickel catalyst. The modified Raney nickel catalyst according to the present invention is useful as a catalyst in the hydrogenation of hydroxy aldehydes, particularly 4-hydroxy-butanal, 2-hydroxy-tetrahydrofuran, and 2-methyl-3-hydroxypropanal. 40 Moreover, the modified Raney nickel catalyst according to the present invention can be used in a process for pro- ducing diols. In the process, hydroxy aldehyde is hydrogenated under a temperature of 50 to 200°C, preferably 75 to 150°C, and a pressure of 10 to 200 kg/cm2G, preferably 20 to 80 kg/cm2G to obtain diols. In the foregoing process, the reactor used therefor depends on the form of catalyst used. If the catalyst is powder type, then a slurry bed reactor is used; while if the catalyst is granule type, a fixed bed reactor is used. The process can 45 be proceeding continuously or in a batchwise manner. In the case of the slurry bed reactor, the amount of the catalyst used is 0.5-20 wt% based on the total weight of solution; and in the case of the fixed bed reactor, the liquid hourly space velocity (LHSV) is 0.1 to 10hr"1. In the process according to the present invention, the hydroxy aldehyde used can be 4-hydroxy-butanal, 2-hydroxy- tetrahydrofuran, or 2-methyl-3-hydroxypropanal. so It is a primary benefit of the modified Raney nickel catalyst according to the present invention that it is of high reac- tion activity and long use life. Examples used to illustrate the present invention are respectively carried out in slurry bed reactor and fixed bed reactor and described in the following. It is to be understood that the scope of the present invention is not to be limited by the following disclosed examples. 55 3 EP 0 807 464 A1 1. Experiments with Slurry Bed Reactor EXAMPLE 1 : 5 0.781 g of carbonylhydrotris(triphenyl phosphine)rhodium, 21 .6 g of triphenyl phosphine, 55.4 g of allyl alcohol, and 73.6 g of toluene were charged to a pressure-resistant glass stirring reactor controlled at a temperature of 60°C and filled with carbon monoxide and hydrogen (in a molar ratio of 1) to have a pressure of 7 kg/cm2G to carry out hydrofor- mylation for a period of 6.5 hours. Then the solution was extracted by deionized water to obtain a top layer of toluene solution containing hydroformylation catalyst and a bottom layer of aqueous solution containing 4-hydroxy-butanal, 2- 10 hydroxy-tetrahydrofuran, and 2-methyl-3-hydroxypropanal.
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