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Synthesis of Morpholine and Derivatives Thereof Via the Reaction of Dialkylene Glycol and Ammonia

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Synthesis of Morpholine and Derivatives Thereof Via the Reaction of Dialkylene Glycol and Ammonia Europaisches Patentamt J» European Patent Office © Publication number: 0036 331 B2 Office europeen des brevets NEW EUROPEAN PATENT SPECIFICATION Date of publication of the new patent specification: mtci C07D 295/02 18.10.89 Application number: 81301126.9 Date of filing: 17.03.81 Synthesis of morpholine and derivatives thereof via the reaction of dialkylene glycol and ammonia. Priority: 17.03.80 US 130782 © Proprietor: AIR PRODUCTS AND CHEMICALS, INC., P.O. Box 538, Allentown, Pennsylvania 18105 (US) Date of publication of application : 23.09.81 Bulletin 81/38 Inventor: Daughenbaugh, Randall Jay, Box 334A, RD No. 1 Barton, PA 19505 (US) Inventor: Dixon, Dale David, Box 53D RD No. 2, @ Publication of the grant of the patent : Kutztown, PA 19530 (US) 01 .08.84 Bulletin 84/31 Inventor: Fowlkes, Robert Lee, 220 Cedar Street, Milton Florida 32570 (US) @ Mention of the opposition decision : 18.10.89 Bulletin 89/42 Representative: Burford, Anthony Frederick et al, W.H. Beck, Greener & Co. 7 Stone Buildings Lincoln's Inn, London WC2A3SZ(GB) Designated Contracting States: AT BE CH DE FR GB IT LI LU NL SE References cited - DE-A-2738115 DE-A-2 758 769 Cfi DE-C- 1 941 633 DE-C-2 040 507 SU-A-175 512 CO US-A-3151 112 US-A-3154 544 O CHEMICAL ABSTRACTS, vol. 75, no. 23, December 6. <0 1971, oage 327, abstract 140871h. COLUMBUS, OHIO O (US) o Q. Ill ACTORUM AG EP 0036 331 B2 Description carrying out the process the reactants are charged to an autoclave and reacted at 240°C and Technical field 25x105 Pa (25 atmospheres) in the presence of This invention relates to an improved process for hydrogen. The improved process relates to the forming morpholine and alkyl and/or phenyl sub- 5 use of a Raney-nickel catalyst having sufficient stituted derivatives thereof. aluminium therein to consume by-product water as it is produced. The effect of water removal is to Description of the prior art extend the catalyst life of the Raney-nickel. U.S. Patent 2412209 discloses a process for U.S. Patent 4091 218 discloses a process for producing aliphatic amines from alcohols and 10 recovering ammonia from a gas stream resulting particularly morpholine by the reaction of dieth- from the catalytic reaction of ammonia and a di- ylene glycol and ammonia. Temperatures from alkylene glycol as described in U.S. 3151 112. In 1 60-400 "C are used and the reaction is carried the process the recovery of the product is effect- out in the presence of a hydrogenation catalyst. ed by contacting the reaction effluent gas stream Examples of hydrogenation catalysts suited for 15 containing unreacted hydrogen, ammonia, and the reaction include Raney nickel, copper chro- methane with a dialkylene glycol feed stock un- mite, copper-nickel-chromite, iron, cobalt, etc. der conditions for adsorbing ammonia and leav- Liquid or gas phase conditions are suggested. ing anhydrous hydrogen and methane. U.S. Patent 3 154544 discloses the preparation British Patent 1 530 570 discloses a process for of substituted morpholines by the vapor phase 20 producing (2-aminoalkoxy)-alkanol (AEE) and conversion of a dialkylene glycol having at least morpholine derivatives from ammonia and oxydi- one secondary hydroxyl group with hydrogen, alkanol under pressures sufficient to maintain and ammonia, in the presence of a hydrogena- liquid conditions. Temperature and pressure are tion/dehydrogenation catalyst. It is noted in the controlled in order to vary the quantity of the reference that diethylene glycol could not be 25 aminoethoxyethanol and morpholine derivative converted to morpholine by reaction with ammo- produced. Temperatures generally are 200- nia in substantial conversion or yield, particularly 220°C while gauge pressures of at least 48x105 under conditions suggested in the prior art e.g. Pa (700 psig) are used. Ammonia to alkanol ratios U.S. 2 412 209 or2 529 923. of 6:1 are used, with the ammonia being in the U.S. Patent 3155 657 discloses a process for 30 anhydrous form. Hydrogen is added to maintain producing polyglycolamines and morpholine by catalyst activity. the reaction of diethylene glycol and ammonia. Temperatures of 150-350°C, pressures of Summary of the invention 20x105-51 x106 Pa (20-500 atmospheres) and a This invention relates to an improved process contact time of from 5 minutes to 4 hours are 35 for forming heterocyclic amines selected from suggested with pressures of 69 x 105-23x 106 Pa morpholine and its alkyl and /or phenyl substitut- (1000-3000 psig) being used. The reaction was ed derivatives. The basic process comprises carried out preferably in the presence of a ruthe- reacting a dialkylene glycol and ammonia in the nium catalyst. Yields of morpholine ranged from presence of hydrogen and a hydrogenation/de- about 14-77% with glycol conversions of from 40 hydrogenation catalyst at conventional tempera- about 48-96%. tures. The improvement constituting the basis of U.S. Patent 3 151 112 shows a process for prod- the invention resides in continuously passing the ucing morpholine and derivatives by the reaction reactants to a trickle-bed catalytic reactor, oper- of dialkylene glycols, e.g. diethylene glycol with ating the reactor so that the reaction conditions ammonia at temperatures of 150-400°C, and 45 do not exceed by more than 10°C the dew point pressures of 30 x 105-41 x 106 Pa (30-400 atmo- of the feed whereby at least 1% of the dialkylene spheres) while maintaining liquid phase condi- glycol is maintained as discontinuous liquid tions. Ammonia is added in large excess to that of phase (i.e. a liquid phase which is not continuous stoichiometric requirements. Yields of up to but consists of discrete quantities, usually drops, about 50% morpholine at the high reaction pres- so of liquid and at least a portion of the heterocyclic sures are shown. amine is present in the vapour phase) and contin- U.S. Patent 3151113 discloses a process of uously removing product. Preferably the condi- preparing N-alkyl morpholine products by the tions are maintained such that the heterocyclic reaction of hydroxy or amino terminated dieth- amine is predominantly in the gas phase. ylene ether feed-stocks with ammonia in the 55 According to a first aspect of the present in- presence of a hydrogenation catalyst under liquid vention, there is provided a process for produc- phase conditions. Pressures of 34x 105-34x 106 ing morpholine or an alkyl of phenyl substituted Pa (500-5000 psig) and temperatures of derivative thereof by contacting an alcohol of the 150-300°C are employed. Conventional hydro- formula genation/dehydrogenation catalysts are used 60 and these may be supported on alumina, kiesel- H R R H guhr, and other various supports or unsupported. Japanese Patent Publication No. 46-32 188, dis- closes a process for producing morpholine by the reaction of diethylene glycol and ammonia. In EP 0036 331 B2 where R, R', and R" may be identical or different, Description of the preferred embodiments each representing a hydrogen atom, alkyl or phe- The feed component suited for practicing the nyl radicals, with ammonia in a reactor said reac- process is a dialkylene glycol of the formula tion being carried out in the presence of hydrog- and hydrogenation-dehydrogenation catal- en a H R R H yst, characterised in that: (a) the dialkylene glycol, ammonia and hydrogen are continuously passed downflow through a I I trickle bed reactor; R' R" R' R" (b) the reactor is operated so that the reaction 10 conditions do not exceed by more than 10°C the be identical different, dew point of the feed whereby at least 1% of the where R, R\ and R" may or atom, alkyl or phe- dialkylene glycol is maintained as a discontinu- each representing a hydrogen R' R" contain typically from 1 to 6 phase and at least a portion of the mor- nyl radicals. R, , ous liquid not is in the phase; and 15 carbon atoms, if alkyl, and preferably more pholine present vapour of amine product is continuously than 2 carbon atoms. For purposes producing (c) heterocyclic amine, i.e. removed from the reactor. a commercially important heterocyclic the glycol is diethylene According to a second aspect of the present in- morpholine, dialkylene result in the production of vention, there is provided a process for preparing glycol (DEG). Others, and substituted morpholine deriva- morpholine by contacting an alcohol which is 20 alkyl phenyl of preferred dialkylene glycol and/or 2-(2-amino-ethoxy) eth- tives. Specific examples diethylene dipropylene anol with ammonia in a reactor in the presence of glycols include diethylene glycol, and dibutylene glycol. hydrogen and a hydrogenation-dehydrogenation glycol As with other the reaction of dialky- catalyst, characterised in that: processes, lene to form heterocyclic amines is carried (a) the alcohol, ammonia and hydrogen are con- 25 glycol the of ammonia. Ammonia to di- tinuously passed downflow trough a trickle bed out in presence alkylene glycol ratios, on a molar basis, are at reactor; but preferably 4to 16:1. the reactor is operated under conditions so least 1:1 and up to 100:1, (b) at least equal molar that the reaction conditions do not exceed by While the process requires to reaction than 10°C the dew point of the feed where- 30 amounts of ammonia to glycol permit more stoichiometric basis, molar ratios higher at least 1% of the alcohol is maintained as a on a by 20:1 do result in significant advan- discontinuous liquid phase and at least a portion than 16 to not Because of the unique nature of the reac- of the morpholine is present in the vapour phase; tages.
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