Title of Invention	A PROCESS FOR THE PREPARATION OF AMINES
Abstract	This invention relates to a process for the preparation of amines of the general formula , Wherein R' and R* are as defined in the text by catalytic amination of alcohols of the general formula R'>-CHRA-OH with nitrogen compoimds of the general formula in the presence of hydrogen and a zirconium/copper/noickel catalyst. PRICE: THIRTY RUEES

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The present invention relates to a process for the preparation of amines by catalytic animation of alcohols with nitrogen compounds and hydrogen in the presence of a zirconium/copper/nickel catalyst at elevated temperatures and pressures using zirconium/copper/nickel catalysts whose active material contains oxygen-containing compounds of molybdenum. DE-A 1,953,263 discloses that it is possible to prepare amines by hydrogenative animation of the corresponding alcohols over catalysts containing cobalt, nickel and copper. The support material used in these catalysts is aluminum or silicon dioxide. With these catalysts good yields can be obtained at high temperatures and pressures. If the process is carried out at lower temperatures and pressures, the conversion and selectivity drop steeply. EP-A 254,335 discloses Ni/Co/Ru catalysts on aluminum oxide or silicon dioxide supports, which additionally contain halides in their active material, for the hydrogenative animation of alcohols. Using these catalysts, conversions of only 61% maximum are achieved at 200°C and 55 bar. US-A 4,151,204 discloses catalysts for the preparation of amino alcohols, which consist of a metal such as cobalt, nickel or copper, preferably nickel or cobalt, and which are optionally doped with small amounts of zirconium, the zirconium being added in relation to the nickel or cobalt, in a molar ratio of from 0.005 : 1 to 0.2 : 1. Higher zirconium contents lead to side reactions such as decomposition of the products. EP-A 382 049 discloses catalysts and processes for the hydrogenative animation of alcohols. These catalysts, whose active material contains oxygen-containing zirconium, copper, cobalt and nickel compounds are characterized by good activity and selectivity, but they have unsatisfactory maximum on-stream times. It was thus the object of the present invention to overcome the aforementioned drawbacks. Accordingly, we have found a novel and improved process for the preparation of amines from primary or secondary alcohols and nitrogen compounds selected from the group consisting of ammonia and primary and secondary amines, at temperatures of from 80°C to 250°C and pressures of from 1 to 400 bar using hydrogen in the presence of zirconium/copper/nickel catalyst, wherein the catalytically active material contains from 20 to 85 wt% of oxygen containing zirconium compounds, calculated as Zr02, from 1 to 30 wt% of oxygen containing compounds of copper, calculated as CuO, from 30 to 70 wt% of oxygen containing compounds of nickel, calculated as NiO, from 0.1 to 5 wt% of oxygen containing compounds of molybdenum, calculated as M0O3, and from 0 to 10 wt% of oxygen containing compounds of aluminum and/or manganese, calculated as AI2O3 or Mn02 respectively. Accordingly the present invention provides a process for the preparation of an amine of the general formula I in which R1 and R2 denotes hydrogen, C1-C20 alkyl, C3-C12 cycloalkyl, aryl, C7-C20 aralkyl and C7-C20 alkykryi or together form (CH2)i-X-(CH2)nb R3 and R4 de note hydrogen, C1-C200 alkyl, C3-C12 cycloalkyl, CrC2o hydroxyalkyl, C1-C20 alkyl substituted by amino and/or hydroxy, C2-C30 alkoxyalkyl, R5-(OCR6R7CR8R9)„-(OCR6R7), aryl, CrQn aralkyl, C7-C20 alkylaryl, (R^N-CCHz), and Y-CCHzVNR^CHa), or together form (CH2)r X-(CH2)m or R2 and R4 together form (CH2)i-X-(CH2)m, R5 denotes hydrogen, C1-C4 alkyl, or C12-C40 alkylphenyl, R6, R7, R8 and R9 denote hydrogen, methyl or ethyl, R10 denotes hydrogen or CrC4 alkyl X denotes CH& oxygen, or N-R6, Y denotes N(R5>2, hydroxy, Cr Q20 alkylaminoalkyl or C3-C20 dialkylaminoalkyl, n is an integer from 1 to 30, 1 is an integer from 2 to 4, m and q are integers from 1 to 4, comprising reacting a primary or secondary alcohol of the general formula II and a nitrogen compound of the general formula III in which R1, R2, R3 and R4 have the aforementioned meanings, at temperatures of from 80°C to 250°C and pressures of from 1 to 400 bar with hydrogen in the presence of a zirconium,copper,nickel catalyst, wherein the catalytically active material contains from 20 to 85 wt% of oxygen containing zirconium compounds, calculated as Z1O2, from 1 to 30 wt% of oxygen containing compounds of copper, calculated as CuO, from 30 to 70 wt% of oxygen containing compounds of nickel, calculated as NiO, from 0.1 to 5 wt% of oxygen containing compounds of molebdenum, calculated as M0O3 and from 0 to 10 wt% of oxygen containing compounds of aluminum and/or manganese, calculated as A1203 or Mn02 respectively and recovering the amine of the general formula I from the reaction mixture in a known manner. Suitable alcohols are virtually all of the primary and secondary aliphatic alcohols. The aliphatic alcohols can be straight-chained, branch-chained, or cyclic. Secondary alcohols are equally well aminated as primary alcohols. No limitations are as yet known as regards the carbon number of aminatable alcohols. Furthermore the alcohols can carry substituents which are inert under the conditions of the hydrogenative amination, for example, alkoxy or alkyleneoxy groups. If polybasic alcohols are to be aminated, it is possible, via control of the reaction conditions, to obtain amino alcohols, cyclic amines, or polyaminated products. The following alcohols are preferably aminated, for example: Methanol, ethanol, /7-propanol, isopropanol, //-butanol, isobutanol, //-pentanol, n-hexanol, 2-ethylhexanol, tridecanol, stearyl alcohol, palmityl alcohol, cyclopentanol, cyclohexanol, ethanolamine, n-propanolamine, isopropanolamine, //-pentanol-amine, ^-hexanolamine, diethanolamine, iV-alkyldiethanolamines, diisopropanol-amine, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 4,4'-bishydroxycyclohexylpropane-(2,2), methoxyethanol, propoxyethanol, butoxyethan-ol, poly(isobutyl alcohoDs, poly(propyl alcohoDs, poly(ethylene glycol ether)s, poly(propylene glycol ether)s and poly(butylene glycol ether)s. The last-named poly(alkylene glycol ether)s are converted to the corresponding amines during the reaction of the invention by conversion of their free hydroxy! groups. Both ammonia and primary or secondary aliphatic or cycloaliphatic amines can be BASFAKTIENQESELLSCHAFT O.Z. 0050/45066 used as aminating agents in the hydrogenative amination of alcohols. When use is made of ammonia as aminating agent the alcoholic hydroxyl groups are first of all converted into free amino groups (-NH2). The primary amines thus s formed can react with more alcohol to form the corresponding secondary amines and these in turn react with more alcohol to form the corresponding symmetrical tertiary amines. Depending on the composition of the reaction batch and the reaction conditions used - pressure, temperature, reaction time - preferably primary, secondary, or tertiary amines can be prepared in this way as desired. 10 Cyclic amines such as pyrrolidines, piperidines, piperazines and morpholines can be prepared in this way from polybasic alcohols by intramolecular hydrogenative amination. is Primary or secondary amines can be used as aminating agents as well as ammonia. These aminating agents are preferably used for the preparation of unsymmetrically substituted di- or tri-alkylamines, such as ethyldiisopropylamine and ethyldicyclo-20 hexylamine. The following mono- and di-alkylamines are preferably used, for example, as aminating agents: methylamine, dimethylamine, ethylamine, diethyl-amine, propylamine, diisopropylamine, butylamine, pentylamine, hexylamine and cyclohexylamine. 25 The aminating agent can be used in a stoichiometric amount in relation to the alcoholic hydroxyl group to be aminated. However the process is preferably carried out using an excess of aminating agent, generally more than a fivefold molar excess per mole of alcoholic hydroxyl group to be aminated. Ammonia, in particular, is generally used in a molar excess of from 5 to 250 times, preferably 30 from 10 to 100 times, and more preferably from 25 to 80 times, the molar amount of alcoholic hydroxyl groups which are to be converted. Higher excesses both of ammonia and of primary or secondary amines are possible. The hydrogen is generally fed to the reaction at a rate of from 5 to 400 L (STP), as preferably at a rate of from 50 to 200 L (STP) per mole of alcohol component. . The reaction generally takes place without the use of additional solvent. During the reaction of high molecular weight or highly viscous starting materials or starting compounds or products which are solid at room temperature, it can be 40 advantageous to make supplementary use of a solvent which is inert under the reaction conditions, such as tetrahydrofuran, dioxane, N-methylpyrrolidone, or BASFAKTIENGESEUSCHAFT o.z.ooso/45066 ethylene glycol dimethyl ether. Usually the reaction is carried out at temperatures of from 80° to 200°C, preferably from 120° to 230°C and more preferably from 150° to 220°C. The s reaction is generally carried out under a pressure of from 1 to 400 bar. Pressures of from 10 to 250 bar are preferably used however, particularly from 30 to 200 bar. The use of higher temperatures and a higher overall pressure is possible. The overall pressure in the reaction vessel, which is equal to the sum of the partial io pressures of the aminating agent, the alcohol component, and the reaction products formed and of any solvent used at the temperatures stated, is advantageously controlled by forcing in hydrogen to establish the desired reaction pressure. is It can be advantageous as regards the selectivity of the present process to mix the shaped catalyst elements in the reactor with inert packing elements, ie, to "dilute" them as it were. The proportion of the packing elements in such catalyst formulations can be from 20 to 80, preferably from 30 to 60 and more preferably from 40 to 50 percent by volume. 20 In practice the process is generally carried out by simultaneously feeding the alcohol and the aminating agent to the catalyst, which is usually present in a preferably externally heated fixed bed reactor, at the desired temperature of reaction and the desired pressure. In this process the specific throughput is 25 generally from 0.02 to 3L, preferably from 0.05 to 2L and more preferably from 0.1 to 1.6 L of alcohol per liter of catalyst per hour. In this case it is advantageous to heat the reactants, preferably to the temperature of reaction, prior to introduction thereof into the reaction vessel. 30 The reactor can be operated in both upward and downward modes, ie the reactants can pass both upwardly and downwardly through the reactor. It is obvious that the process can be carried out batchwise or continuously. In both cases the excess aminating agent can be recycled along with the hydrogen. If the conversion achieved during the reaction is incomplete, unconverted starting as material can likewise be recycled to the reaction zone. The excess aminating agent and the hydrogen are removed from the effluent, advantageously after this has been depressurized, and the aminated products obtained are purified by distillation, liquid extraction, or crystallization. The excess AO aminating agent and the hydrogen are advantageously recycled to the reaction zone. The same applies tor any unconverted or incompletely converted alcohol The water of reaction formed in the course of the reaction generally has no adverse effect on the degree of conversion, the reaction rate, the selectivity, or the s maximum on-stream time of the catalyst and is therefore advantageously not removed from the reaction product until purification of the latter, by distillation, takes place. The catalysts of the invention are preferably generally used in the form of solid 10 catalysts. By the term "solid catalyst" is meant a catalyst which, unlike a supported catalyst, consists of catalytically active material only. Solid catalysts can be used by placing the catalytically active material, ground to a powder, in the reaction vessel or by using the catalytically active material, following milling, mixing with molding agents, shaping and tempering, in the form of shaped catalyst elements -is for example, as balls, cylinders, rings, or spirals - and placing said elements in the reactor. The catalytically active material of the catalysts of the invention contains, in addition to oxygen-containing compounds of zirconium, oxygen-containing com-zo pounds of nickel, copper and molybdenum. Since the concentration data relate in each case -'unless otherwise stated - to the catalytically active material of the catalyst, the catalytically active material of the catalyst is defined below as the sum of the weights of the catalytically active zs constituents zirconium, nickel, copper, and molybdenum present in the catalyst, always calculated as Zr02, NiO, CuO, or Mo03 respectively, following its last heat treatment and prior to its reduction with hydrogen. Generally the zirconium oxide content of the catalysts of the invention is between 30 20 and 85wt%, preferably from 70 to 80 wt%. The other components nickel and copper are generally present in a total amount of from 15 to 80 wt%, preferably from 15 to 60wt%, in particular from 15 to 50wt%, and molybdenum is generally present in amounts of from 0.1 to 5wt%, preferably 35 from 0.5 to 3.5 wt%, in the catalytically active material. Preferred catalysts contain in their catalytically active material from 20 to85wt%, preferably from 25 to 60wt%, of oxygen-containing zirconium compounds, from 1 to 30wt%, preferably from 10 to 25wt%, of oxygen-containing copper compounds, 40 from 30 to 70wt%, preferably from 40 to 70wt% and more preferably from 45 to 60wi%, of oxygen-cotitaihfng compounds of nickel; from 0.1 to 5 wt%, preferably from 0.5 to 3.5 wt%, of oxygen-containing compounds of molybdenum, and from 0 to 10 wt% of oxygen-containing compounds of aluminum and/or manganese. Various procedures are possible for the preparation of the solid catalysts. They can s be obtained, for example, by forming a paste of pulverulent mixtures of the hydroxides, carbonates, oxides, and/or other salts of the components zirconium, nickel, and copper with water followed by extrusion and tempering of the material thus obtained. io Generally however, precipitation methods are used for the preparation of the catalysts of the invention. Thus they can be obtained, for example, by concurrent precipitation of the nickel and copper components from an aqueous salt solution containing these elements by means of mineral bases in the presence of a slurry of a difficultly soluble, oxygen-containing zirconium compound followed by washing, is drying and calcination of the precipitate obtained. As difficultly soluble, oxygen-containing zirconium compounds there can be used for example, zirconium dioxide, zirconium oxide hydrate, and zirconium phosphates, borates and silicates. The slurries of the difficultly soluble zirconium compounds can be prepared by suspending fine-grained powders of these compounds in water with vigorous 20 stirring. These slurries are advantageously obtained by precipitating the difficultly soluble zirconium compounds from aqueous zirconium salt solutions by means of mineral bases. The catalysts of the invention are preferably prepared via concurrent precipitation 25 (mixed precipitation) of all of its components. To this end, an aqueous salt solution containing the catalyst components is advantageously admixed, with heating and stirring, with an aqueous mineral base, in particular an alkali metal base - for example sodium carbonate, sodium hydroxide, potassium carbonate, or potassium hydroxide - until precipitation is complete. The nature of the salts used is not so generally crucial. SincefiVhen using this procedure, the water-solubility of the "salts is the~guiding factor, one criterion to be observedis^uffteient water-solubility to allow for the preparation of these relatively highly concentrated salt solutions. It is to be regarded as self-evident that ^when-seleeting-th^ sa4ts of the individual -- components, naturally only those salts are chosen which have anions such as do as not lead to false reactions, for example to undesirable precipitations or to the hindrance or prevention of precipitation due to complex formation. Catalysts of the invention having particularly advantageous properties are obtainable by precipitating a portion of the zirconium component of the catalyst, 40 advantageously from an aqueous zirconium salt solution separately in precipitating 7 eqlwpmejit^ precipitated zirconium oxide hydrate thus obtained the remaining portion of the zirconium component of the catalyst can then be precipitated together with the other catalytically active components, by mixed precipitation as described above. It has been found to be particularly advantageous to effect preliminary precipitation s of from 10 to 80wt%, preferably from 30 to 70 wt% and more preferably from 40 to 60wt%, of the total amount of zirconium. The precipitates obtained in these precipitation reactions are generally chemically uniform and consist inter alia of mixtures of the oxides, oxide hydrates, hydroxides, io carbonates and insoluble and basic salts of said metals. Ageing of the precipitates may have a favorable effect on their filterability, ie, ageing achieved by leaving them to stand for a while after precipitation, optionally with heating or aeration. The precipitates obtained in these precipitation reactions are processed in the is usual manner to form the catalysts of the invention. After being washed, they are generally dried at from 80° to 200°C and preferably from 100° to 150°C and are then calcined. Calcination is generally carried out at temperatures between 300° and 800°C, preferably at from 400° to 600°C and more preferably at from 450° to 550°C. 20 Following calcination, the catalyst is advantageously conditioned, for example by milling it to a specific grain size, or by milling it and then mixing it with molding agents such as graphite or stearic acid followed by compression to shaped articles by means of a pelleting press and tempering. The tempering temperatures used in 25 this process are generally the same as those used during calcination. The catalysts prepared in this manner contain the catalytically active metals in the form of a mixture of their oxygen-containing compounds ie in particular in the form of oxides and mixed_oxides^_ _ The catalysts prepared in this manner are stored and, if desired,; traded as such. Prior to their use as catalysts for hydrogenative amination they are usually sttbjected^o pretiffltoary reduction. However-they can be-used withoutpreliminary reduction if desired, in which case they are then reduced under the conditions of ■s 4he hydrogenative amination by-the hydrogen present in the reactor. To effect preliminary reduction, the catalysts" are generally first of all exposed to a nitrogen/hydrogen atmosphere at a temperature of from 150° to 200°C over a period of from 12 to 20 h, and then treated in a hydrogen atmosphere at from 200° to 300°C for up to approximately 24 h. In this preliminary reduction process part of o the oxygen-containing metal compounds present in the catalysts is reduced to -lorwirW^ff espnoln compounds, are present in the active form of the catalyst. The substituents R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 and the indices /, m, and n in the compounds I, II, and III independently have the following meanings: R1, R2, R3, R4, R5, R6, R7, R8t R9f R10 - hydrogen, R3,R4 (VC200 a|kyl. preferably CrC8 alkyl such as methyl, ethyl, /7-propyl, isopropyl, w-butyl, isobutyl, 5ec-butyl, tert-butyl, w-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, w-hexyl, isohexyl, .sec-hexyl, w-heptyl, isoheptyl.w-octyl, isooctyl, 2-ethylhexyl, w-decyl, 2-Ar-propyl-w-heptyl, w-tridecyl, 2-rt-butyl-w-nonyl and 3-n-butyl-«-nonyl, more preferably isopropyl, 2-ethyl¬hexyl, n-decyl, 2-«-propyl-n-heptyl, ^-tridecyl, 2-/7-butyl-/7-nonyl and 3-n-butyl-w-nonyl and preferably c40-C200 alkyl such as polybutyl, polyisobutyl, polypropyl, polyisopropyl and polyethyl, more preferably polybutyl and polyisobutyl, R1 and R2 or R3 and p.4 or R2 and R4 together form a -(CH2)/-X-(CH?),M group, R1, R2, R3, and R4 C3-C12 cycloalkyl, preferably C3-C8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, more preferably cyclo-pentyl, cyclohexyl and cyclooctyl, aryl, such as^3t*eTTylr1-naptt^ and 9- " "ahWyT ^pretlraBly phenyl, 1 -napfithyl and 2-haphthyl, more preferably phenyl, ---■- C7-e20alkyfaryl,^preferably C7-c12 ajkylphenyj-such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphen-yl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyt 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-/?-propylphenyl, 3-/7-propyl-phenyl and 4-w-propylphenyl, ^c2o«ra1kytrpreferatt^ phenethyl, 1 -phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, more preferably benzyl, 1-phenethyl, and 2-phenethyl, R2 0,-020 alky'> preferably c,-C8 alkyl such as methyl, ethyl, ^-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, terf-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, /r-hexyl, isohexyl, sec-hexyl, w-heptyl, isoheptyl, w-octyl, isooctyl, more preferably 0,-04 alkyl such as methyl, ethyl, w-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl and terf-butyl, R4 ci~c2o hydroxyalkyl, preferably C,-C8 hydroxyalkyl, more preferably 0,-04 hydroxyalkyl such as hydroxymethyl, 1 -hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-w-propyl, 3-hydroxy-/?-propyl and 1-hydroxy-methylethyl, C,-C2o alkyl substituted by amino and hydroxy, preferably C,-C8 alkyl substitut¬ed by amino and/or hydroxy, more preferably c,-c4 alkyl such as N-(hydroxyethyi)aminoethyl and AMaminoethyl)aminoethyl substituted by amino and/or hydroxy, C2-C30 alkoxyalkyl, preferably C2-C20 alkoxyalkyl, more preferably c2-C8 alkoxy-alkyl such as methoxymethyi, ethoxymethyl, /7-propoxymethyl, isopropoxy-methyl, n-butoxym ethyl, isobutoxymethyl, sec-butoxymethyl, tert-buXoxy-methyl, 1 -methoxyethyl and 2-methoxyethyl, more preferably c2-c4 alkoxy¬alkyl such as methoxymethyi, ethoxymethyl, w-propoxymethyl, isopropoxy-methyT, ^/t-^b^^ii^!Ryii isoEtufracyirfietti^l. sec-birtoxyrnethyl, rerf-butoxy-methyl, 1-methoxyethyl, and 2-methoxyethyl, R5-(OCR6R7CR8R9)n-(OCR6R7), preferably R5-(OCHR7CHR9)„-(OCR8R7), more prefer¬ably Rs-(OeH20HR9)„-(OCR6R7), (R5)2N-(CH2)9, Y-(CH2)w-NrtMCH2)9, (VC,, alkyl such as methyl, ethyl, ^-propyl, isopropyl, w-butyl, isobutyl, sec-butyl and /erf-butyl, preferably methyl and ethyl, more preferably methyl, R6, R7, R8, R9 methyl or ethyl, preferably methyl, x - CH2, oxygen, N-R6, Y - N(R5)2, hydroxy, C2-C20 alkylaminoalkyl, preferably C2-C16 alkylaminoalkyl such asmethylamino-methyl, methylaminoethyl, ethylaminomethyl, ethylaminoethyl and isopropyl-aminoalkyl, an integer from 2 to 4 such as 2, 3 or 4, preferably 2 or 3, more preferably 2, m and q , an integer from 1 to 4 such as 1, 2, 3 or 4, preferably 2, 3 or 4, more preferably 2 or 3, *R5 C12-C40 alkylphenyl, preferably C14-c40 alkylphenyl such as 2-, 3-, and 4-nonylphenyl, 2-, 3-, and 4-decylphenyl. 2,3-, 2,4-, 2,5-, 3,4-, and 3,5-dinonylphenyl, 2,3-, 2,4-, 2,5-, 3,4-, and 3,5-didecylphenyl, n an integer from 1 to 10, preferably an integer from 1 to 8 such as 1, 2, 3, 4, 5, 6, 7 or 8, more preferably an integer from 1 to 6 such as 1, 2, 3, 4, 5 or 6. The amines that can be produced in the present invention are suitable inter alia as intermediates for the preparation of fuel additives WS-A 3,275,554; DE-A 2,125,039 and DE-A 3,611,230), surfactants, medicines, plant protectants, and vulcanization promotors. Examples For the evaluation of the mechanical stability of the catalysts a fast screening method was developed. Under the usual conditions of the hydrogenative amination of polydsobutene oxo alcohoDs reactions were carried out in batch autoclave tests under standardized conditions over various catalysts. The catalysts described in the present invention were distinguished by their high mechanical stability on completion of the test, particularly when compared with catalysts described in EP-A 382,049. Catalyst preparation Preparation of catalyst A "Anaqueous solution of nickel nitrate, copper nitrate, and zirconium acetate, which contained 4.48 % of NiO. 1.52 % of CuO, and 2.82 % of Zr02, was precipitated in a stirred vessel at a constant rate of flow simultaneously with a 20% strength aqueous sodium carbonate solution, at a temperature of 70°C, such that the pH measured with a glass electrode was maintained at 7.0. The suspension obtained was filtered and the filter cake washed with demineral-ized water until the electrical conductivity of the filtrate was ca 20 MS. Ammonium heptamolybdate was then incorporated into the moist filter cake until the oxide * mixture stated below was obtained. Afterwards the filter cake was dried at a temperature of 150°C in a drying cabinet or a spray dryer. The hydroxide/carbon¬ate mixture obtained in this way was then tempered at a temperature of 500°C over a period of 4 h. i The catalyst thus obtained had the following composition: 50wt% of NiO, 17wt% of CuO, 1.5wt% of Mo03 and 31.5wt% of Zr02. The catalyst powder was mixed with 3wt% of graphite and compressed to form 6x3 mm pellets. The pellets had a porosity (determined by measuring the water uptake) of 0.20 mL/g and a hardness of 3500N/cm2. Preparation of catalyst B For comparative tests a catalyst was prepared in accordance with EP-A 382,049, as follows. A solution of zirconium, copper(ll), cobalt(ll), and nickel(ll) salts was pumped concurrently with a sodium carbonate solution having a density of 1.208kg/L into precipitating equipment in which freshly precipitated zirconium dioxide was present, suspended in water. The pH of the solution was kept at a constant value of 6.0 during precipitation and raised to pH 7.5 following consumption of the mineral salt solution. The precipitate was washed, dried to constant weight at 120°C and calcined to contant weight at 400°C. The crude catalyst material obtained was milled, mixed with 3 wt% of graphite, pelletized, and again calcined at 520°C for a period of 3 h. The reaction was carried out in an autoclave having a capacity of 2 L. The i standard stroke stirrer was equipped with a V2A„con.tainer having a capacity of 100mL, in Which 90mL of catalyst was placed, in each test. In each test, 450g of polyOsobutene oxoalcohol) (50%strength solution in dodecane) were caused to react with 450 mL of of liquid ammonia at a hydrogen pressure of 40 bar at 230°C and a reaction time of 4h. On completion of the experiment, the finished catalyst was washed 3 times with tetrahydrofuran, dried over a period of 8 h at 125°C in vacuo (1 mbar), after which the mechanical stability was determined. The comparative test showed that the mechanical stability on completion of the experiment in the case of usage of catalyst A is distinctly greater than in the case of usage of catalyst B. Example 1 Hydrogenative amination of polyOsobutene oxoalcohol) A continuous high-pressure reactor was packed with 500 cm3 of catalyst A and 1200 cm3 of polyisobutene-oxoalkohoJ(50% strength solution in dodecane) and Example 2 Hydrogenative amination of tridecanol s A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 180 cm3 of tridecanol and 1200 cm3 of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 200°C and the pressure in the reactor was kept constant at 200bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The collected effluents were distilled and analyzed by gas chromato¬graphy: 73.8 % of tridecylamine 25.4 % of ditridecylamine No tridecanol Remainder 0.7 % Example 3 i Hydrogenative amination of diisononylphenol x 24 butylene oxide A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 100 cm3 of diisononylphenol x 24 butylene oxide (Keropur ES 3213) and 300 cm3 of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 220°C and the pressure in the reactor was kept constant at 200 bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The analysis of the collected effluents aave the followina values: Example 4 Hydrogenative dimethylamination of ethanol A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 1800 cm3 of a mixture of ethanol and dimethylamine in a molar ratio of 4:1 were passed through, per hour. The catalyst temperature was adjusted to 160°C and the pressure in the reactor was kept constant at 60 bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, i following depressurization thereof. The collected effluents were analyzed by gas chromatography: Dimethylamine: Trimethylamine: 1.5% Dimethylethylamine: 24.0% Methyldiethylamine: 1.5% Ethanol: 60 % Water: 6 % , Example 5 Hydrogenative amination of diglycol (target, morpholine) A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 90 cm3 of diglycol and 350 cm3 of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 200°C and the pressure in the reactor was kept constant at 200bar, by concurrently forcing in hydrogen. Excess Example 6 Hydrogenative amination of diglycol (target, aminodiglycol) A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 270 cm3 of diglycol and 350 cm3 of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 200°C and the pressure in the reactor was kept constant at 200 bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The collected effluents were analyzed by gas chromatography: Morpholine: 35.3 % Aminodiglycol: 29.3 % Diglycol: 30.7 % Other by-products: 4.7 % Example 7 Hydrogenative amination of ethylglycol A continuous high-pressure reactor was packed with 500 cm3 of catalyst A, and 150 cm3 of ethyl glycol and 350 cm3 of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 210°C and the pressure in the reactor was kept constant at 200 bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The collected effluents were analyzed by gas chromatography: hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The analysis of the collected effluents gave the following values: Total amine number: 9.66 eq/g of crude effluent Total acetylation number: 1.02 cq/g of crude effluent OH number: 0.52 eq/g of crude effluent sec-amine number: 0.61 eq/g of crude effluent tert-am'me number: 0.03 eq/g of crude effluent Example 9 Hydrogenative amination of poly(propylene glycol) A continuous high-pressure reactor was packed with 2200 cm3 of catalyst A, and 50 L of poly(propylene glycol) (average molar mass: 1000) and 240 L of liquid ammonia were passed through, per hour. The catalyst temperature was adjusted to 200°c and the pressure in the reactor was kept constant at 250 bar, by concurrently forcing in hydrogen. Excess ammonia was removed from the effluent, by distillation, following depressurization thereof. The analysis of the collected effluents gave the following values: Total amine number: 0.98 eq/g of crude effluent Total acetylation number: 1.00 eq/g of crude effluent OH number: 0.02 eq/g of crude effluent sec/tert-am\ne number: 0.03 eq/g of crude effluent 75.7 % of N,N - diisopropylethylenediamine 1.0 % of N,N-diisopropyl-N-methylethylenediamine 5.4 % of 2-diisopropylethanolamine 17.8 % of other compounds WE CLAIM: 1. A process for the preparation of an amine of the general formula I in which R1 and R2 denotes hydrogen, C1-C20 alkyl, C3-C12 cycloalkyl, aryl, C7-C20 aralkyl and C7-C20 alkylaryl or together form (CH2)i-X-(CH2)m, R3 and R4 de note hydrogen, C1-C200 alkyl, C3-Ci2 cycloalkyl, C1-C20 hydroxyalkyl, C1-C20 alkyl substituted by amino and/or hydroxy, C2-C30 alkoxyalkyl, R5^OCR6R7CRV)n-(OCR6R7), aryl, C7Q20 aralkyl, QrQo alkylaryl, (R5>2N-(CH2)q and Y-CCH2)-NR-(CH) or together form (CH2)r X-(CH2)m or R2 and R4 together form (CH2)1-X-(CH2)in, R5 denotes hydrogen, C1-C4 alkyl, or C12-C4o alkylphenyl, R6, R7, R8 and R9 denote hydrogen, methyl or ethyl, R10 denotes hydrogen or CrC4 alkyl X denotes CH2, oxygen, or N-R6, Y denotes N(R5>2, hydroxy, Cr C20 alkylaminoalkyl or C3-C20 dialkylaminoalkyl, n is an integer from 1 to 30, 1 is an integer from 2 to 4, m and q are integers from 1 to 4, comprising reacting a primary or secondary alcohol of the general formula II R4-CHR3-OH (II) and a nitrogen compound of the general formula III in which R1, R2, R3 and R4 have the aforementioned meanings, at temperatures of from 80°C to 250°C and pressures of from 1 to 400 bar with hydrogen in the presence of a zirconium,copper,nickel catalyst, wherein the catalytically active material contains from 20 to 85 wt% of oxygen containing zirconium compounds, calculated as Zr02, from 1 to 30 wt% of oxygen containing compounds of copper, calculated as CuO, from 30 to 70 wt% of oxygen containing compounds of nickel, calculated as NiO, from 0.1 to 5 wt% of oxygen containing compounds of molebdenum, calculated as M0O3 and from 0 to 10 wt% of oxygen containing compounds of aluminum and/or manganese, calculated as A1203 or Mn02 respectively and recovering the amine of the general formula I from the reaction mixture in a known manner. 2. The process for the preparation of said amine as claimed in claim 1, wherein the catalytically active material contains from 40 to 70 wt% of oxygen containing compounds of nickel calculated as NiO. 3. The process for the preparation of said amine as claimed in claim 1, wherein the catalytically active material contains from 45 to 60 wt % of oxygen containing compound of nickel, calculated as NiO. 4. The process for the preparation of said amine as claimed in claim 1, wherein the catalytically active material contains from 0.5 to 3.5 wt% of oxygen containing compound of molybdenum, calculated as M0O3. The process for the preparation of said amine as claimed in claim 1, wherein the catalytically active material contains from 25 to 60 wt% of oxygen containing zirconium compound calculated as Zr02. The process for the preparation of said amine as claimed in claim 1, wherein the catalytically active material contains from 10 to 25 wt% of oxygen containing compound of copper calculated as CuO. The process for the preparation of said amine as claimed in claim 1, wherein the reaction is carried out at temperatures of from 120°C to 230°C. The process for the preparation of said amine as claimed in claim 1, wherein the reaction is carried out under pressures of from 10 to 250 bar. The process for the preparation of said amine as claimed in claim 1, wherein the reaction is carried out under pressures from 30 to 220 bar. A process for the preparation of an amine of the general formula I substantially as herein described.

Documents:

988-mas-1995 abstract.pdf

988-mas-1995 claims.pdf

988-mas-1995 correspondence -others.pdf

988-mas-1995 correspondence -po.pdf

988-mas-1995 description (complete).pdf

988-mas-1995 form -1.pdf

988-mas-1995 form -4.pdf

988-mas-1995 form-26.pdf

988-mas-1995 others.pdf