Title of Invention

A PROCESS FOR PREPATING DIAMINES

Abstract

This invention relates to a process for preparing diamines of the general formula 1 (I) Where R<SUP>1</SUP> R<SUP>2</SUP> R<SUP>3</SUP> R<SUP>4</SUP> are C1 to C20 -alkyl, C3 - to C12 - cycloalkyl, aryl, C7 - to C20 -aralky) and C7-C20-alkyiaryl or together (CH2)n-X-(CH2)m R<SUP>1</SUP> ,R<SUP>2</SUP> can also be hyrogen X is oxygen. CH2 or N-R, R5 is hydrogen, C1- to C20-alkyl, C3 - to C12-cycloalkyl, aryl, C7-to C10-aralkyl and C7-C20-alkylaryl. Y is a C2-C12-alkylene chain which may be unsubstituted or monosubslituted to penta-substituled by C1 to C4-alkyl, n.m are integers from i to 4, from aminoalcohols of the general formula II (U) and nitrogen compounds of the general formula III (III) where R<SUP>1</SUP> , R<SUP>2</SUP> , R<SUP>3</SUP> , R<SUP>4</SUP> , R<SUP>5</SUP> , X,Y and the indices n and m are as Jeflned above, at from 80 to 250C and pressures of from I to 400 bar using hydrogen in the presence of a zirconium, copper,nickel catalyst, wherein the catalytically active composition comprises from 20 to 85% by weight of oxygen-containing zirconium compounds, calculated as ZrO3. from 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO. from 30 to 70% by weight of oxygen-containing compounds of nickel, calculated as NiO, from 0.1 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as MoO3. and from 0 to 10% by weight of oxygen-containing compounds of aluminum and/or manganese, calculated as AI2O3 and MnO2 respectively. PRICE: THIRTY RUPEES.

Full Text

The present invention relates to a process for preparing diamines for the Catalytic amination of aminoalcohols using nitrogen compounds and hydrogen in the presence of zirconium, copper, nickel Catalyst at elevated temperatures and pressures, using zirconium, copper, nickel Catalysts whose active composition contains oxygen-containing componds of molybdenum- DE-A-19 53 263 discloses the preparation of amines by the hydrogenative amination of the corresponding alcohols over Catalysts containing cobalt, nickel and copper. In these Catalysts, aluminum or silicon dioxide Is used as support material. These Catalysts enable good conversions to be obtained at high temperatures and pressures. If the reaction is Carried out at a lower temperatures and pressures, the conversion and selectivity are greatly reduced. EP-A-254 335 discloses Ni-Co-Ru Catalysts on aluminum oxide or silicon dioxide supports, which Catalysts additionally contain halides in their active composition, for the hydrogenative amination of alcohols. These Catalysts give yields of only 61 and at most at 200°C and 55 bar. US-A.-4 151 204 discloses Catalysts for preparing aminoalcohols, which Catalysts comprise a metal such as cobalt, nickel or copper, preferably nickel or cobalt, and may be undoped or doped with small amounts of zirconium, with the zirconium being added in a molar ratio of from 0.005:1 to 02:1, based on the nickel or cobalt. Higher zirconium contents lead to a secondary reactions such as decomposition of the products. EP-A.-382 049 discloses Catalysts and processes for the hydrogenative amination of alcohols. These Catalysts, whose active composition comprises oxygen-containing zirconium, copper, cobalt and nickel compounds, do have good activity and selectivity, but have operating lives which warrant improvement. It Is an object of the present invention to overcome said disadvantages. Accordingly the present invention provides a process for preparing diamines of the general formula I Where R1 R2 R3 R4 are C1 - to C20 -alkyl, C3 - to C12 -cycloalkyl, aryl C7 - to C20-aralkyl and C7 - C20 -alkylaryl or together (CH2 ) n-X-(CH2)m, R1 , R2 Can also be hyrogen, X is oxygen, CH2 or N-R, R5 is hydrogen, C1 - to C20 -alkyl, C3 - to C12 -cycloalkyl, aryl, C7 - to C20-aralkyl and C7 - C20 -alkylaryl, Y is a C2 - C12 -alkylene chain which may be unsubstituted or monosubstituted to penta-substituted by C1 - to C4 -alkyl, n, m are integers from 1 to 4, from aminoalcohols of the general formula II (11) and nitrogen compounds of the general formula III (Ill) where R1 R2 R3 R4 , R5, X, Y and the indices n and m are as defined above, at from 80 to 250°C and pressures of from 1 to 400 bar using hydrogen in the presence of a zirconium, copper, nickel Catalyst and isolating the diamines in a known manner, wherein the Catalytically active composition comprises from 20 to 85% by weight of oxygen-containing zirconium compounds, Calculated as ZrO-, from 1 to 30% by weight of oxygen-containing compounds of copper, Calculated as CuO, from 30 to 70% by weight of oxygen-containing compounds of nickel, Calculated as NiO, from 0.1 to 5% by weight of oxygen-containing compounds of molybdenum, Calculated as M0O3, and from 0 to 10% by weight of oxygen-containing compounds of aluminum and/or manganese, Calculated as AI2O3 and Mn02 respectively. Suitable aminoalcohols are virtually all primary and secondary aliphatic aminoalcohols. The aliphatic aminoalcohols Can be linear, branched or cyclic. Secondary aminoalcohols are aminated the same as primary aminoalcohols. No restrictions are hitherto known on the number of Carbon atoms in the aminatable amino¬alcohols. The aminoalcohols Can also bear substituents which are inert under the conditions of the hydrogenated amination. Preference is given to aminating, for example, the following aminoalcohols: ► N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-di-n- propylaminoethanol, N,N-di-iso-propylaminoethanol, N,N-di-n-butylaminoethanol, N,N-di-iso-butylaminoethanol, N,N-di-sec-butylaminoethanol, N,N-di-tert-butylaminoethanol, N,N-dimethyl-aminopropanol, N,N-diethylaminopropanol, N,N-di-n-propylamino-propanol, N,N-di-iso-propylaminopropanol, N,N-di-n-butylamino-propanol, N,N-di-iso-butylaminopropanol, N,N-di-sec-butylamino-propanol, N,N-di-tert-butylaminopropanol, dimethylaminopentan-4-ol and diethylaminopentan-4-ol. Suitable aminating agents in the hydrogenative amination of aminoalcohols are ammonia or primary or secondary, aliphatic or cycloaliphatic amines. If ammonia is used as aminating agent, the alcohol hydroxyls are first converted into free amino groups (—NH2). The primary amines thus formed Can react with further alcohol to give the corres¬ponding secondary amines and these Can in turn react with further alcohol to give the corresponding, symmetric tertiary amines. Depending on the composition of the reaction mixture and the reaction conditions used, viz. pressure, temperature, reaction time, this method Can be used to prepare primary, secondary or tertiary amines as desired. Primary or secondary amines Can, like ammonia, be used as aminating agent. Preference is given to using, for example, the following mono-alkylamines and dialkylamines as aminating agent: methylamine, dimethylamine, ethylamine, diethylamine, propylamine, diiso-propylamine, butylaimine, pentylamine, hexylamine and cyclohexylamine. The aminating agent Can be used in a stoichiometric amount based on the alcohol hydroxyl to be aminated. However, preference is given to using an excess of aminating agent, generally a greater than 5 molar excess per mole of alcohol hydroxyl to be aminated. Ammonia spe C1fi Cally is generally used in a from 1.5 to 250-fold, preferably from 5 to 100-fold, in particular from 10 to 50-fold, molar excess per mole of alcohol hydroxyls to be reacted. Higher excesses both of ammonia and of primary or secondary amines are possible. •particularly from 30 to 60 and most particularly from 40 to 50, parts by volume. In practice, the reaction is generally Carried out by simultan¬eously feeding the alcohol and the aminating agent to the Cata¬lyst, which is usually lo Cated in a fixed-bed reactor preferably heated externally, at the desired reaction temperature and the desired pressure. The space velo C1ty over the Catalyst is generally from 0.02 to 3 1, preferably from 0.05 to 2 1 and particularly preferably from 0.1 to 1.6 1, of alcohol per liter of Catalyst and hour. It is advantageous to heat the reactants, preferably to the reaction temperature, before feeding them into the reaction vessel. The Catalyti Cally active composition of the Catalysts of the invention contains not only oxygen-containing compounds of zirconium, but also oxygen-containing compounds of nickel, copper and molybdenum. Since the concentrations stated are each based, unless otherwise indi Cated, on the Catalyti Cally active mass of the Catalyst, the Catalyti Cally active mass of the Catalyst is hereinafter defined as the sum of the masses of the Catalyti Cally active constituents zirconium, nickel, copper and molybdenum in the Catalyst, in each Case Calculated as ZrO2, NiO, CuO or M0O3, after the Catalyst has undergone its last heat treatment and before it is reduced with hydrogen. In general the zirconium oxide content of the Catalysts of the invention is from 20 to 85% by weight, preferably from 25 to 60% by weight. a sparingly soluble, oxygen-containing zirconium compound and subsequent washing, drying and Cal C1nation of the pre C1pitate obtained. Sparingly soluble, oxygen-containing zirconium com¬pounds which Can be used are, for ex C1mple, zirconium dioxide, zirconium oxide hydrate, zirconium phosphates, borates and sili Cates. The slurries of the sparingly soluble zirconium compounds Can be prepared by suspending fine powders of these compounds in water with vigorous stirring; they are advanta¬geously obtained by pre C1pitating the sparingly soluble zirconium compounds from aqueous zirconium salt solutions by means of mineral bases. by leaving them to stand for some time after pre C1pitation, if desired while being kept hot or while passing in air. The pre C1pitates obtained by these pre C1pitation methods are processed into the Catalysts of the invention using customary methods. After washing, they are generally dried at from 8 0 to 200*C, preferably at from 100 to 150*C, and then Cal C1nated. The Cal C1nation is generally Carried out at from 300 to 800*C, preferably at from 400 to 600*C, in particular at from 450 to 550'C. 1,2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, particularly preferably C1- to C4-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, C3- to C12-cycloalkyl, preferably C3- to Ca-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, particularly preferably cyclopentyl, cyclo¬hexyl and cyclooctyl, An aqueous solution of nickel nitrate, copper nitrate and zirconium acetate, containing 4.48% of NiO, 1.52% of CuO and 2.82% of ZrO2, was pre C1pitated by mixing constant streams of this solution and a 20% strength aqueous sodium Carbonate solution in a stirred vessel at 70°C, in such a way that the pH measured using a glass electrode was kept at 7.0.

Documents:

1020-mas-1995 abstract.pdf

1020-mas-1995 claims.pdf

1020-mas-1995 correspondence-others.pdf

1020-mas-1995 correspondence-po.pdf

1020-mas-1995 description (complete).pdf

1020-mas-1995 form-1.pdf

1020-mas-1995 form-26.pdf

1020-mas-1995 form-4.pdf

1020-mas-1995 others.pdf

1020-mas-1995 petition.pdf