SYNTHESIS OF LOWER ALKYL AMINES

Abstract: A process for producing lower alkyl amines by reacting a gaseous alcohol with ammonia at a temperature of from 177°C to 260°C in the presence of hydrogen and a catalyst comprising a Group 8 metal carried on an alumina support is characterized in that the alcohol is a lower alkanol and the support has been rendered neutral or substantially neutral by the incorporation therein of a basic material containing an alkaline earth metal. By neutralising or substantially neutralis­ ing the support the amount of hydrocarbon by product formed is reduced thereby increasing the effect life of the catalyst. Further reduction in the amount of hydrocarbon pro­ duced can also be achieved by varying the ratio of lower alkanol to ammonia to hydrogen and ratios of 10-16/1/0.25-1 seem particularly suitable.

Description: This invention relates to a process for producing lower alkyl amines and, more particularly but not exclusively, is concerned with a process for producing ethyl, n-propyl, isopropyl, n-butyl and isobutylamine. It has been proposed to produce amines by reacting a gaseous alcohol with ammonia at a temperature of from 177 C to 260 C in the presence of hydrogen and a catalyst comprising a Group 8 metal carried on an alumina support. One of the difficulties associated with this process is that the catalyst readily becomes coated with carbon and is thus inhibited. We believe that the source of this carbon is the hydrocarbon which is produced as a by product and the problem was to reduce the amount of hydrocarbon produced whilst maintaining an acceptable conversion. This aim is generally met, when the alcohol is a lower alkanol i.e. containing 1 to 6 and preferably 1 to 4 carbon atoms, by neutralising or substantially neutralising the support by the incorporation therein of a basic material comprising an alkaline earth metal. Preferably, the alkaline earth metal is calcium, barium, magnesium or mixtures thereof. Suitable basic materials are the hydroxides of calcium or barium and the salts thereof. Preferably, the support should have a pH from 6.5 to 7.5. In addition to neutralising or substantially neutralising the support it also appears to us that the relative amounts of alkanol, ammonia and hydrogen are important and whereas the general ratio of 2-20/1/0.25-4 (by moles) should give reasonable results it may be found more beneficial to operate in the range 10-16/1/0.25-1 more particularly, but not exclusively, in the conversion of ethanol to monoethylamine. Preferably, the gas hourly space velocity (GHSV) is maintained between 500 and 5000 volumes of reactant per volume of catalyst per hour with preferred GHSV's being from 1000 to 3000 volumes of reactant per volume of catalyst per hour. The supported catalyst can conveniently be made by mixing ammonium hydroxide with an acidic solution of aluminium chloride, a slurry of barium hydroxide and a nickel salt. The gel which forms is separated from the liquid and is calcined at 1000 to 12000F for a period of four hours. The following Examples are provided to compare preferred embodiments of the present invention with the prior art and are not intended to restrict the scope of the present invention. EXAMPLE 1 The conversion of ethanol to monoethylamine by reaction with ammonia in the presence of hydrogen was effected in a laboratory reactor at a temperature of 216 C and a pressure of 17 bars gauge. The volume of catalyst in the laboratory reactor was 100 cubic cm of a Girdler-62RS cobalt catalyst. This catalyst contain ed approximately 34% cobalt supported on a neutralised alumina substrate. The surface area in meters squared per gram was approximately 42 with a DWL crush strength of 6.8 Kg. The bulk density was approximately 50 plus or minus 5 pounds per cubic foot. Table 1 shows the results of the ammonolysis with variations in reaction conditions. The heading (N/R/H) refers to the ratio of ammonia to ethanol to hydrogen on a molar basis and the heading (GHSV) refers to the gas hourly space velocity. The percent conversion is related to the amount of monoethylamine produced based on the ethanol charged and the remaining figures refer to the molar yield (in percent) of monoethylamine (MEA), diethylamine (DEA), triethylamine (TEA), acetonitrile (ACN), mono n-butylamine (MNBA), and the hydrocarbon content (HC). T A B L E 1 Ethylamines From Ethanol Molar Yield N/R/H GHSV % Conv. MEA DEA TEA ACN MNBA HC 2/1/1 1000 88.03 46.79 44.27 6.73 0.06 2.15 5.78 2/1/1 2000 82.01 50.73 39.10 10.01 0.16 0 1.64 2/1/1 3000 69.96 55.97 38.25 5.21 5.21 0.53 4/1/1 1000 95.98 52.43 40.47 6.86 0.03 0.21 2.67 4/1/1 2000 76.22 72.57 23.24 3.03 1.01 0.09 2.50 4/1/1 3000 72.47 68.64 27.17 2.01 0.22 0.43 3.01 8/1/1 1000 82.69 76.55 17.84 0 5.60 0 8/1/1 2000 72.87 72.97 10.68 2.76 13.32 0 2.72 8/1/1 3000 61.69 79.16 14.51 0 6.34 0 3.01 10/1/1 1000 77.48 58.95 36.74 5.21 0.41 0 10/1/1 2000 72.45 75.33 17.47 1.51 0.54 0 10/1/1 3000 66.19 67.29 17.48 7.32 7.55 0.36 16/1/1 1000 81.13 69.63 4.65 1.16 15.82 3.31 16/1/1 2000 73.97 57.22 8.43 17.17 12.56 4.61 16/1/1 3000 81.39 61.36 0.85 0 34.51 3.27 4/1/2 1000 87.90 28.05 59.46 11.55 0 0.94 7.10 4/1/0.5 1000 58.52 81.19 16.37 1.25 0 1.20 4/1/0.25 1000 54.72 71.93 21.29 2.55 1.15 3.10 1.55 2/1/1 1000 71.80 78.86 10.84 0 10.10 0.21 4/1/1 1000 83.54 50.85 41.79 7.36 0 0 3.29 8/1/1 1000 65.28 64.47 25.73 8.01 0 0.21 3.74 The results in Table 1 show that good conversion to amines was obtained with very little to practically no hydrocarbon being produced particularly where the molar ratio of ammonia to ethanol to hydrogen ranged from 10-16/1/1. On the other hand, the percent conversion increased slightly with increasing molar concentration of ammonia and the concentration of monoethylamine on a molar basis, increased as compared to runs made at lower ammonia to ethanol to hydrogen ratios. It is important to note that as the molar concentration of ammonia to ethanol to hydrogen increased to about 16/1/1, the concentration of by-product acetonitrile increased substantially and, for these reasons, it would seem that the better results were obtained at a level of about 8-10/1/1. Table 1 also shows as the hydrogen concentration increased above a 1:1 to that of ethanol, a higher concentration of hydrocarbon was produced. On the other hand, as the ratio of alkanol to hydrogen increased above 1, e.g. 1/0.5 and 1/0.25, the hydrocarbon content was reduced. Although the data does not specifically show results, it is anticipated that if the ratio of ammonia to ethanol ranged from about 4-10 to 1, and the ratio of hydrogen to ethanol was greater than 1, higher concentrations of monoethylamine would be produced. EXAMPLE 2 The procedure of Example 1 was repeated with various nickel catalysts supported on silica and silica-alumina supports as taught in the prior art. The ratio of ammonia to ethanol to hydrogen was 4/1/1 and the reaction temperature was 2160C. Table 2 below represents the results for various proprietary nickel catalysts all of which are sold by the Harshaw Chemical Co. T A B L E 2 Catalyst Yield Mole % % Molar Conv. N/R/H GHSV T F MEA DEA TEA ACN Et2O MNBA CO2 HC Ni-3210T 64.9 4/1/1 1000 420 44.0 33.2 4.47 0.80 ND 0.20 0.22 17.13 Ni-0148T 41.2 4/1/1 1000 420 43.4 44.3 10.9 0.50 ND 0.12 0.05 0.78 Ni-3266E 84.5 4/1/1 1000 420 27.1 32.3 6.43 ND ND ND X's = 33.6 Ni-0104T 87.8 4/1/1 1000 420 41.4 42.6 5.50 0.93 ND 2.18 0.90 6.52 Nix649-93T 85.7 4/1/1 1000 420 29.7 45.5 17.2 0.19 ND ND 0.04 8.34 ND = Non-detectable The results of Table 2 show that many nickel catalysts utilized in the prior art for the production of monoethylamine resulted in substantially lower quantities of monoethylamine as compared to the monoethylamine content prepared by the catalyst having a neutral alumina support. It should also be noted that with one exception, where the molar conversion was unacceptable, the hydrocarbon content in the reaction mixture generally was substantially higher than that in Example 1.

Claims: CLAIMS 1. A process for producing amines by reacting a gaseous alcohol with ammonia at a temperature of from 1770C to 2600C in the presence of hydrogen and a catalyst comprising a Group 8 metal carried on an alumina support, characterized in that said alcohol is a lower alkanol and said support has been rendered neutral or substantially neutral by the incorporation therein of a basic material comprising an alkaline earth metal. 2. A process according to Claim 1, characterized in that said alkaline earth metal is calcium, barium, magnesium or mixtures thereof. 3. A process according to Claim 1 or 2, characterized in that said basic material is the hydroxide of calcium or barium or a salt thereof. 4. A process according to Claim 1, 2 or 3, characterized in that said support has a pH of from 6.5 to 7.5. 5. A process according to Claim 1, 2, 3 or 4, characterized in that said lower alkanol, ammonia and hydrogen are brought together in the ratio of 2-20/1/0.25-4 (by moles). 6. A process according to Claim 5, characterized in that said ratio is 10-16/1/0.25-1.

Inventors: FOWLKES, ROBERT LEE, MARTINEZ DE PINILLOS, JOAQUIN VICTOR
Applicants: AIR PRODUCTS AND CHEMICALS, INC.
Application year: 1979
Main classification: C07C85
IPC codes: B01J23, B01J21, C07B61, F16D31, C07C209, C07C211, C07C67