AMINES VIA THE AMINATION OF OLEFINS USING OFFRETITE

Abstract: This invention relates to an improvement in the vapor phase catalytic production of an amine by the reaction of a mixture comprising a C₂₋₄ olefin and ammonia. The improve­ ment which provides for high conversion and selectivity to the amine resides in the use of an acidic offretite as the catalyst.

Description: AMINES VIA THE AMINATION OF OLEFINS USING OFFRETITE TECHNICAL FIELD This invention relates tp a process for producing amines by the reaction of ammonia or ammonia type compound with an olefin. BACKGROUND OF THE PRIOR ART The earliest work relating to the manufacture of amines by the amination of olefins particularly ethylamines by the amination of ethylene, appears to have been done by Teter et al as noted in U.S. Patents 2,623,061; 2,479,879; 2,417,892; 2,381,470; 2,658,041; 2,381,709; 2,392,107 and 2,398,899. These patents show that ammonia can be made to react with olefins, e.g ethylene to produce amines. As noted by others through improvements in the process, substantial quantities of polyamines and polyolefins were produced by the Teter et al catalyst which is a metal supported on a spinel type support, silica and diatomaceous earth and the like. Olin et al in U.S. Patents 2,422,631 and 2,422,632, discloses a process for producing amines and amides by the reaction of d monounsaturated olefin, carbon-monoxide and an amine or ammonia. The catalyst used is a combination of a dehydrating and a hydrogenation catalyst, e.g. nickel and activated alumina, copper and silica gel, etc. Whitman, U.S. 2,501,556 discloses a liquid phase reaction of ammonia and ethylene in the presence of an alkali metal catalyst to form ethylamine. McClain, U.S. 3,412,158 discloses a gas phase process for producing primary alkyl amines from low molecular weight olefins and ammonia by carrying out the gas phase process in the presence of a noblemetal containing catalyst at temperatures of from 90-1750C, at pressures of from atmospheric to 2,000 psig. Peterson et al., U.S. 4,289,908 shows that aluminosilicates and particularly zeolites can be used for effecting amination of olefins at temperatures of 200-5000C, pressures from 300-6,000 psig. High yields and selectivity are reported. SUMMARY OF THE INVENTION This invention relates to an improved process for the preparation of C24 alkyl amines by the vapor phase catalytic reaction of a C2 4 olefin and ammonia. In the basic process, the olefin is reacted at a temperature and pressure sufficient to effect formation of the amine. The improvement generally resides in the use of (a) a temperature from 300-400DC, (b) a pressure of from 300-2,000 psig and (c) an acidic offretite catalyst. There are several advantages either singly or combination associated with the invention as compared to many prior art processes. These advantages include: an ability to produce C24 alkyl amines, and particularly ethylamines in high selectivity, without producing substantial by-products. The production of polymers has been a serious problem with many of the prior art processes; an ability to use a gas phase reaction which permits a high production rate in producing amines; an ability to reduce the amount of by-product in the form of by-product nitrogen compounds e.g. nitriles as compared to prior art processes; an ability to aminate multiple olefins, e.g. propylene ethylene without effecting a catalyst change in the reactor; an ability to obtain good to high conversion of olefin to amine by virtue of the use of the particular catalyst under the conditions employed and to obtain good catalyst life; and an ability to obtain a low aging rate with the particular offretite catalysts. DESCRIPTION OF THE PREFERRED EMBODIMENT In the amination process, the olefin is reacted with ammonia to produce the amine. Higher molecular weight olefins, e.g. propylene and butylene are more difficult to aminate with these catalysts, but in contrast to similar zeolites, e.g., clinoptilolite and erionite, offretite is more active and will effect amination of the higher olefins. In the process, ammonia-is reacted with the C2-C4 olefin at temperatures broadly from about 300-4000C. Lower temperatures result in lower conversion, and higher temperatures often result in lower selectivity which generally appears in the form of a nitrile or unreacted hydrocarbon. Pressures suited for practicing the invention are from about 300-2,000 psig with preferred pressures of from about 600-1100 psig. Generally, pressures lower than about 600 psig result in poor conversion of ethylene to amine. On the other hand, as the pressure is increased above about 1500 psig, conversion is increased only slightly. In order to minimize the recovery problems associated with separating the amine from the reactants and other by-products, higher conversions can be waived and pressures of from about 600-1100 psig used as this permits extremely high selectivities, e.g. greater than 95%. Another important variable in the gas phase amina-. tion of the olefin is the mole ratio of ammonia to olefin in the feed. Generally, the mole ratio can be from about 0.2-20 moles ammonia per mole of olefin with preferred ranges being from about 1-10 to 1 ammonia to olefin. Mole ratios higher than about 10:1 of course require greater energy expenditure to handle the larger guantities of gas that pass through the reactor, and there seems to be no significant advantage in terms of increased selectivity or conversion at these higher ratios of ammonia to olefin On the other hand, as the mole ratio of ammonia to olefin falls below about 0.2, there is a loss of selectivity to the amine. The gas hourly space velocity (GHSv), which has units of volume of gas per volume of catalyst in unit time i.e. (cc gas at STP)/(cc catalyst hours 1), can be from about 500-5,000 with a preferred range being from about 750-2,000. As the space velocity is increased' toward the upper end of the range, conversion generally falls dramatically, particularly above about 3,000. On the other hand, as the space velocity approaches the lower level of 500, selectivity decreases and by-products form in greater concentration. One of the important factors in achieving high selectivity to amines without the concomitant production of substantial amounts of by products in the form of polymer, e.g. polyethylene; or hydrocarbons or nitrogen compounds as encountered in the prior art processes including those using zeolites, is the use of a highly acidic offretite. This zeolite is highly selective for the amination of ethylene and propylene and produces unique results in terms of conversion. For example chabazite, which is a natural zeolite, gives lower conversion and selectivity. So does clinoptilolite and erionite and, from an energy viewpoint, higher selectivity and conversions can be achieved with the acidic offretite at lower temperatures. Thus, in the reaction1 at least about 80% by weight and preferably all of the catalyst employed should be an acidic offretite. It is believed the high acidity and narrow pore size of this material plays an important role in the catalyst activity and selectivity. Various ions can be incorporated into the offretite by conventional techniques to provide acidity. Trivalent ions, and particularly the rare earth mentals, i.e. lanthanum, neodymium, praseodymium, are well suited for preparing exchanged zeolites. Other cations which may be used in place of the original metal cations of the offretite include hydrogen, barium, beryllium, calcium, cerium, magnesium, potassium, silver and zinc. However, sodium and potassium tend to reduce activity presumably due to the lowering of the acidity of the catalyst. The alumino-silicate, offretite, of the present invention may be employed alone or in combination with various binder or matrix materials (organic or inorganic materials, resins, clays, gels or the like). The physical form of the catalyst may be adapted to use in any conventional catalytic system (e.g. slurry or fluidized bed systems, beads, pellets or the like for use in fixed or moving bed catalysts). As is known, the hydrogen form of offretite can be prepared from the ammonium form and for purposes herein is preferred to as the hydrogen form. The preferred ions for the exchanged offretite are lanthanum and hydrogen as the exchanged offretite provide good yields, good selectivity and good catalyst life. The following examples are provided to illustrate preferred embodiments of the invention and are not intended to restrict the scope thereof. EXAMPLE 1 A series of amination reactions were carried out using a reactor consisting of a stainless steel tubing 9 inches long of 3/4" outside diameter and 5/16s' inside diameter. The stainless steel reactor was mounted inside a close fitting block of Inconel metal which was instrumented for temperature control. A thermowell extending axially through the reactor was used to measure reactor temperature. The catalyst volume for the reactor was approximately 6 cubic centimeters, and the catalyst was held in place by a quartz wool plug. The catalysts were sieved to pass through a 12 U.S. standard sieve but retained on an 18 mesh sieve. In the runs the experimental catalysts were prepared by conventional techniques, as for example, by the technique set forth in U.S. 3,758,539, which technique is incorporporated by reference. Such H-form offretite catalysts used here were generally prepared by synthesizing the tetramethyl ammonium form followed, pelletizing and heat treating at 1,0000F. Comparisons were made against Linde SK-500 zeolite (REY - a rare earth exchanged zeolite), and H forms of clinoptilolite and erionite. Table 1 represents results for the various catalysts tried including reactor conditions. Table 2 is an average summary of work carried out in the manner of Table 1 including runs 1-8. TABLE 1 ETHYLENE CONVERSION OVER H-OFFRETITE Moles NH3/ Conv. % Selectivity Run Olefin Catalyst T, C PSIG GHSV Olefin (%) Monoamine Diamine Other 1 Ethylene H-offretite 320 750 2000 4.2 4.0 100 2 " " 340 750 2000 4.1 7.2 95 4 3 " " 360 750 2000 4.0 12.3 93 5 4 " " 380 750 2000 4.2 16.9 90 6 5 " " 340 750 2000 4.2 7.3 95 4 6 " " 340 750 1180 1.8 10.1 88 11 7 " " 350 750 1180 1.7 11.9 86 12.5 8 " " 360 750 1180 1.7 14.6 84 14 9 Propylene " 300 750 2000 4.0 0.55 100 10 " " 320 750 2000 4.0 1.60 100 11 " " 340 750 2000 4.0 3.67 95.5 4.5 12 " " 350 750 2000 4.0 4.48 95.0 5.0 13 " " 350 750 1000 4.0 6.40 93 7 14 " " 350 750 500 4.0 7.20 90 8 15 " " 300 750 2000 2.0 1.0 95 5 16 " " 320 750 2000 2.0 2.1 96.4 3.6 17 " " 340 750 2000 2.0 3.6 95 5 18 " " 350 750 2000 2.0 4.2 94 6 19 " " 350 750 1000 2.0 5.2 90.2 6.5 3.7 20 " " 350 750 500 2.0 5.2 87 7 6 21 Ethylene Clinoptilotite 340 750 2000 4.5 4.4 100 22 " " 340 750 2000 4.9 6.6 100 23 " " 360 750 2000 4.6 11.4 100 24 " " 370 750 2000 4.4 13.7 93.1 6.9 25 " " 370 750 2000 4.6 14.9 91.4 8.6 26 " " 380 750 2000 4.4 14.8 91.9 8.1 27 " " 380 750 2000 4.7 14.4 92 8 28 " " 390 750 2000 4.4 15.7 91 9 29 " " 400 750 2000 4.7 18 90.2 9.8 30 " SK-500 350 750 2000 4.6 3.9 100 31 " " 360 750 2000 4.3 7.5 100 32 " " 370 750 2000 4.3 9.4 96 4 33 " " 380 750 2000 4.2 12.1 92.6 5.4 34 " " 390 750 2000 4.0 12.8 81.9 4.5 13.6 35 " " 400 750 2000 3.8 13 69 2.0 28.9 TABLE 1 (CONTINUED) AMINATION OF OLEFINS Moles NH3/ % Selectivity Run Olefin Catalyst T, C Psig GHSV Olefin % Conv. Monoamine Diamine Other 36 Ethylene H-Erionite 360 750 2000 3.4 4.0 88.5 10.7 0.8 37 " " 375 750 2000 8.0 15.5 88.4 10.5 1.1 38 " " 380 750 2000 3.5 12.3 84.7 13.8 1.5 39 " " 380 750 2000 5.2 9.9 88.5 8.8 2.7 40 " " 380 750 2000 4.1 13.5 83.3 12.3 2.6 41 " " 380 750 2000 4.7 12.9 87.8 10.0 2.2 42 " " 380 750 2000 5.5 13.0 88.4 8.7 2.9 43 " " 380 750 2000 5.6 14.4 87 8.5 4.5 44 " " 390 750 2000 5.8 15.1 86.2 8.4 5.0 45 " " 390 750 2000 5.8 16.3 84.3 8.6 5.6 46 " " 400 750 2000 5.7 17.5 77.7 7.7 14.6 47 " " 400 750 2000 5.8 17.9 78.6 7.9 13.2 48 " " 320 750 2000 3.8 1.6 90.8 3.7 5.5 49 " " 320 750 2000 4.3 2.8 95.4 4.5 50 " " 340 750 2000 4.7 3.5 97.2 2.7 51 " " 360 750 2000 4.5 7.4 92.4 6.7 0.8 52 " " 360 750 2000 3.0 8.7 88.6 10.5 1.0 53 " " 370 750 2000 2.7 10.2 86.2 12.5 1.2 54 " " 380 750 2000 3.2 13.4 85.4 11.7 1.7 55 " " 380 750 2000 4.0 15.2 85.7 12.5 2.3 56 " " 400 750 2000 3.9 16.5 84.2 13.1 2.5 57 Propylene " 320 750 2000 4.1 0.14 100 58 Propylene " 340 750 2000 4.5 0.46 100 59 Propylene " 360 750 2000 5.0 1.5 90.7 60 Propylene " 380 750 2000 4.6 2.1 89.8 61 Propylene " 400 750 2000 4.7 2.7 75.5 17.8 62 Propylene H-Clinoptilo- 320 750 2000 4.0 0.13 68 lite 63 Propylene " 340 750 2000 3.9 0.34 100 64 Propylene " 360 750 2000 4.1 1.0 88.1 - Table 2 Comparison of Ethylene Conversion and Amine Selectivity as a Function of temperature SK-500 clinoptilolite H-erionite H-offretite Temp. A B A B A B A B 340 5.6 100 5.26 100 7.7 99.8 350 8.3 100 360 5.3 100 9.7 100 8.76 99.2 12.3 99.7 370 8.0 100 11.7 100 12.52 98.7 17.1 99.6 380 10.3 98 12.6 100 11.13 97.8 17.2 98.8 390 10.8 86.4 14.6 100 400 11.0 71 15.3 99.6 17.79 94 = % C2H4 conversion was corrected by introducing correction factors of 0.7 and 0.6 for C2H4 and MEA respectively. A = Z ethylene conversion. B = selectivity to ethylamines. The data in Tables 1 and 2 shows that the H-offretite and H-erionite consistently gave better selectivity and better conversion than SK-500 at a given temperature and mole ratio, etc. The data in Table 1 also shows generally better conversion for H-offretite than Hclinoptilolite or H-erionite at a given temperature. (Note Runs 3, 4, 8, 25, 26, 33-35, 38, 44-47, 55 and 56.) Runs 9-19, particularly, runs 12-14 and 57-64 show that Hoffretite is much more effective for aminating propylene than H-clinoptilolite and H-erionite. Because of this ability, H-offretite offers an advantage over previous catalyst systems in that it can be used to aminate multiple olefin feedstocks without a catalyst charge. H-clinoptilolite and H-erionite are not effective for propylene. Table 2 shows high conversion for H-offretite at temperatures from 370-3800C. Although there were instances where high conversions were obtained with other catalysts, H-offretite on the average, gave better results. From the data in the tables it is clear that the H-offretite is extremely effective for the amination of ethylene, and it is more effective than the standard Linde SX-500 zeolite (a rare earth exchanged Y zeolite), H-erionite and H-clinoptilolite Conversions were significantly higher than were achieved with the B- clinoptilolite and H-erionite catalysts at temperatures from about 370-4000C. In those cases where conversions were forced to a higher level with SK-500, the corresponding selectivity to the desired amine products was lower than where higher conversions were achieved using clinoptilotite and erionite, note runs 19-30 and Table 2. Another interesting point about H-offretite is that, like H-clinoptilolite and H-erionite, only a small fraction of the reaction product was non-amine, even at high conversions, whereas higher by-product levels were experienced with SK-500. STATEMENT OF INDUSTRIAL APPLICATION This invention permits the formation of lower alkyl (C2 4) amines by the reaction of relatively inexpensive raw materials. The lower alkyl amines have numerous uses as chemicals for the manufacture of herbicides, as catalysts and other uses.

Claims: What is Claimed is: 1. In a vapor phase catalytic amination process for the production of amines from a reaction mixture comprising a C24 olefin and ammonia at a temperature and pressure sufficient for effecting formation of said amine the improvement which comprises: employing an acidic offretite as a catalyst for said process. 2. The process of Claim 1 wherein said acidic offretite is rare earth or hydrogen ion exchanged 3. The process of Claim 2 wherein the pressure in said amination is from 600-1100 psig, and the gas hourly space velocity is from 500-5,000. 4. The process of Claim 3 wherein the temperature in said amination is from 300-400"C. 5. The process of Claim 3 wherein said olefin is ethylene and the mole feed ratio of ammonia to ethylene is from about 1-10:1. 6. A method for making amines which comprises contacting ethylene and ammonia in the vapor phase with a catalyst comprising an acidic offretite under amination conditions which include a temperature in the range of about 300-4000C, a pressure in the range of about 600-1100 psig, a mole ratio of ammonia to ethylene of about 1-10:1 and a gas hourly space velocity of about 500-5000. 7. The process of Claim 6 wherein said acidity is provided by trivalent rare earth metal or hydrogen ions. P9-C

Inventors: AMBS, WILLIAM JOSEPH, DEEBA, MICHEL, WHITE, JAMES FERGUSON
Applicants: AIR PRODUCTS AND CHEMICALS, INC.
Application year: 1983
Main classification: C07C85
IPC codes: C07B61, C07C211, B01J21, C07C67, C07C209