Patent Publication Number: US-4254061-A

Title: Preparation of monomethylamine

Description:
DESCRIPTION 
     1. Technical Field 
     This invention relates to the preparation of monomethylamine by a catalytic process from methanol and ammonia. 
     2. Background 
     It is well known in the art that the catalyzed reaction of methanol and ammonia can be employed to produce mono-, di- and/or trimethylamine. To facilitate the formation of any one of the methylamines various expedients can be used. For example, it is known that the use of dimethyl ether in conjunction with or in place of methanol, recycling unwanted methylamines, the use of varying molar ratios of the reactants and the use of specific dehydrating or aminating catalysts can be employed to alter the relative amounts of the various amines in the product. 
     Exemplary, but not intended to be all inclusive, of such art, U.S. Pat. No. 3,278,598 discloses an improved, Raney nickel-catalyzed, liquid phase process of reacting primary and secondary alcohols and ammonia, the improvement comprising the use of a rhodium, palladium or ruthenium cocatalyst, to provide increased formation of secondary amine. Similarly, U.S. Pat. No. 3,387,032 discloses a catalytic process for providing increased amounts of dimethylamine from methanol and/or dimethyl ether and ammonia, using as the catalyst a silica gel-based alumina which has been partially steam deactivated and then impregnated with silver phosphate rhenium heptasulfide, molybdenum sulfide or cobalt sulfide. U.S. Pat. Nos. 2,394,515 and 2,394,516 disclose catalytic processes for preparing polyalkylamines, with lesser quantities of the monoalkylamine, from an alcohol and/or ether of 1-5 carbon atoms and ammonia, using as the catalyst an aluminum oxide or salt which has been coated, first with silica and then with a vanadium salt or molybdenum oxide. The related U.S. Pat. No. 2,349,222 utilizes as the catalyst a granular alumina which has been coated with a nickel, cobalt or chromium oxide hydrogenation/dehydrogenation catalyst. U.S. Pat. No. 2,456,559 discloses that higher amounts of mono- and dimethylamine, and a reduced amount of trimethylamine, can be achieved in the catalyzed process wherein water is introduced along with the methanol and ammonia. U.S. Pat. No. 1,799,722 and U.S. Pat. No. Re. 19,632 disclose catalytic processes wherein trimethylamine is introduced with the methanol and ammonia to suppress the formation of trimethylamine and provide increased amounts of dimethylamine. U.S. Pat. No. 1,992,935 discloses a catalytic process for preparing a mixture of primary, secondary and tertiary methylamines, principally dimethylamine, from methanol and ammonia, using as the catalyst a dehydrating oxide supported on a porous rigid gel such as silica gel. British Pat. No. 422,563 discloses a catalytic process for producing secondary amine by employing the primary amine as starting material in addition to ammonia and alcohol. 
     Restelli et al. in A.I.Ch.E. Journal, Vol. 12, No. 2, 292-296, March, 1966, describe studies of transmethylation reactions of monomethylamine and dimethylamine over montmorillonite, a hydrated magnesium/calcium oxide-containing aluminosilicate. With the reactions being carried out at about 320°-371° C., at low conversions the monomethylamine is converted to dimethylamine, the rate being directly proportional to the amine partial pressure, thus indicating that adsorption of monomethylamine on the catalyst surface is rate-determining. 
     U.S. Pat. No. 3,384,667 discloses a process for producing monosubstituted and disubstituted amines, in preference to trisubstituted amines, by reacting an alcohol and ammonia over a dehydrated crystalline metal aluminosilicate catalyst having pores of a diameter that pass the monosubstituted and disubstituted amine products but not the trisubstituted amine products. The related U.S. Pat. No. 4,082,805 discloses a process for producing primary aliphatic amines, in preference to secondary and tertiary amines, from a C 1  -C 5  alcohol or ether and ammonia over a natural or synthetic dehydrated crystalline aluminosilicate having the structure of ZSM-5, ZSM-11 or ZSM-21, at 300°-500° C., at one atmosphere to 1000 psig pressure, the feed rate of alcohol or ether and ammonia being within the ratio 1:1 to 5:1. 
     Methylamines presently are generally produced commercially by a continuous process for methanol and ammonia, using an amorphous silica-alumina catalyst. Even at low methanol conversions such processes generally produce more trimethylamine than mono- and dimethylamine. Production of the maximum amount of monomethylamine is achieved when equilibrium is reached, at high methanol conversion. However, the relative amounts of the three amines produced at equilibrium depend, to a large extent, on the carbon/nitrogen (C/N) ratio, that is, the methanol/ammonia ratio in the reactants. At carbon/nitrogen ratios of about one the product mixture contains, on a mole basis, about 55% ammonia, 22% trimethylamine (TMA), 12% monomethylamine (MMA) and 12% dimethylamine (DMA). The product mixture can be separated and the less desirable methylamine can be recycled. 
     Monomethylamine is employed in the manufacture of: pharmaceutical intermediates for the xanthine alkaloids, theophylline, caffeine, the symphatomimetic drugs such as ephedrine and the analgesic meperidine; surface active agents; photographic developers; dyes; and soil fumigants, fungicides and insecticides for agriculture. 
     An object of this invention, therefore, is to provide a process for selectively preparing monomethylamine directly from methanol and ammonia, which process minimizes the formation of dimethylamine and trimethylamine. Other objects will become apparent hereinafter. 
    
    
     BRIEF DESCRIPTION OF DRAWINGS 
     The accompanying drawings form a material part of this disclosure. 
     FIG. 1 provides plots showing the equilibrium distribution of ammonia, monomethylamine, dimethylamine and trimethylamine at various C/N ratios (0 to 3.0). FIGS. 2 and 3 provide plots showing the selectivity of the catalyst of the invention process, as compared to the use of a conventional amorphous silica-alumina catalyst which is outside the invention, in preparing monomethylamine from methanol and ammonia at two different C/N feed ratios. 
     More specifically, the drawings provide plots showing the percentages of monomethylamine in the monomethylamine/dimethylamine/trimethylamine products obtained at varying conversions of methanol with the aforesaid catalysts. 
    
    
     DISCLOSURE OF INVENTION 
     For further comprehension of the invention, and of the objects and advantages thereof, reference may be made to the following description and accompanying drawings and to the appended claims in which the various novel features of the invention are not particularly set forth. 
     The invention herein resides in an improved catalytic process, for example, over those of U.S. Pat. Nos. 4,082,805 and 3,384,667, for preparing monomethylamine from methanol and ammonia. More specifically, the invention resides in the catalytic process, which can be carried out continuously, wherein methanol and ammonia, in such amounts so as to provide a carbon/nirogen (C/N) ratio, from the methanol and ammonia reactants, of 0.5 to 1.5, are reacted over a dehydrated crystalline aluminosilicate (Zeolite) catalyst selected from 
     (a) mordenite wherein the primary cation is Li, Na, HNa having at least 2% Na by weight (for example, 2-4.3% Na), K, Ca, Sr, Ba, Ce, Zn or Cr 
     (b) ferrierite wherein the primary metal cation is Li, Na, K, Ca, Sr, Ba, Ce or Fe 
     (c) erionite ore 
     (d) calcium erionite and 
     (e) clinoptilolite ore, 
     at a temperature of 250°-475° C., a pressure of 1-1000 psi (7-7000 kPa), a contact time, normalized to 7 kPa pressure, of 0.1-60 seconds and a methanol conversion of 15-95%. Preferably, the process is carried out with the Na or HNa mordenite catalyst at 350°-400° C. and 10-500 psi (70-3000 kPa), especially 300 psi (2000 kPa), at a contact time of 1-10 seconds. The preferred catalysts herein are sodium mordenite because it provides good selectivity and the HNa mordenite because it provides both a high reaction rate and good selectivity. Use of the term &#34;HNa&#34; in the description of mordenite is intended to indicate the presence of both H +  and Na +  cations. 
     Table I shows relative rate constants derived for the seven types of reactions commonly involved in methylamine production from methanol and ammonia, using three conventional catalysts and the catalysts of the process of this invention, the latter being exemplified in this instance by sodium mordenite. For each catalyst type the rates are relative to that of reaction (1) arbitrarily selected as 1 (written as .tbd.1). 
     
                       TABLE I                                                     
______________________________________                                    
              So-                                                         
              dium                                                        
              Mor-    Amorphous                                           
              den-    Silica-                                             
Equation      ite     Alumina   Al.sub.2 O.sub.3                          
                                      REX*                                
______________________________________                                    
(1) NH.sub.3 + MeOH →                                              
                  .tbd.1  .tbd.1  .tbd.1                                  
                                        .tbd.1                            
    MMA + H.sub.2 O                                                       
(2) MMA + MeOH →                                                   
                  0.7     20      15    &gt;100                              
    DMA + H.sub.2 O                                                       
(3) DMA + MeOH →                                                   
                  0.5     120     45    &gt;10,000                           
    TMA + H.sub. 2 O                                                      
(4) MMA + MMA →                                                    
                  0.09    4       **    **                                
    DMA + NH.sub.3                                                        
(5) DMA + DMA →                                                    
                  0.0022  7.2     **    **                                
    TMA + MMA                                                             
(6) MMA + DMA →                                                    
                  0.045   20.4    **    **                                
    TMA + NH.sub.3                                                        
(7) MeOH + MeOH →                                                  
                  &lt;0.01   ˜1                                        
                                  &gt;&gt;1   ˜1                          
    DME + H.sub.2 O                                                       
______________________________________                                    
 *REX = Rare Earth X Zeolite                                              
  **In the same ratios as on amorphous silicaalumina for reactions (4), (5
 and (6).                                                                 
 &lt; = less than                                                            
 &gt; = greater than                                                         
 &gt;&gt; = much greater than                                                   
 ˜ = about-                                                         
 
    
     From the table it may be seen that the rate of each of the undesirable reactions (2) through (7) is substantially less when the catalyst of the invention process is used. 
     Most of the catalysts which are useful herein are commonly available or can be prepared readily by one skilled in the art. Following are examples of preparative procedures which can be employed. 
     Sodium-hydrogen mordenite can be prepared by admixing sodium mordenite extrusions and aqueous hydrochloric acid, in appropriate amounts, allowing the mixture to stand overnight, removing the solids by filtration, washing the recovered solids with distilled water, and then air drying and calcining the solids at 400° C. for four hours. 
     Calcium mordenite can be prepared by refluxing an aqueous calcium chloride solution (25 grams of calcium chloride in 150 ml of distilled water) containing 20 grams of sodium mordenite for three days, decanting the supernatant, adding fresh aqueous calcium chloride solution, refluxing another three days, removing the solids by filtration, washing the recovered solids with distilled water to remove chloride, and then air drying and calcining the solids. 
     Calcium erionite can be prepared by refluxing an aqueous calcium chloride solution containing erionite ore for several hours, decanting the supernatant, and washing the recovered solids with water to remove chloride. 
     Other crystalline aluminosilicates (Zeolites) such as strontium, barium or cerium mordenite and calcium, strontium, barium or cerium ferrierite can be prepared by refluxing 10 grams of the appropriate Zeolite and 10 grams of the nitrate salt in 100 ml of water, removing the solids by filtration, washing the recovered solids with distilled water, and then drying the solids for two hours at 110° C., two hours at 200° C. and 4 hours at 400° C. 
     Process variables of this invention include methanol/ammonia (C/N) ratio, temperature, pressure and contact time (flow rate). If the temperature is too low, the conversion of methanol and ammonia to monomethylamine will be low. If the temperature is too high, equilibration and coking (carbonization) may result unless the contact time is reduced. Unduly large reaction vessels are required if the process is carried out at very low pressure, and the products must be refrigerated to condense them for further purification; costly thick-walled vessels are required at excessively high pressures. Short contact times result in low methanol-ammonia conversions and long contact times may result either in inefficient use of catalyst at low temperatures, or equilibration and coking at high temperatures. Generally, contact times of 0.1-60 seconds, normalized to 7 kPa pressure, are satisfactory, with 1-10 seconds being preferred (corresponding to flow rates of 0.04-25 g of methanol/g of catalyst/hour, preferably 0.25-2.5 g of methanol/g of catalyst/hour). 
     The reactant ratio of methanol and ammonia (the C/N ratio) is vitally important, as can be seen from FIG. 1 which illustrates the effect of the C/N ratio on the ammonia-amine distribution at equilibrium. At a low C/N ratio, for example, less than about 0.5, monomethylamine is favored regardless of the catalyst employed. As the C/N ratio increases, production of trimethylamine increases sharply but the amounts of monomethylamine and dimethylamine produced change to a lesser degree, decreasing to zero at a C/N ratio of 3.0, as the trimethylamine production reaches 100%. Coking also occurs at high C/N ratios. As already indicated, the process of this invention provides monomethylamine in substantial amounts, while minimizing the formation of dimethylamine and, especially, trimethylamine. A C/N ratio of about 1 is desirable in the process of the invention to maximize the amount of monomethylamine formed. 
     The efficiency of the catalyst employed herein is defined by the conversion of methanol and the selectivity to monomethylamine. As the term is used used herein, methanol conversion, assuming little or no contribution from reaction (7), in %, is 100--100  [MeOH/(MeOH+MMA+2DMA+3TMA)] and selectivity, in %, is 100 [MMA/(MMA+DMA+TMA)]. Stated in another way, conversion is determined from the amount of methanol (considered to be uncoverted) in the product mixture of methanol and the three amines. Selectivity is determined from the amount of monomethylamine relative to the monomethylamine, dimethylamine and trimethylamine in the product mixture, that is, the amount of primary amine which is produced from that portion of the methanol which has been converted. If there is significant contribution from reaction (7), conversion, in %, is 100--100 [(MMA+2DMA+3TMA)/(C/N) ratio] where MMA+DMA+TMA+NH 3  is 1. 
     A catalyst is considered non-selective herein if: (1) the observed selectivity was significantly less than that calculated (using the data of Table I and the procedures set forth at the end of Example 1) for the conventional amorphous silica-alumina catalyst, or (2) if a preponderance of unwanted TMA was produced. The relevant parameter distingluishing a selective catalyst from a non-selective catalyst is the relative adsorption (on the catalyst) of methanol vs. the three amines. Non-selective catalysts adsorb the species on the basis of their basicities: DMA&gt;MMA&gt;NH 3  &gt;MeOH; selective catalysts adsorb the species on the basis of their heats of condensation: MeOH&gt;NH 3  &gt;MMA&gt;DMA. 
     The following examples are provided to illustrate specific embodiments of the invention. 
     EXAMPLE 1 
     Methanol and ammonia in such amounts so as to provide C/N ratios within the ranges 0.95-1.05, that is, about 1.0, and 1.40-1.60, that is, about 1.5, were passed over 3 of sodium mordenite catalyst in a Vycor® tubular reactor 0.5 inch (1.3 cm) in diameter and having a 3 inch (8 cm) zone heated with a split tube furnace, at atmospheric pressure, at a variety of temperatures and contact times (flow rates) within the scope of the process of the invention. The reactor effluent was analyzed by gas chromatography using a 10 foot (3 m)×0.125 inch (0.32 cm) column of polyethylene oxide (25% Carbowax® 400), 2.5% NaOH on 80/100 mesh (U.S. Sieve Series) diatomaceous earth (Chromosorb® WAW). The temperature was held at 65° C. for four minutes to elute the three amines and ammonia in the order: TMA, NH 3 , DMA and MMA, and then programmed to 100° C. at 32° C./minute to elute methanol and water. 
     FIGS. 2 and 3 which are a part of this specification compare MMA selectivity and methanol conversion for the invention process using sodium mordenite as the catalyst and for a conventional process (carried out at atmospheric pressure except as noted, at C/N ratios within the ranges 0.90-1.10, that is, about 1.0, and 1.41-1.60, that is, about 1.5) using an amorphous silica-alumina catalyst. The points included on FIGS. 2 and 3 reflect the experimental data (shown in Tables II and III of this Example and Table VI of Example 4) which were obtained by carrying out the aforesaid procedures at the respective C/N ratios of about 1.0 and about 1.5. The curves depicted in FIGS. 2 and 3 were formulated from calculations using the parameters outlined in Table I according to the procedures set forth at the end of this example. It can be seen that there is good agreement between the experimental data and the calculated curves. The deviation (scattering) of the points (experimental data) from the curves (calculated data) represents variances in the reaction conditions as they relate to temperature, contact time, pressure and analytical measurement errors and the neglect of the amine hydrolytic reaction, that is, the reverse of reactions (1)--(3) of Table I. The figures demonstrate that the invention process using sodium mordenite catalyst, at each C/N ratio, is vastly superior to the conventional process at all levels of methanol conversion in the practical operating range of 15-95%. 
     PROCEDURE FOR OBTAINING CALCULATED SELECTIVITIES 
     The basis for the calculation is the set of relative rate constants given in Table I. These rate constants were obtained by visually fitting theoretical reaction profiles, derived as explained below, to experimental data such as given in FIGS. 2 and 3. In addition to data obtained from starting with various ratios of methanol and ammonia, the rate constants also fit data equilibrating pure or mixed amines in the absence of methanol, and three component feeds which simulate a recycle of unwanted amines to the methanol-amine reactor. 
     The kinetic model involves nine equations: three methanol-amine synthesis reactions, three amine equilibration reactions, and their reverses. The three methanol-amine reaction rate constants are obtained by fitting the methanol-ammonia reaction data at low and medium methanol conversions, where amine disproportionations are negligible. The three forward equilibrium. reaction rate constants are obtained from monomethylamine disproportionation data. Their reverses are obtained from thermodynamic data at 400° C. This method introduces only a minor error when reaction profiles at other temperatures are considered. The relationship between the two sets of rate constants is best obtained from the high conversion portion of the methanol-ammonia reaction. 
     Given the nine rate constants, the evolution of an initial methanol-ammonia reaction mixture under the influence of the catalyst can be calculated. These calculations have been performed for the standard silica-alumina catalyst at three different C/N ratios and have included consideration of the monomethylamine selectivity at three different methanol conversions. From these nine points a second-order regression equation for monomethylamine selectivity in terms of C/N ratio and methanol conversion was developed. This equation was used to calculate the expected MMA selectivity for the conventional silica-alumina catalyst as a function of C/N ratio and methanol conversion to which the observed MMA selectivities of the catalyst of the invention process are compared. 
     
                       TABLE II                                                    
______________________________________                                    
 Temp  Contact   C/N      MeOH  STY    MMA                                
(°C.)                                                              
       Time (sec)                                                         
                 Ratio    Conv. g/g/hr Selectivity                        
______________________________________                                    
Sodium Mordenite Catalyst                                                 
394    1.18      1.05     22    0.202  99                                 
350    0.69      1.05     24    0.367  87                                 
356    1.08      1.05     24    0.190  95                                 
398    0.98      1.00     24    0.252  87                                 
274    3.68      1.02     25    0.073  88                                 
398    0.95      0.98     25    0.254  87                                 
328    0.78      0.96     28    0.141  89                                 
300    1.55      1.01     28    0.207  87                                 
399    0.82      1.03     30    0.328  89                                 
350    1.36      0.99     31    0.243  95                                 
274    3.48      1.02     38    0.110  83                                 
400    2.03      1.00     43    0.216  81                                 
330    1.49      0.96     47    0.316  75                                 
330    1.06      1.02     48    0.344  77                                 
400    0.99      0.99     49    0.349  87                                 
340    1.45      1.04     52    0.370  73                                 
300    0.59      1.04     52    0.494  81                                 
358    1.46      0.95     53    0.330  80                                 
325    1.24      1.05     56    0.567  57                                 
400    1.94      0.98     66    0.300  77                                 
350    1.42      0.97     66    0.150  47                                 
375    1.43      0.95     67    0.440  74                                 
400    0.54      1.04     68    0.616  68                                 
350    1.83      0.96     69    0.298  71                                 
351    1.63      0.97     71    0.472  71                                 
325    1.52      0.95     74    0.486  64                                 
350    1.47      0.95     75    0.495  62                                 
350    2.24      1.01     76    0.338  61                                 
400    1.94      1.05     82    0.370  58                                 
400    1.72      1.03     82    0.199  47                                 
350    2.10      1.04     84    0.382  63                                 
400    1.13      0.97     89    0.198  47                                 
Amorphous Silica-Alumina Catalyst                                         
349    0.62      1.00     23    0.364  46                                 
287    4.77      0.90     24    0.048  36                                 
349    0.61      0.96     25    0.379  46                                 
310    4.34      1.09     37    0.087  25                                 
 348*  0.64      0.97     41    0.613  32                                 
 350*  0.66      1.03     45    0.717  40                                 
  354**                                                                   
       0.73      1.05     54    0.860  32                                 
  352**                                                                   
       0.72      1.05     56    0.894  33                                 
331    3.56      1.08     56    0.128  20                                 
398    0.58      1.03     57    0.95   35                                 
399    0.57      1.05     66    1.062  35                                 
250    2.17      1.09     68    0.427   4                                 
250    2.66      1.05     71    0.430   7                                 
383    2.24      1.05     71    0.350  25                                 
350    5.02      1.07     76    0.169  15                                 
 399***                                                                   
       0.75      1.10     80    1.334  27                                 
 399***                                                                   
       0.72      1.09     81    1.329  26                                 
383    2.69      0.91     84    0.339  30                                 
394    2.70      1.02     88    0.398  20                                 
374    5.80      0.96     90    0.183  22                                 
400    3.98      1.10     94    0.327  19                                 
______________________________________                                    
  *at 40 psi (280 kPa)                                                    
  **at 75 psi (525 kPa)                                                   
  ***at 42 psi (294 kPa)                                                  
 
    
     
                       TABLE III                                                   
______________________________________                                    
 Temp  Contact   C/N      MeOH  STY    MMA                                
(°C.)                                                              
       Time (sec)                                                         
                 Ratio    Conv. g/g/hr Selectivity                        
______________________________________                                    
Sodium Mordenite Catalyst                                                 
300    1.33      1.46     20    0.217  88                                 
347    0.76      1.45     23    0.220  75                                 
347    0.72      1.58     24    0.251  79                                 
300    2.31      1.54     24    0.130  81                                 
347    0.73      1.57     24    0.253  78                                 
347    0.74      1.60     25    0.268  79                                 
347    0.77      1.58     25    0.269  78                                 
347    0.77      1.59     26    0.274  78                                 
345    0.73      1.44     26    0.248  79                                 
328    0.90      1.42     29    0.205  80                                 
250    15.56*    1.47     29    0.025  83                                 
399    1.54      1.58     31    0.127  84                                 
400    1.46      1.44     32    0.243  72                                 
350    1.48      1.45     32    0.227  74                                 
402    0.35      1.47     33    0.965  73                                 
333    1.01      1.50     36    0.454  78                                 
420    1.41      1.42     37    0.281  70                                 
325    1.33      1.43     39    0.406  79                                 
450    1.15      1.60     41    0.343  65                                 
377    1.66      1.48     44    0.262  71                                 
350    0.96      1.40     45    0.425  72                                 
400    1.00      1.50     46    0.525  88                                 
350    1.63      1.58     46    0.346  82                                 
400    0.95      1.52     47    0.482  68                                 
400    0.69      1.46     49    0.690  65                                 
350    1.34      1.47     52    0.560  79                                 
450    0.86      1.60     55    0.601  58                                 
450    1.81      1.40     59    0.273  61                                 
400    1.32      1.53     63    0.422  62                                 
400    2.01      1.43     66    0.335  71                                 
400    1.15      1.42     71    0.686  59                                 
475    0.77      1.53     74    0.737  46                                 
372    5.80      1.52     75    0.160  62                                 
400    0.99      1.43     76    0.729  54                                 
425    1.39      1.60     78    0.521  45                                 
350    2.01      1.43     80    0.485  53                                 
399    5.49      1.40     80    0.147  38                                 
425    0.93      1.52     80    0.799  47                                 
400    1.74      1.48     82    0.515  53                                 
375    2.94      1.40     83    0.316  53                                 
400    1.42      1.43     85    0.560  41                                 
350    6.23      1.41     87    0.167  52                                 
400    0.95      1.54     87    0.839  28                                 
400    1.02      1.47     91    0.844  28                                 
Amorphous Silica-Alumina Catalyst                                         
307    3.35      1.60     22    0.091  25                                 
317    2.67      1.49     27    0.103  24                                 
346    1.04      1.41     48    0.469   7                                 
347    1.93      1.50     53    0.203  22                                 
356    3.71      1.57     58    0.227  14                                 
400    1.07      1.45     84    0.751  19                                 
404    2.32      1.53     87    0.636  10                                 
______________________________________                                    
  *more than 3 g of catalyst used; therefore, lower rate of flow and longe
 contact time                                                             
 
    
     EXAMPLE 2 
     In a manner similar to that described in Example 1, methanol and ammonia were reacted at atmospheric pressure over selected crystalline aluminosilicates (other than sodium mordenite) of the process of the invention at C/N ratios in the range 0.55 to 1.5; 3 g of catalyst was employed and the temperature was within the range 250°-458° C., contact time were 0.2-4.0 seconds (0.6-12.5 g of of methanol/g of catalyst/hour). These and control runs using various conventional (nonselective) catalysts run under substantially similar conditions for comparison are listed in Table IV. In the table, STY refers to space-time-yield, that is, grams of amines produced/gram of catalyst/hour. 
     
                                           TABLE IV                                
__________________________________________________________________________
                                             Selectivity                  
                                                        Calcd (as in      
                                                        Ex. 1) for        
                              Amines                    Amorph.           
             Contact                                                      
                   C/N        (Distribution)            Silica-alumina    
Catalyst                                                                  
       Temp (°C.)                                                  
             Time (sec)                                                   
                   Ratio                                                  
                       MeOH Conv.                                         
                              NH.sub.3                                    
                                 MMA DMA TMA STY g/g/hr                   
                                                   Observed               
                                                        Catalyst          
__________________________________________________________________________
Clinop-                                                                   
tilolite                                                                  
Ore    350   1.4   0.97                                                   
                       38     78 11  7   4   0.244 51   40                
Ferrierite                                                                
Ore    314   2.1   0.95                                                   
                       29     80 13  7   0   0.131 63   48                
       335   2.0   1.08                                                   
                       34     76 14  10  1   0.166 55   41                
       355   4.0   0.95                                                   
                       42     74 14  12  1   0.091 53   37                
       356   1.9   1.05                                                   
                       28     80 12  8   0   0.136 58   48                
       358   2.3   1.01                                                   
                       57     57 28  13  1   0.277 66   26                
       375   1.1   1.35                                                   
                       30     73 15  11  1   0.274 56   40                
       378   1.9   1.00                                                   
                       56     64 17  16  2   0.252 48   27                
       381   3.8   0.91                                                   
                       62     63 19  16  2   0.128 52   27                
       399   3.9   0.85                                                   
                       76     59 21  18  3   0.145 50   26                
       400   1.1   1.35                                                   
                       69     46 21  28  6   0.598 39   17                
       400   1.0   1.45                                                   
                       53     53 21  22  4   0.504 44   21                
       401   2.0   1.06                                                   
                       63     58 21  19  3   0.303 49   23                
       422   2.5   1.03                                                   
                       76     51 26  17  6   0.356 54   22                
       422   3.4   0.85                                                   
                       83     56 22  18  4   0.158 49   27                
       425   1.1   1.32                                                   
                       72     42 28  24  6   0.625 48   17                
       437   1.8   0.94                                                   
                       77     53 24  20  3   0.330 51   24                
       458   1.7   0.93                                                   
                       81     53 24  19  5   0.339 51   24                
Ca                                                                        
Ferrierite                                                                
       300   1.9   1.26                                                   
                       33     72 15  12  1   0.178 54   39                
       302   1.7   0.74                                                   
                       29     84 11  5   0   0.142 70   54                
       325   2.0   1.18                                                   
                       29     77 13  9   1   0.150 56   44                
       326   1.6   0.80                                                   
                       39     76 18  6   0   0.212 75   43                
       340   1.7   0.80                                                   
                       39     76 20  4   0   0.201 85   47                
       350   2.0   1.19                                                   
                       64     54 21  22  4   0.315 44   20                
       352   1.5   0.82                                                   
                       50     69 22  8   1   0.278 71   35                
       375   1.9   1.27                                                   
                       77     45 21  26  9   0.397 38   17                
       375   0.8   1.40                                                   
                       33     70 16  13  2   0.393 52   36                
       375   1.5   0.73                                                   
                       69     64 23  11  2   0.335 64   30                
       400   0.3   1.37                                                   
                       42     65 16  17  3   1.443 45   30                
       400   1.9   1.20                                                   
                       83     44 22  24  10  0.407 40   19                
       400   1.5   0.71                                                   
                       76     63 23  12  2   0.354 61   30                
       400   2.1   0.96                                                   
                       80     54 21  19  6   0.321 45   24                
       408   1.1   1.25                                                   
                       40     64 26  9   2   0.335 70   33                
       408   1.4   0.80                                                   
                       21     70 21  7   2   0.276 70   35                
       408   1.5   0.76                                                   
                       71     63 23  10  3   0.354 63   29                
       425   0.2   1.43                                                   
                       42     61 18  17  4   1.605 47   26                
       425   1.8   1.13                                                   
                       86     45 23  20  12  0.403 42   21                
       450   0.2   1.48                                                   
                       43     63 18  16  3   1.503 47   29                
       450   0.3   1.36                                                   
                       47     61 18  17  4   1.605 47   26                
Fe Fer.                                                                   
       400   1.8   0.87                                                   
                       66     67 16  10  7   0.240 48   27                
Sr Fer.                                                                   
       400   1.7   1.23                                                   
                       73     47 25  20  8   0.373 47   18                
K Fer. 400   1.8   1.13                                                   
                       72     52 21  19  7   0.338 45   20                
Li Fer.                                                                   
       400   2.1   0.91                                                   
                       81     55 21  19  5   0.309 46   25                
Ba Fer.                                                                   
       400   2.1   0.88                                                   
                       80     58 21  15  7   0.295 49   26                
Ce Fer.                                                                   
       400   1.8   1.14                                                   
                       69     55 19  19  7   0.322 43   20                
Erionite                                                                  
       300   1.6   0.78                                                   
                       39     80 12  7   2   0.196 58   44                
ore    400   1.2   1.26                                                   
                       87     46 17  19  18  0.668 31   19                
Ca Erionite                                                               
       300   1.7   0.98                                                   
                       35     78 12  7   3   0.218 55   42                
       300   1.8   0.97                                                   
                       41     76 13  8   4   0.253 52   37                
       325   1.2   1.29                                                   
                       37     71 15  10  5   0.304 51   34                
       350   1.2   1.42                                                   
                       49     60 17  15  8   0.434 43   24                
       350   1.7   1.08                                                   
                       60     63 16  14  7   0.399 44   24                
       350   1.8   1.12                                                   
                       84     54 15  16  16  0.565 32   21                
       357   1.7   1.03                                                   
                       84     56 15  15  14  0.524 34   23                
       359   1.6   1.12                                                   
                       55     63 17  14  6   0.388 47   25                
       375   1.5   1.12                                                   
                       74     55 18  18  10  0.508 39   20                
       383   0.8   1.33                                                   
                       62     54 19  18  9   0.506 42   19                
       400   1.2   1.42                                                   
                       81     43 18  21  18  0.689 31   15                
       400   1.4   1.19                                                   
                       89     49 15  17  19  0.635 29   20                
       422   1.0   1.34                                                   
                       91     44 15  16  25  0.727 27   18                
       425   1.3   1.33                                                   
                       93     42 17  19  23  0.736 28   19                
       425   2.5   1.40                                                   
                       94     42 14  16  28  0.455 24   18                
Ca Mord.                                                                  
       250   1.7   0.70                                                   
                       75     66 19  11  4   0.340 55   31                
       275   2.0   0.57                                                   
                       51     74 22  3   0   0.213 87   41                
       275   1.4   0.88                                                   
                       79     54 26  15  5   0.454 58   26                
       275   2.1   1.04                                                   
                       47     60 31  8   1   0.228 79   31                
       275   2.2   1.22                                                   
                       32     67 28  6   0   0.186 83   40                
       300   1.4   1.22                                                   
                       43     57 33  9   0   0.377 77   34                
       300   1.5   1.02                                                   
                       40     68 24  7   0   0.281 76   37                
       300   1.6   0.96                                                   
                       51     60 31  8   1   0.344 78   31                
       300   1.3   1.08                                                   
                       86     45 28  18  10  0.589 50   22                
       300   1.2   1.15                                                   
                       36     65 29  6   0   0.356 82   38                
       300   2.0   1.30                                                   
                       51     49 37  13  1   0.302 72   24                
       325   1.8   0.61                                                   
                       89     61 26  12  2   0.363 65   35                
       325   1.6   1.06                                                   
                       93     46 24  18  13  0.611 43   24                
       325   2.0   1.06                                                   
                       83     42 33  20  5   0.376 56   22                
       325   2.0   1.18                                                   
                       57     49 37  13  2   0.303 72   23                
       350   1.7   0.69                                                   
                       94     57 22  15  4   0.417 54   34                
Ca Mord.                                                                  
       350   1.1   1.13                                                   
                       72     43 37  18  3   0.652 63   20                
       350   2.0   1.23                                                   
                       86     35 33  23  9   0.446 51   19                
       350   0.3   1.47                                                   
                       44     55 28  15  2   1.685 63   27                
       354   1.5   0.88                                                   
                       88     51 26  18  5   0.488 54   27                
       356   1.4   0.98                                                   
                       87     44 30  21  4   0.544 54   24                
       375   1.2   1.01                                                   
                       90     44 29  21  7   0.702 50   25                
       375   1.8   1.15                                                   
                       89     40 27  24  9   0.425 45   21                
       410   1.3   0.95                                                   
                       93     48 25  19  9   0.549 47   27                
       450   0.2   1.49                                                   
                       77     38 25  21  16  0.812 41   14                
       457   1.3   0.80                                                   
                       62     64 26  6   4   0.338 72   30                
Sr Mord.                                                                  
       400   1.63  1.40                                                   
                       93     34 20  27  19  0.524 30   18                
Zn Mord.                                                                  
       400   1.15  1.09                                                   
                       28     83 9   4   4   0.125 50   47                
K Mord.                                                                   
       400   1.34  1.34                                                   
                       26     77 13  7   3   0.151 57   45                
Ba Mord.                                                                  
       324   1.75  1.22                                                   
                       39     61 33  7   1   0.262 82   34                
       345   1.66  1.12                                                   
                       59     48 40  12  1   0.358 76   23                
       365   1.68  1.06                                                   
                       76     40 41  16  3   0.427 68   21                
       377   1.64  1.07                                                   
                       39     66 27  6   1   0.232 80   36                
       385   1.64  1.08                                                   
                       82     41 35  20  5   0.451 59   21                
       396   1.59  1.05                                                   
                       56     56 32  9   3   0.313 73   26                
       400   0.26  1.42                                                   
                       26     73 19  7   1   0.997 69   44                
       406   1.60  0.97                                                   
                       89     45 29  19  7   0.434 54   25                
       419   1.53  0.97                                                   
                       77     51 20  13  6   0.382 61   23                
       425   1.60  0.88                                                   
                       87     54 23  15  8   0.381 51   27                
Natural                                                                   
Mord. Ore                                                                 
       400   1.96  1.16                                                   
                       89     45 24  15  17  0.639 44   21                
       402   1.42  1.19                                                   
                       91     48 16  16  20  0.650 32   21                
Cr Mord.                                                                  
       400   1.94  0.84                                                   
                       92     61 15  10  14  0.316 38   30                
Li Mord.                                                                  
       403   3.40  0.94                                                   
                       26     82 14  2   2   0.065 78   52                
NaH Mord.                                                                 
       330   1.20  0.97                                                   
                       38     69 25  6   0   0.185 80   40                
(4.2% Na)                                                                 
       330   1.25  0.97                                                   
                       29     75 23  3   0   0.209 88   48                
       330   1.21  0.96                                                   
                       28     76 21  3   0   0.193 88   50                
       330   1.25  1.03                                                   
                       36     69 25  6   0   0.187 81   40                
       330   1.18  0.71                                                   
                       36     77 20  3   0   0.265 89   48                
       330   1.19  0.86                                                   
                       36     73 24  4   0   0.324 86   44                
       330   1.08  0.85                                                   
                       46     68 26  7   0   0.274 79   37                
CONTROL EXAMPLES (Conventional Catalysts)                                 
Ca-Na-A                                                                   
       400   1.2   1.47                                                   
                       95     38 17  14  32  0.871 27   18                
Zeolite                                                                   
       300   2.2   1.25                                                   
                       80     58 10  7   25  0.394 24   18                
Silica-                                                                   
       400   1.0   1.45                                                   
                       84     51 9   7   33  0.751 19   15                
Alumina                                                                   
       347   1.9   1.50                                                   
                       53     68 7   3   23  0.203 22   20                
K-Na-A 400   1.0   1.24                                                   
                       55     65 13  10  12  0.438 36   23                
Zeolite                                                                   
Na-Y   400   0.9   1.45                                                   
                       90     43 14  12  31  0.818 24   17                
Zeolite                                                                   
       300   2.3   1.02                                                   
                       38     86 1   1   12  0.148 7    39                
Ca-X   400   1.0   1.24                                                   
                       93     48 14  13  25  0.721 26   21                
Zeolite                                                                   
Na-X   400   0.8   1.36                                                   
                       84     55 7   6   31  0.699 16   43                
Zeolite                                                                   
       300   2.2   1.19                                                   
                       65     73 1   0   25  0.298 4    20                
Hydrogen                                                                  
       300   2.0   1.50                                                   
                       69     64 2   2   33  0.399 5    15                
Mordenite                                                                 
       265   1.0   1.30                                                   
                       53     66 13  6   15  0.604 39   23                
γ-Al.sub.2 O.sub.3                                                  
       346   4.0   1.19                                                   
                       84     59 9   7   26  0.252 21   19                
       328   4.0   1.21                                                   
                       91     56 8   7   29  0.278 18   21                
Rare Earth-                                                               
X Zeolite                                                                 
       273   1.8   1.04                                                   
                       39     86 1   0   13  0.238 6    37                
       300   1.0   1.10                                                   
                       83     68 2   3   28  1.126 6    21                
       319   0.8   1.06                                                   
                       94     61 4   9   26  1.558 11   25                
       332   1.8   1.22                                                   
                       89     55 9   10  27  0.637 19   20                
Na ZSM-8                                                                  
       298   2.2   1.09                                                   
                       78     67 3   8   22  0.492 9    21                
Zeolite                                                                   
HZSM-5 268   1.9   1.03                                                   
                       45     84 1   1   15  0.250 4    33                
Zeolite                                                                   
       290   2.1   1.00                                                   
                       81     72 1   2   25  0.434 4    23                
       327   2.1   1.02                                                   
                       99     60 8   8   23  0.516 21   25                
NaZSM-5                                                                   
       337   1.4   1.11                                                   
                       40     83 2   3   12  0.279 14   35                
Zeolite                                                                   
       359   1.5   0.99                                                   
                       63     77 2   3   18  0.385 8    25                
       397   1.5   1.04                                                   
                       93     59 11  11  21  0.615 25   25                
Chabazite                                                                 
       350   1.5   1.14                                                   
                       93     52 13  13  22  0.629 26   22                
__________________________________________________________________________
 
    
     EXAMPLE 3 
     In this example, the preferred catalyst for MMA selectivity, sodium mordenite, was utilized in two runs conducted under elevated pressure. An equimolar mixture of methanol and ammonia was passed at a rate of 22 mmole/minute over sodium mordenite (11.5 g) contained in a 0.5 inch (1.3 cm), outer diameter,×9 inch (23 cm) tubular reactor. A Grove® valve was used to regulate the reaction pressure and temperature was maintained at 400° C. by immersion of the reactor in a sand bath. Table V summarizes the experimental data obtained. The contact time is the time at the indicated pressure; the STY is the space-time-yield in g of product/gram of catalyst/hour. 
     
                                           TABLE V                                 
__________________________________________________________________________
Contact                                                                   
      Pressure                                                            
            STY STY STY STY MeOH                                          
                                MMA                                       
Time (sec)                                                                
      (psig (kPa))                                                        
            MMA DMA TMA Amines                                            
                            Conv                                          
                                Selec                                     
__________________________________________________________________________
 7.2  100 (700)                                                           
            353 44  22  .419                                              
                            19  90                                        
21.6  300 (2000)                                                          
            270 42  24  .336                                              
                            24  88                                        
__________________________________________________________________________
 
    
     EXAMPLE 4 
     In a manner similar to that described in Example 3, except that the tubular reactor was 0.125 inch (0.32 cm)×6 inches (15.2 cm), methanol and ammonia were reacted over 3 g of sodium mordenite or calcium ferrierite at various C/N ratios, temperatures, pressures and contact times. The data for these runs are tabulated in Tables VI (for sodium mordenite) and VII (for calcium ferrierite). 
     
                                           TABLE VI                                
__________________________________________________________________________
                         Amines                                           
Pressure                                                                  
      Temp                                                                
          Contact Time                                                    
                 C/N MeOH                                                 
                         (Distribution) STY MMA                           
(psig (kPa))                                                              
      (°C.)                                                        
          (sec) at 1 atm                                                  
                 Ratio                                                    
                     Conv.                                                
                         NH.sub.3                                         
                            MMA DMA TMA g/g/hr                            
                                            Selectivity                   
__________________________________________________________________________
10 (70)                                                                   
      336 1.1    1.00                                                     
                     35  73 22  6   0   0.334                             
                                            85                            
20 (140)                                                                  
      394 1.3    0.84                                                     
                     28  78 20  2   0   0.213                             
                                            91                            
28 (190)                                                                  
      399 1.0    0.96                                                     
                     22  83 15  2   0   0.199                             
                                            88                            
40 (280)                                                                  
      334 1.3    0.86                                                     
                     43  69 26  5   0   0.374                             
                                            84                            
44 (300)                                                                  
      325 1.1    0.54                                                     
                     27  89 9   2   1   0.197                             
                                            75                            
46 (320)                                                                  
      326 1.0    0.74                                                     
                     38  78 16  6   0   0.375                             
                                            73                            
46 (320)                                                                  
      394 1.5    0.66                                                     
                     51  70 27  3   0   0.295                             
                                            90                            
59 (410)                                                                  
      393 1.6    0.47                                                     
                     58  76 21  2   0   0.202                             
                                            91                            
61 (420)                                                                  
      393 1.3    0.84                                                     
                     36  74 24  3   0   0.263                             
                                            89                            
70 (480)                                                                  
      399 1.5    1.58                                                     
                     32  58 35  6   1   0.127                             
                                            83                            
70 (480)                                                                  
      399 3.9    0.84                                                     
                     52  66 27  5   1   0.105                             
                                            82                            
70 (480)                                                                  
      399 4.0    0.80                                                     
                     55  67 26  5   1   0.102                             
                                            81                            
72 (500)                                                                  
      400 1.0    0.98                                                     
                     26  80 18  2   1   0.248                             
                                            86                            
72 (500)                                                                  
      400 1.7    1.02                                                     
                     36  70 28  0   2   0.180                             
                                            93                            
72 (500)                                                                  
      400 1.1    0.77                                                     
                     40  74 22  3   1   0.311                             
                                            88                            
72 (500)                                                                  
      400 1.0    0.93                                                     
                     31  76 20  6   0   0.322                             
                                            77                            
72 (500)                                                                  
      400 1.1    0.92                                                     
                     20  85 14  1   0   0.184                             
                                            93                            
72 (500)                                                                  
      400 2.0    1.00                                                     
                     45  65 29  5   1   0.217                             
                                            83                            
72 (500)                                                                  
      400 1.1    0.77                                                     
                     48  70 25  5   1   0.368                             
                                            81                            
72 (500)                                                                  
      400 1.2    0.87                                                     
                     51  67 27  6   1   0.414                             
                                            79                            
72 (500)                                                                  
      400 1.1    1.10                                                     
                     57  57 31  9   3   0.552                             
                                            72                            
74 (510)                                                                  
      425 2.0    0.93                                                     
                     75  50 37  11  3   0.391                             
                                            73                            
75 (520)                                                                  
      341 0.9    1.34                                                     
                     21  75 23  2   1   0.177                             
                                            88                            
75 (520)                                                                  
      341 0.9    0.99                                                     
                     23  80 18  2   0   0.281                             
                                            90                            
75 (520)                                                                  
      341 0.9    1.37                                                     
                     27  72 23  5   1   0.212                             
                                            79                            
75 (520)                                                                  
      341 0.9    1.02                                                     
                     32  70 27  3   0   0.208                             
                                            90                            
75 (520)                                                                  
      341 0.9    1.14                                                     
                     37  69 21  10  0   0.339                             
                                            68                            
75 (520)                                                                  
      374 0.9    0.79                                                     
                     42  71 26  3   1   0.413                             
                                            87                            
75 (520)                                                                  
      373 0.9    0.72                                                     
                     45  72 25  3   0   0.401                             
                                            89                            
75 (520)                                                                  
      341 1.0    0.77                                                     
                     52  71 18  10  1   0.323                             
                                            60                            
75 (520)                                                                  
      399 1.1    0.75                                                     
                     59  65 29  5   1   0.514                             
                                            83                            
75 (520)                                                                  
      422 1.0    0.83                                                     
                     64  58 33  8   1   0.621                             
                                            80                            
75 (520)                                                                  
      398 1.3    0.78                                                     
                     69  53 43  4   1   0.666                             
                                            90                            
75 (520)                                                                  
      406 2.4    0.83                                                     
                     76  50 41  8   2   0.279                             
                                            80                            
76 (520)                                                                  
      394 1.5    0.52                                                     
                     60  73 24  8   0   0.270                             
                                            89                            
77 (530)                                                                  
      407 2.2    0.84                                                     
                     79  49 39  9   2   0.382                             
                                            78                            
77 (530)                                                                  
      408 2.3    0.79                                                     
                     76  53 38  8   2   0.349                             
                                            79                            
77 (530)                                                                  
      422 1.1    0.76                                                     
                     67  61 31  7   2   0.587                             
                                            78                            
77 (530)                                                                  
      425 1.2    1.31                                                     
                     56  44 43  11  2   0.424                             
                                            77                            
78 (540)                                                                  
      390 1.5    0.47                                                     
                     60  75 23  2   0   0.251                             
                                            92                            
80 (550)                                                                  
      399 0.6    1.19                                                     
                     30  69 28  3   1   0.370                             
                                            88                            
80 (550)                                                                  
      335 1.2    0.85                                                     
                     36  73 25  2   0   0.317                             
                                            93                            
80 (550)                                                                  
      399 0.9    0.93                                                     
                     41  68 28  3   1   0.317                             
                                            88                            
80 (550)                                                                  
      399 0.9    0.95                                                     
                     44  65 31  4   1   0.413                             
                                            89                            
80 (550)                                                                  
      399 1.0    1.01                                                     
                     48  59 35  5   1   0.483                             
                                            85                            
80 (550)                                                                  
      399 1.2    0.87                                                     
                     60  56 38  6   1   0.525                             
                                            86                            
95 (650)                                                                  
      397 1.2    0.78                                                     
                     20  85 14  1   0   0.100                             
                                            93                            
95 (650)                                                                  
      395 0.8    0.91                                                     
                     23  80 18  1   0   0.191                             
                                            95                            
95 (650)                                                                  
      395 0.8    0.66                                                     
                     27  84 15  1   0   0.159                             
                                            94                            
95 (650)                                                                  
      392 0.9    0.91                                                     
                     24  79 20  1   0   0.140                             
                                            95                            
97 (670)                                                                  
      395 0.8    0.50                                                     
                     26  88 11  1   0   0.166                             
                                            92                            
101 (700)                                                                 
      396 0.8    0.91                                                     
                     24  80 19  1   0   0.197                             
                                            95                            
102 (700)                                                                 
      323 1.1    0.62                                                     
                     42  80 15  5   0   0.353                             
                                            75                            
111 (760)                                                                 
      326 1.8    0.56                                                     
                     52  78 15  7   0   0.219                             
                                            68                            
115 (790)                                                                 
      326 1.0    0.63                                                     
                     41  80 15  5   0   0.346                             
                                            75                            
122 (840)                                                                 
      400 1.6    0.91                                                     
                     49  63 31  6   1   0.345                             
                                            82                            
122 (840)                                                                 
      400 1.6    0.78                                                     
                     58  64 30  5   1   0.333                             
                                            83                            
122 (840)                                                                 
      400 1.3    0.81                                                     
                     61  63 29  7   1   0.355                             
                                            78                            
__________________________________________________________________________
 
    
     
                                           TABLE VII                               
__________________________________________________________________________
                         Amines                                           
Pressure                                                                  
      Temp                                                                
          Contact Time                                                    
                 C/N MeOH                                                 
                         (Distribution) STY MMA                           
(psig (kPa))                                                              
      (°C.)                                                        
          (sec) at 1 atm                                                  
                 Ratio                                                    
                     Conv.                                                
                         NH.sub.3                                         
                            MMA DMA TMA g/g/hr                            
                                            Selectivity                   
__________________________________________________________________________
77 (530)                                                                  
      340 1.7    0.82                                                     
                     34  76 20  4   0   0.201                             
                                            83                            
77 (530)                                                                  
      370 1.0    2.17                                                     
                     26  55 35  9   1   0.387                             
                                            78                            
77 (530)                                                                  
      370 2.0    0.94                                                     
                     56  57 35  7   1   0.371                             
                                            81                            
77 (530)                                                                  
      400 1.1    0.99                                                     
                     50  68 21  9   3   0.306                             
                                            64                            
77 (530)                                                                  
      400 1.1    1.23                                                     
                     46  62 25  11  3   0.361                             
                                            64                            
77 (530)                                                                  
      426 1.1    0.94                                                     
                     56  68 21  7   4   0.313                             
                                            65                            
77 (530)                                                                  
      425 1.2    1.26                                                     
                     35  73 18  6   4   0.264                             
                                            64                            
77 (530)                                                                  
      428 0.7    0.88                                                     
                     26  85 12  2   1   0.263                             
                                            80                            
__________________________________________________________________________
 
    
     EXAMPLE 5 
     In a manner similar to that described in Example 1, methanol and ammonia were reacted at atmospheric pressure, at 358° C., over sodium mordenite, various sodium hydrogen mordenites of the process of the invention and a sodium hydrogen mordenite and a hydrogen mordenite outside the process of the invention; 3 g of each catalyst was used. The data for these runs are tabulated in Table VIII, the last two runs being the control runs. 
     
                                           TABLE VIII                              
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                           Amines                                         
            Contact Time                                                  
                   C/N MeOH                                               
                           (Distribution) STY MMA                         
Catalyst                                                                  
        % Na                                                              
            (sec)  Ratio                                                  
                       Conv.                                              
                           NH.sub.3                                       
                              MMA DMA TMA g/g/hr                          
                                              Selectivity                 
__________________________________________________________________________
Na Mordenite                                                              
        4.4 1.3    1.28                                                   
                       42  55 37  8   1   0.360                           
                                              80                          
NaH Mordenite                                                             
        4.3 1.4    1.33                                                   
                       59  44 35  21  1   0.460                           
                                              61                          
NaH Mordenite                                                             
        4.2 1.4    1.15                                                   
                       65  45 37  17  1   0.480                           
                                              67                          
NaH Mordenite                                                             
        2.7 1.3    1.13                                                   
                       56  44 19  20  17  0.620                           
                                              34                          
NaH Mordenite                                                             
        1.4 1.3    1.35                                                   
                       59  41 14  19  27  0.720                           
                                              23                          
H Mordenite                                                               
        --  1.3    1.40                                                   
                       98  41 14  33  33  0.755                           
                                              23                          
__________________________________________________________________________