Preparation of monomethylamine

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.degree.-371.degree. 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.sub.1 -C.sub.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.degree.-500.degree. 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.degree.-475.degree. 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.degree.-400.degree. 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 "HNa" in the description of mordenite is intended to indicate the presence of both H.sup.+ and Na.sup.+ 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 .fwdarw. .tbd.1 .tbd.1 .tbd.1 .tbd.1 MMA + H.sub.2 O(2) MMA + MeOH .fwdarw. 0.7 20 15 >100 DMA + H.sub.2 O(3) DMA + MeOH .fwdarw. 0.5 120 45 >10,000 TMA + H.sub. 2 O(4) MMA + MMA .fwdarw. 0.09 4 ** ** DMA + NH.sub.3(5) DMA + DMA .fwdarw. 0.0022 7.2 ** ** TMA + MMA(6) MMA + DMA .fwdarw. 0.045 20.4 ** ** TMA + NH.sub.3(7) MeOH + MeOH .fwdarw. <0.01 .about.1 >>1 .about.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). < = less than > = greater than >> = much greater than .about. = 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.degree. 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.degree. C., two hours at 200.degree. C. and 4 hours at 400.degree. 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.sub.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>MMA>NH.sub.3 >MeOH; selective catalysts adsorb the species on the basis of their heats of condensation: MeOH>NH.sub.3 >MMA>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.RTM. 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).times.0.125 inch (0.32 cm) column of polyethylene oxide (25% Carbowax.RTM. 400), 2.5% NaOH on 80/100 mesh (U.S. Sieve Series) diatomaceous earth (Chromosorb.RTM. WAW). The temperature was held at 65.degree. C. for four minutes to elute the three amines and ammonia in the order: TMA, NH.sub.3, DMA and MMA, and then programmed to 100.degree. C. at 32.degree. 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.degree. 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(.degree.C.) Time (sec) Ratio Conv. g/g/hr Selectivity______________________________________Sodium Mordenite Catalyst394 1.18 1.05 22 0.202 99350 0.69 1.05 24 0.367 87356 1.08 1.05 24 0.190 95398 0.98 1.00 24 0.252 87274 3.68 1.02 25 0.073 88398 0.95 0.98 25 0.254 87328 0.78 0.96 28 0.141 89300 1.55 1.01 28 0.207 87399 0.82 1.03 30 0.328 89350 1.36 0.99 31 0.243 95274 3.48 1.02 38 0.110 83400 2.03 1.00 43 0.216 81330 1.49 0.96 47 0.316 75330 1.06 1.02 48 0.344 77400 0.99 0.99 49 0.349 87340 1.45 1.04 52 0.370 73300 0.59 1.04 52 0.494 81358 1.46 0.95 53 0.330 80325 1.24 1.05 56 0.567 57400 1.94 0.98 66 0.300 77350 1.42 0.97 66 0.150 47375 1.43 0.95 67 0.440 74400 0.54 1.04 68 0.616 68350 1.83 0.96 69 0.298 71351 1.63 0.97 71 0.472 71325 1.52 0.95 74 0.486 64350 1.47 0.95 75 0.495 62350 2.24 1.01 76 0.338 61400 1.94 1.05 82 0.370 58400 1.72 1.03 82 0.199 47350 2.10 1.04 84 0.382 63400 1.13 0.97 89 0.198 47Amorphous Silica-Alumina Catalyst349 0.62 1.00 23 0.364 46287 4.77 0.90 24 0.048 36349 0.61 0.96 25 0.379 46310 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 33331 3.56 1.08 56 0.128 20398 0.58 1.03 57 0.95 35399 0.57 1.05 66 1.062 35250 2.17 1.09 68 0.427 4250 2.66 1.05 71 0.430 7383 2.24 1.05 71 0.350 25350 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 26383 2.69 0.91 84 0.339 30394 2.70 1.02 88 0.398 20374 5.80 0.96 90 0.183 22400 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(.degree.C.) Time (sec) Ratio Conv. g/g/hr Selectivity______________________________________Sodium Mordenite Catalyst300 1.33 1.46 20 0.217 88347 0.76 1.45 23 0.220 75347 0.72 1.58 24 0.251 79300 2.31 1.54 24 0.130 81347 0.73 1.57 24 0.253 78347 0.74 1.60 25 0.268 79347 0.77 1.58 25 0.269 78347 0.77 1.59 26 0.274 78345 0.73 1.44 26 0.248 79328 0.90 1.42 29 0.205 80250 15.56* 1.47 29 0.025 83399 1.54 1.58 31 0.127 84400 1.46 1.44 32 0.243 72350 1.48 1.45 32 0.227 74402 0.35 1.47 33 0.965 73333 1.01 1.50 36 0.454 78420 1.41 1.42 37 0.281 70325 1.33 1.43 39 0.406 79450 1.15 1.60 41 0.343 65377 1.66 1.48 44 0.262 71350 0.96 1.40 45 0.425 72400 1.00 1.50 46 0.525 88350 1.63 1.58 46 0.346 82400 0.95 1.52 47 0.482 68400 0.69 1.46 49 0.690 65350 1.34 1.47 52 0.560 79450 0.86 1.60 55 0.601 58450 1.81 1.40 59 0.273 61400 1.32 1.53 63 0.422 62400 2.01 1.43 66 0.335 71400 1.15 1.42 71 0.686 59475 0.77 1.53 74 0.737 46372 5.80 1.52 75 0.160 62400 0.99 1.43 76 0.729 54425 1.39 1.60 78 0.521 45350 2.01 1.43 80 0.485 53399 5.49 1.40 80 0.147 38425 0.93 1.52 80 0.799 47400 1.74 1.48 82 0.515 53375 2.94 1.40 83 0.316 53400 1.42 1.43 85 0.560 41350 6.23 1.41 87 0.167 52400 0.95 1.54 87 0.839 28400 1.02 1.47 91 0.844 28Amorphous Silica-Alumina Catalyst307 3.35 1.60 22 0.091 25317 2.67 1.49 27 0.103 24346 1.04 1.41 48 0.469 7347 1.93 1.50 53 0.203 22356 3.71 1.57 58 0.227 14400 1.07 1.45 84 0.751 19404 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.degree.-458.degree. 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-aluminaCatalyst Temp (.degree.C.) Time (sec) Ratio MeOH Conv. NH.sub.3 MMA DMA TMA STY g/g/hr Observed Catalyst__________________________________________________________________________Clinop-tiloliteOre 350 1.4 0.97 38 78 11 7 4 0.244 51 40FerrieriteOre 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 24CaFerrierite 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 26Fe Fer. 400 1.8 0.87 66 67 16 10 7 0.240 48 27Sr Fer. 400 1.7 1.23 73 47 25 20 8 0.373 47 18K Fer. 400 1.8 1.13 72 52 21 19 7 0.338 45 20Li Fer. 400 2.1 0.91 81 55 21 19 5 0.309 46 25Ba Fer. 400 2.1 0.88 80 58 21 15 7 0.295 49 26Ce Fer. 400 1.8 1.14 69 55 19 19 7 0.322 43 20Erionite 300 1.6 0.78 39 80 12 7 2 0.196 58 44ore 400 1.2 1.26 87 46 17 19 18 0.668 31 19Ca 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 18Ca 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 34Ca 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 30Sr Mord. 400 1.63 1.40 93 34 20 27 19 0.524 30 18Zn Mord. 400 1.15 1.09 28 83 9 4 4 0.125 50 47K Mord. 400 1.34 1.34 26 77 13 7 3 0.151 57 45Ba 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 27NaturalMord. 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 21Cr Mord. 400 1.94 0.84 92 61 15 10 14 0.316 38 30Li Mord. 403 3.40 0.94 26 82 14 2 2 0.065 78 52NaH 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 37CONTROL EXAMPLES (Conventional Catalysts)Ca-Na-A 400 1.2 1.47 95 38 17 14 32 0.871 27 18Zeolite 300 2.2 1.25 80 58 10 7 25 0.394 24 18Silica- 400 1.0 1.45 84 51 9 7 33 0.751 19 15Alumina 347 1.9 1.50 53 68 7 3 23 0.203 22 20K-Na-A 400 1.0 1.24 55 65 13 10 12 0.438 36 23ZeoliteNa-Y 400 0.9 1.45 90 43 14 12 31 0.818 24 17Zeolite 300 2.3 1.02 38 86 1 1 12 0.148 7 39Ca-X 400 1.0 1.24 93 48 14 13 25 0.721 26 21ZeoliteNa-X 400 0.8 1.36 84 55 7 6 31 0.699 16 43Zeolite 300 2.2 1.19 65 73 1 0 25 0.298 4 20Hydrogen 300 2.0 1.50 69 64 2 2 33 0.399 5 15Mordenite 265 1.0 1.30 53 66 13 6 15 0.604 39 23.gamma.-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 21Rare 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 20Na ZSM-8 298 2.2 1.09 78 67 3 8 22 0.492 9 21ZeoliteHZSM-5 268 1.9 1.03 45 84 1 1 15 0.250 4 33Zeolite 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 25NaZSM-5 337 1.4 1.11 40 83 2 3 12 0.279 14 35Zeolite 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 25Chabazite 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,.times.9 inch (23 cm) tubular reactor. A Grove.RTM. valve was used to regulate the reaction pressure and temperature was maintained at 400.degree. 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 MMATime (sec) (psig (kPa)) MMA DMA TMA Amines Conv Selec__________________________________________________________________________ 7.2 100 (700) 353 44 22 .419 19 9021.6 300 (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).times.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__________________________________________________________________________ AminesPressure Temp Contact Time C/N MeOH (Distribution) STY MMA(psig (kPa)) (.degree.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 8520 (140) 394 1.3 0.84 28 78 20 2 0 0.213 9128 (190) 399 1.0 0.96 22 83 15 2 0 0.199 8840 (280) 334 1.3 0.86 43 69 26 5 0 0.374 8444 (300) 325 1.1 0.54 27 89 9 2 1 0.197 7546 (320) 326 1.0 0.74 38 78 16 6 0 0.375 7346 (320) 394 1.5 0.66 51 70 27 3 0 0.295 9059 (410) 393 1.6 0.47 58 76 21 2 0 0.202 9161 (420) 393 1.3 0.84 36 74 24 3 0 0.263 8970 (480) 399 1.5 1.58 32 58 35 6 1 0.127 8370 (480) 399 3.9 0.84 52 66 27 5 1 0.105 8270 (480) 399 4.0 0.80 55 67 26 5 1 0.102 8172 (500) 400 1.0 0.98 26 80 18 2 1 0.248 8672 (500) 400 1.7 1.02 36 70 28 0 2 0.180 9372 (500) 400 1.1 0.77 40 74 22 3 1 0.311 8872 (500) 400 1.0 0.93 31 76 20 6 0 0.322 7772 (500) 400 1.1 0.92 20 85 14 1 0 0.184 9372 (500) 400 2.0 1.00 45 65 29 5 1 0.217 8372 (500) 400 1.1 0.77 48 70 25 5 1 0.368 8172 (500) 400 1.2 0.87 51 67 27 6 1 0.414 7972 (500) 400 1.1 1.10 57 57 31 9 3 0.552 7274 (510) 425 2.0 0.93 75 50 37 11 3 0.391 7375 (520) 341 0.9 1.34 21 75 23 2 1 0.177 8875 (520) 341 0.9 0.99 23 80 18 2 0 0.281 9075 (520) 341 0.9 1.37 27 72 23 5 1 0.212 7975 (520) 341 0.9 1.02 32 70 27 3 0 0.208 9075 (520) 341 0.9 1.14 37 69 21 10 0 0.339 6875 (520) 374 0.9 0.79 42 71 26 3 1 0.413 8775 (520) 373 0.9 0.72 45 72 25 3 0 0.401 8975 (520) 341 1.0 0.77 52 71 18 10 1 0.323 6075 (520) 399 1.1 0.75 59 65 29 5 1 0.514 8375 (520) 422 1.0 0.83 64 58 33 8 1 0.621 8075 (520) 398 1.3 0.78 69 53 43 4 1 0.666 9075 (520) 406 2.4 0.83 76 50 41 8 2 0.279 8076 (520) 394 1.5 0.52 60 73 24 8 0 0.270 8977 (530) 407 2.2 0.84 79 49 39 9 2 0.382 7877 (530) 408 2.3 0.79 76 53 38 8 2 0.349 7977 (530) 422 1.1 0.76 67 61 31 7 2 0.587 7877 (530) 425 1.2 1.31 56 44 43 11 2 0.424 7778 (540) 390 1.5 0.47 60 75 23 2 0 0.251 9280 (550) 399 0.6 1.19 30 69 28 3 1 0.370 8880 (550) 335 1.2 0.85 36 73 25 2 0 0.317 9380 (550) 399 0.9 0.93 41 68 28 3 1 0.317 8880 (550) 399 0.9 0.95 44 65 31 4 1 0.413 8980 (550) 399 1.0 1.01 48 59 35 5 1 0.483 8580 (550) 399 1.2 0.87 60 56 38 6 1 0.525 8695 (650) 397 1.2 0.78 20 85 14 1 0 0.100 9395 (650) 395 0.8 0.91 23 80 18 1 0 0.191 9595 (650) 395 0.8 0.66 27 84 15 1 0 0.159 9495 (650) 392 0.9 0.91 24 79 20 1 0 0.140 9597 (670) 395 0.8 0.50 26 88 11 1 0 0.166 92101 (700) 396 0.8 0.91 24 80 19 1 0 0.197 95102 (700) 323 1.1 0.62 42 80 15 5 0 0.353 75111 (760) 326 1.8 0.56 52 78 15 7 0 0.219 68115 (790) 326 1.0 0.63 41 80 15 5 0 0.346 75122 (840) 400 1.6 0.91 49 63 31 6 1 0.345 82122 (840) 400 1.6 0.78 58 64 30 5 1 0.333 83122 (840) 400 1.3 0.81 61 63 29 7 1 0.355 78__________________________________________________________________________
TABLE VII__________________________________________________________________________ AminesPressure Temp Contact Time C/N MeOH (Distribution) STY MMA(psig (kPa)) (.degree.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 8377 (530) 370 1.0 2.17 26 55 35 9 1 0.387 7877 (530) 370 2.0 0.94 56 57 35 7 1 0.371 8177 (530) 400 1.1 0.99 50 68 21 9 3 0.306 6477 (530) 400 1.1 1.23 46 62 25 11 3 0.361 6477 (530) 426 1.1 0.94 56 68 21 7 4 0.313 6577 (530) 425 1.2 1.26 35 73 18 6 4 0.264 6477 (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.degree. 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__________________________________________________________________________ Amines Contact Time C/N MeOH (Distribution) STY MMACatalyst % 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 80NaH Mordenite 4.3 1.4 1.33 59 44 35 21 1 0.460 61NaH Mordenite 4.2 1.4 1.15 65 45 37 17 1 0.480 67NaH Mordenite 2.7 1.3 1.13 56 44 19 20 17 0.620 34NaH Mordenite 1.4 1.3 1.35 59 41 14 19 27 0.720 23H Mordenite -- 1.3 1.40 98 41 14 33 33 0.755 23__________________________________________________________________________

Number	Name	Date
1875747	Martin	Sep 1932
2012333	Arnold	Aug 1935
2092431	Swallen et al.	Sep 1937
2113241	Punnett	Apr 1938
4082805	Kaeding	Apr 1978

Preparation of monomethylamine

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