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BACKGROUND OF THE INVENTION
1. Field of the Art
This invention relates to a process for producing dimethylamine by the gas
phase catalytic reaction of methanol and ammonia. More specifically, the
present invention relates to a process for producing dimethylamine having
a specific feature in the catalyst employed.
Dimethylamine is an important chemical intermediate as the starting
material for various solvents, pharmaceuticals, organic rubbers,
surfactants, dyeing aids, etc., and is generally produced by reacting
methanol with ammonia in gas phase at an elevated temperature (around
400.degree. C.) in the presence of a solid acid catalyst (hereinafter
called the conventional catalyst) having dehydration and amination action
such as .gamma.-alumina, silica, silica-alumina and thoria. In this
reaction, other than dimethylamine (hereinafter abbreviated DMA),
monomethylamine (hereinafter abbreviated MMA) and trimethylamine
(hereinafter abbreviated TMA) are also produced almost inevitably, and
these by-product amines, for which demand is less than that for DMA, are
separated from the reaction product and then transferred to the reaction
system for reutilization.
Dimethylamine is separated from the reaction product of methylamines by
distillation. However, since TMA forms complicated azeotropic mixtures
with ammonia, MMA and DMA, very cumbersome and large scale distillation
operations are required, whereby the energy consumption in the DMA
recovery process becomes very great. Examples of the recovery process are
shown in detail in, for example, "Revised Complete Collection of
Manufacturing Flow Chart" (published by Kagaku Kogyo Sha Co., Ltd., Apr.
25, 1978).
For realization of reduction in production cost of DMA and in the size of
the device, it is critically important to suppress formation of the
methylamines other than DMA (MMA, TMA), particularly TMA, to a minimum,
thereby promoting formation of DMA. However, the final proportion of the
three kinds of methylamines formed in governed by thermodynamic
equilibrium, and the proportion of MMA and DMA formed will be higher as
the temperature becomes higher, and the ratio N/C of the number of
nitrogen atoms to the number of carbon atoms in the reaction mixture
becomes higher, with the proportion of TMA becoming smaller. For example,
when the reaction temperature is 400.degree. C., and the ratio of ammonia
to methanol is 1:1 (weight ratio), the equilibrium proportions of the
respective amines formed, calculated thermodynamically, are 0.284 for MMA,
0.280 for DMA and 0.436 for TMA.
In the case where the above conventional catalyst is used, the MMA
formation reaction or TMA formation reaction is relatively rapid, and
therefore the proportion of DMA formed in the three kinds of methylamines
throughout the entire reaction region will never surpass this equilibrium
value. Thus, large amounts of MMA and TMA must always be recycled together
with unreacted ammonia to the reaction system.
Various methods have been known for promotion or suppression of a specific
amine among the three kinds of methylamines. For example, by varying the
reaction conditions, the level of equilibrium itself can be shifted to
control the yield in favor of a specific amine. Generally speaking, as the
reaction temperature and the ratio (N/C) of the number of nitrogen atoms
to the number of carbon atoms become higher, MMA and DMA will be more
advantageously formed. However, as shown in Table 1 set forth hereinafter,
the change in the DMA formation ratio at the equilibrium does not greatly
depend on the change in the reaction temperature and N/C. At higher
reaction temperatures, the amounts of impurities produced such as carbon
dioxide, methane, formaldehyde, higher amines, etc. are increased. On the
other hand, at higher ratios N/C, the amount of ammonia to be circulated
is increased, resulting in enlargement of the apparatus. For the reasons
given above, it is not recommended to use reaction conditions outside
those generally employed, namely, a reaction temperature of 360.degree. C.
to 450.degree. C. and N/C of 1.2 to 3.0.
2. Prior Art
The method of promoting formation of DMA by modifying chemically the
conventional catalyst such as silica-alumina has been proposed. For
example, Japanese Patent Publication No. 486/1970 discloses a method for
improving the yield of DMA by the use of a catalyst based on the
silica-alumina impregnated with a sulfide such as that of Re, Ag or Co.
In recent years, as the catalyst for producing a specific methylamine
(e.g., MMA or DMA) with high selectivity, various zeolites are coming to
the fore of interest. Among them, mordenite type zeolites are also
included. For example, Japanese Laid-Open Patent Publication No.
113747/1981 discloses a method for obtaining selectively MMA from ammonia
and methanol with the use of various zeolites inclusive of mordenite.
Also, Japanese Laid-Open Patent Publication No. 46846/1981 discloses a
method for producing DMA from MMA with the use of the same catalyst as
mentioned above. Japanese Laid-Open Patent Publication Nos. 148708/1979
and 104234/1980 disclose the method for promoting formation of primary and
secondary amines from alcohol and ammonia by the use of the synthetic
zeolite FU-1 produced from materials containing a quaternary ammonium
salt. U.S. Pat. No. 4,082,805 discloses that primary and secondary amines
are obtained preferentially from alcohol and ammonia by the use of the
synthetic zeolite ZSM-5 and others.
In any of the methods employing such a zeolite as the catalyst, the
proportions of MMA and DMA formed surpass the thermodynamic equilibrium
values. This is probably due to the effect of the so-called molecular
shape selectivity, resulting from selective blocking of molecules
sterically expanded (TMA) at the fine pore inlets, since the sizes of the
fine pores within the crystalline structure of zeolite are at the level of
molecular sizes.
Zeolites exhibiting shape selectivity for the reaction to form methylamines
from ammonia and methanol known in the art are inclusive of mordenite,
erionite, clinoptilolite, zeolite A and other special synthetic zeolites.
Among them, particularly, mordenite is disclosed to have a marked effect
of suppressing formation of TMA in Japanese Laid-open Patent Publication
No. 169444/1982.
Mordenite is a crystalline aluminosilicate represented by a formula
Me.sub.1/n.(AlSi.sub.5 O.sub.12).3H.sub.2 O (where Me is a n-valent metal
atom, hydrogen atom, etc.). By the use of mordenite for synthesis of
methylamines, the selectivity of TMA is reduced to a great extent, and the
selectivity of MMA or DMA is increased. However, mordenite is liable to
form coke, and its catalytic properties are very susceptible to influence
by coke deposition due to its crystalline structure. For this reason, the
synthesis temperature (around 400.degree. C.) poses a problem in the
aspect of the catalyst life, and practically it is necessary for
prevention of coke formation to carry out the reaction at a temperature
not higher than 360.degree. C., preferably not higher than 340.degree. C.
Accordingly, a necessary condition for practical use of mordenite is that
it has a sufficiently high catalyst activity at such a low temperature.
Me of mordenite is exchangeable with cations such as those of various
metals, hydrogen and ammonia, and, depending on these cations and their
amounts, the fine pore size and the acidic nature on the fine pore
surfaces within the crystalline structure or the acidic nature on the fine
pore surfaces based on interstices between the primary particles is
influenced, whereby the catalyst activity and the selectivities of the
amines vary greatly.
SUMMARY OF THE INVENTION
We have found that, among these cations, particularly Na, K and Li
influence greatly the catalyst activity and selectivities of the amines,
and that when employing a mordenite catalyst for production of
methylamines, in order to maintain a commercially satisfactory reaction
rate under the very limited conditions as described above (for example, a
reaction temperature of not higher than 360.degree. C., preferably not
higher than 340.degree. C.) and yet obtain a sufficiently high selectivity
of DMA, while suppressing the formation of TMA and MMA to a minimum, the
contents of Na, K and Li must be restricted strictly within specific lower
ranges.
The above discoveries we have made are not believed disclosed or suggested
in any of the prior art disclosures as enumerated above, which disclose
the advantageousness of employing mordenite in the production of
methylamines (MMA, DMA and TMA). For example, in the above Japanese
Laid-Open Patent Publication Nos. 113747/1981 and 46846/1981, a Na-H type
mordenite with Na content of at least 2% by weight (e.g., 2 to 4.3%) is
described as a preferable example, and claim 2 of both Publications,
showing a preferred embodiment, recommends a reaction temperature within
the range from 350.degree. to 400.degree. C.
These are in contrast to the corresponding conditions in the present
invention as described hereinafter. Also, Japanese Laid-Open Patent
Publication No. 169444/1982 describes the marked effect of suppressing
formation of TMA possessed by mordenite from the standpoint of the shape
selectivity as described above. However, the main characteristic of the
invention disclosed in this Patent Publication resides in use of a
mordenite type zeolite having an effective pore size of about 1 to 5
.ANG., and no particular interest is directed toward the contents of Na,
etc., and the reaction temperature is recommended to be within the range
of from 350.degree. to 400.degree. C.
An object of the present invention is to provide a mordenite type zeolite
catalyst having a content of an alkali metal of the group of Na, K and Li
within specifically low, strictly restricted ranges, which can produce a
sufficiently high selectivity of DMA, while maintaining a commercially
satisfactory reaction rate under the very limited reaction conditions (for
example, a reaction temperature not higher than 360.degree. C., preferably
not higher than 340.degree. C.) and yet suppressing formation of TMA and
MMA to a minimum, in the production of methylamines by the reaction of
methanol (or a mixture of methylamines and ammonia, or a mixture of
methylamines) and ammonia. The "mixture of methylamines" is a mixture
consisting essentially of mono- and tri-methylamines.
Another object of the present invention is to provide reaction conditions
which can produce a high DMA selectivity during production of
methylamines, particularly dimethylamine by the use of such a catalyst.
According to the present invention, there is provided a process for
producing dimethylamine with high selectivity by carrying out a reaction
(a) between methanol and ammonia, (b) between methanol, ammonia and a
mixture of methylamines or (c) between ammonia and a mixture of
methyamines in gas phase in the presence of a catalyst, in which process
the catalyst is a mordenite type zeolite with an Na content of 0.2 to 3.9
g per 100 g of the catalyst and an alkali metal content of 0.01 to 0.20
mole as a total selected from the group consisting of Na, K and Li per 100
g of the catalyst.
DETAILED DESCRIPTION OF THE INVENTION
In general, with an increase of an alkali metal content in a solid acid
catalyst, the reaction rate is lowered. In order to obtain a practical
reaction rate at a low reaction temperature (not higher than 360.degree.
C., preferably not higher than 340.degree. C.), the amount of the alkali
metals must be limited. Also, if the alkali metal content exceeds a
certain value, the amount of MMA formed will be abruptly increased to
result in a reduction of the proportion of DMA in methylamines formed.
From these facts, the upper limit value of the alkali metal content has
been selected as specified above. On the other hand, an H-type mordenite
gives a low selectivity when employed as the catalyst. From this
standpoint, the lower limit value of Na has been selected.
In a preferred embodiment of this invention, the Na content in the
mordenite catalyst is preferably 0.2 to 3.9 g, particularly preferably 0.2
to 3.0 g, most preferably 0.4 to 2.0 and the total content of Na, K and Li
in the mordenite catalyst is preferably 0.01 to 0.20 mole, particularly
preferably 0.01 to 0.17 mole, most preferably 0.03 to 0.17 mole.
The reaction is conducted preferably at a temperature of 260.degree. to
360.degree. C., more preferably 270.degree. to 350.degree. C., most
preferably 280.degree. to 340.degree. C., an N/C of 1.0 to 5.0, more
preferably 1.0 to 4.0, most preferably 1.2 to 3.0, an SV of 700 to 5,000,
more preferably 800 to 4,000, most preferably 1,000 to 3,000 and a
methanol conversion of 80 to 97%, more preferably 85 to 96%, most
preferably 90 to 95%. A reaction temperature higher than 360.degree. C. is
not desirable, because the catalyst life will be lowered by accumulation
of coke as described above (the drawback of the prior art). A reaction
temperature lower than 260.degree. C. is also not desirable because it is
difficult to maintain a commercially satisfactory reaction rate. It is
important to maintain the methanol conversion at 80 to 97% for ensuring
high selectivity of DMA. This point is in contrast to the methanol
conversion (preferably 97% or higher in most cases) in the case of the
catalyst of the prior art. The SV, a space velocity, in hour.sup.-1, is
shown in terms a gas volume at NTP conditions, namely 0.degree. C./1 atm.
The other conditions (N/C, SV) are necessary conditions for obtaining DMA
with high selectivity and high formation rate under the above conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In order to indicate more fully the nature, utility, and significance of
the unique characteristics of this invention, the following specific
examples of practice and comparative examples are set forth, it being
understood that these examples are presented as illustrative only and are
not intended to limit the scope of the invention.
The comparative examples show the results obtained when the reactions were
carried out under various conditions with the use of prior art catalysts.
In the case of the conventional catalysts, with the reaction temperature
of 360.degree. C., the reaction rate is very low, and the reaction rate at
this time may be deemed to be the lower limit of a commercially
satisfactory rate from the economical standpoint. In short, the level
capable of accomplishing about 90% of methanol conversion at an SV of
1,000 corresponds to this limit. This is shown in Run 7 set forth in Table
2. The proportion of DMA formed becomes slightly higher with increase of
the temperature and N/C, but the amine yield is lowered at higher
temperatures because of increased amount of produced impurities. For these
reasons, a temperature around 400.degree. C. is suitable as the reaction
temperature. In these catalysts, the proportion of DMA among the three
kinds of amines formed coincides with the thermodynamic equilibrium
composition as shown in Table 1 at approximately 100% of methanol
conversion, and the DMA will never surpass this value in the course of the
reaction.
Comparative Example 2 indicates an example in which a catalyst based on a
synthetic mordenite is employed. As the synthetic mordenite, it is
generally possible to use a commercially available product, but it can
also be easily prepared according to a known method, for example,
according to the method of Barrer (J. Chem. Soc., 1948, 2158) which
comprises crystallization of a gel with a composition of Na.sub.2
O.Al.sub.2 O.sub.3.10SiO.sub.2 by maintaining it under the hydrothermal
conditions at 280.degree. C. for 20 hours. The mordenite thus prepared is
of Na type and contains about 5.3% of Na. This exhibits substantially no
acidity as it is, and its activity is very low. See Run 20 set forth in
Table 3. The activity can be abruptly increased by exchange of a part of
Na with H. The H.Na mordenite containing 4.1% of Na exhibits an activity
on the threshold of a commercially applicable level, with both MMA and DMA
exceeding the equilibrium proportions, but the selectivity of the MMA is
higher as compared with that of the DMA. See Run 23 set forth in Table 3.
The H-mordenite with Na content of 0.1% has a markedly high activity. See
Runs 30 through 33 set forth in Table 3. However, the selectivity of the
DMA is low, being slightly in excess of the equilibrium proportion.
Mordenites containing metals other than Na and H, for example, those of
Li-H type, Runs 34 and 35; K-H type, Runs 36 and 37; and Ca-H type, Run
38, exhibit higher DMA selectivities than H-mordenite, but they are
inferior to Na-H mordenites as indicated in the examples set forth
hereinafter.
A mordenite with a medium content of Na (0.2%-4%) exhibits a high DMA
selectivity, but the reaction rate will be markedly lowered when the total
content of K, Li and Na exceeds 0.20 mole per 100 g of mordenite. See Runs
24 through 26 set forth in Table 3.
Comparative Example 3 shows an example of a naturally occurring mordenite
in which the amounts of metals were controlled. Here also, a tendency
similar to that in Comparative Example 2 is exhibited. A typical naturally
occurring mordenite contains about 2% of Na (0.09 mole per 100 g), about
2.2% of K (0.06 mole per 100 g), and other metals such as Mg, Ca, etc.
With the increase of an alkali metal such as Na, K or Li in this
mordenite, the reaction rate is abruptly decreased, and the selectivity
shifted preferentially for the MMA, but the catalyst performance will not
be influenced by an increase or a decrease in the amount of Mg or Ca. A
mordenite in which most of these metals are removed, namely, the H type
natural mordenite has a markedly high activity, but the selectivity of the
DMA is low, being nearly the equilibrium value. See Runs 46 and 47. Also,
the amount of impurities is relatively large, and the yield of
methylamines is low.
Thus, according to any of the processes in which the catalysts of the prior
art are used, the DMA selectivity is not higher than the equilibrium
value, there being a constant accompaniment of by-production of large
amounts of MMA and TMA. In the mordenite catalyst, when the alkali metal
content is outside the range as specified in the present invention, the
DMA selectivity can exceed the equilibrium only to a small extent, if any,
or the reaction rate is markedly lower. Therefore, it is extremely
difficult to use such a catalyst practically, and the advantage of use is
very small even when put to practical use. In contrast, the Examples set
forth below show clearly the effect of the present invention.
Example 1 shows an example of the present invention using a catalyst based
on a synthetic mordenite. In a mordenite wherein the Na content is within
the range from 0.2 to 3.9 per 100 g of the catalyst, and the total content
of Na, Li and K is 0.20 or lower per 100 g of the catalyst, the DMA
selectivity is conspicuously high, and the catalyst also maintains a
commercially satisfactory high activity. In particular, in the case of an
Na content ranging from 0.2% (0.01 mole per 100 g of the catalyst) to 2%
(0.09 mole per 100 g) of the catalyst and a total content of Na+K+Li of
0.20 mole or lower per 100 g of the catalyst, as shown in Runs 55 through
61 and Runs 64 through 71 set forth in Tables 5 and 6, the DMA selectivity
exhibited is 2-fold or more as compared with that in the case wherein the
Na content is less than 0.2 g per 100 g of the catalyst, as shown in Runs
27 through 39 and Runs 46 through 49 set forth in Tables 3 and 4 and the
activity exhibited is 2-fold or more, as compared with that in the case
wherein the total content of Na, Li and K is more than 0.2 mole or more,
as shown in Runs 24 through 26 and Runs 42 through 45 set forth in Tables
3 and 4. The catalyst performance is not substantially influenced by the
presence of other metals (Ca, Mg, etc.), provided that the Na content and
the total content of Na, K and Li are within the specified ranges.
Concerning impurities, such a catalyst contains a very small amount of
impurities formed as compared with, of course, the prior art catalyst or
even with an H-type mordenite, and a high amine yield is obtained.
As will be apparent from Example 1 and Example 2, in the mordenite
catalyst, the proportion of DMA among the three kinds of amines formed
surpasses greatly the equilibrium value at 75 to 90% of methanol
conversion to exhibit the maximum value. However, it is not desirable from
viewpoint of recovery cost to permit a substantial amount of unconverted
methanol to remain, and therefore the reaction should be completed at a
methanol conversion between 80% and 97%. It is also one of the specific
features of the mordenite catalyst that the amount of excessive ammonia
can be reduced to a great extent without the proportion of DMA formed
being influenced by N/C as much as in the conventional catalyst.
As previously mentioned, since the mordenite catalyst is liable to form
carbon and is sensitively influenced thereby, and also for prevention of
production of other impurities, it is preferable to conduct the reaction
at a temperature not higher than 360.degree. C., preferably not higher
than 340.degree. C. Accordingly, the catalyst must have a commercially
satisfactory reaction activity even at such a low temperature. Each of the
catalysts set forth in the examples exhibits a perfectly satisfactory
reaction rate as a commercial catalyst for production of methylamines at a
temperature around 300.degree. C.
Example 2 shows an example of the present invention based on a naturally
occurring mordenite. Natural mordenites, in general, contain 1.4% to 2.6%
of Na, 1.0 to 2.7% of K and other metals such as Ca, K, Fe, etc., their
amounts varying depending on the places where they are obtained. A typical
natural mordenite contains about 2.0% of Na and about 2.2% of K. This
mordenite exhibits a high DMA selectivity but it is not necessarily
satisfactory on the point of activity. By removing a small amount of the
alkali metals from this mordenite so that their quantities will be of the
level of, e.g., 1.7% of Na and 1.6% of K, the activity can be improved to
a great extent while retaining the high DMA selectivity. Furthermore, the
catalyst performance will be influenced by the presence of other metals
(Ca, Mg, etc.) only to a small extent provided that the Na content and the
total content of Na, K and Li are within the ranges as specified in the
present invention.
Production of undesirable impurities with zeolite catalysts of which the
alkali metal contents are controlled in a manner specified in the present
invention is smaller than that with H type zeolites.
As described above, the present invention provides a method for producing
DMA by a gaseous catalytic reaction of NH.sub.3 and methanol using a
zeolite catalyst which exhibits the shape selectivity for said reaction,
especially when said zeolite catalyst is mordenite type zeolite, where the
range of alkali metal content of the catalyst is determined in order to
obtain a commercially practical reaction activity and the maximum DMA
selectivity, as follows.
An H type mordenite has low DMA selectivity. For obtaining a DMA
selectivity markedly higher than the equilibrium composition, the Na
content should be 0.2% at least, preferably 0.3% or higher, more
preferably 0.4% or higher.
When the Na content is high in excess of a certain level, the activity is
abruptly lowered, the DMA selectivity being also lowered. Thus, the Na
content should be not higher than 3.9%, preferably 3.0% or lower, most
preferably 2.0% or lower.
If the total content of Na, K and Li is high in excess of a certain level,
the activity will be abruptly lowered. The total content of an alkali
metal of the group of Na, K and Li must be 0.01 to 0.20 mole, preferably
0.01 to 0.17 mole, more preferably 0.03 to 0.17.
The mordenite used in the present invention is a crystalline
aluminosilicate represented by the formula Me.sub.1/n.(AlSi.sub.5
O.sub.12).3H.sub.2 O (Me is an n-valent metal atom or hydrogen) as
mentioned above, which may be either a synthetic or a natural product.
With respect to Me, there is the limitation as described above.
Comparative Example 1
A 1/2 B stainless-steel reaction tube of 800-mm length was packed with
.gamma.-alumina or a silica-alumina with an alumina content of 18% in the
form of pellets of 4-mm diameter, and a mixture of ammonia and methanol
containing 50 to 60% by weight of ammonia (N/C 1.9-2.8) was fed into the
tube at a rate of 0.5 to 2.0 g per minute (space velocity SV: 500-6,000
liters/hour) to obtain methylamine mixtures with the compositions
indicated in Table 2.
Analysis was conducted by gas chromatography with the use of styrene
polymer beads (trade name: Polapack Q) impregnated with 3% of KOH.
Comparative Example 2
An Na-type synthetic mordenite prepared according to the method of Barrer
was boiled under reflux in 20-fold amount of 3N NH.sub.4 NO.sub.3 solution
for 6 hours, which operation was repeated for 4 times, and then after
washing dried at 130.degree. C. for 6 hours, followed by calcination at
450.degree. C. for 3 hours, to obtain an H-type mordenite. By dipping this
H-type mordenite in a 5- to 20-fold amount of 0.2 to 4N solution of
nitrates or chlorides of Li, Na, K, Mg and Ca and maintaining it at
10.degree. to 80.degree. C. for 4 to 40 hours, or by boiling under reflux
in the same solution for 2 to 8 hours, or by repeating or combining these
treatments, the amounts of the metals within the mordenite were controlled
thereby to prepare various mordenites. For example, by boiling 100 g of
the Na-type mordenite in 1.5 liter of 1N Ca(NO.sub. 3).sub.2 solution for
2 hours, a Ca--H mordenite containing 1.1% of Ca was obtained.
These mordenites were extruded into cylinders of 3-mm diameter, calcined at
450.degree. C. for 3 hours and provided for use as catalysts. According to
the same procedure as in Comparative Example 1, reactions between ammonia
and methanol were carried out each at 310.degree. to 400.degree. C., 18
Kg/cm.sup.2 and SV 1,000 to 5,000 liters/hour thereby to obtain
methylamine mixtures of the compositions indicated in Table 3.
Comparative Example 3
A naturally occurring mordenite was crushed, and the amounts of metals were
controlled according to the same method as in Comparative Example 2 to
prepare variour mordenites. For example, by boiling 100 g of an H-type
natural mordenite obtained according to the same method as in Comparative
Example 2 in 1.5 liter of 1N NaNO.sub.3 for 2 hours, a mordenite
containing 2.4% of Na was obtained.
These mordenites were extruded into cylinders of 3-mm diameter, calcined at
450.degree. C. for 3 hours and provided for use as catalysts. According to
the same procedure as in Comparative Example 2, reactions were carried out
to obtain methylamine mixtures of the compositions indicated in Table 4.
EXAMPLE 1
Various mordenites were prepared containing alkali metals in amounts within
the composition ranges as specified in the present invention by
controlling the metal contents in the synthetic mordenite according to the
method of Comparative Example 1. For example, by treating 100 g of H-type
synthetic mordenite in 1 liter of 1N NaNO.sub.3 solution at 40.degree. C.
for 20 hours, a mordenite containing 0.4% Na was obtained.
These mordenites were extruded into cylinders of 3-mm diameter. According
to the same procedure as in Comparative Example 1, reactions between
ammonia and methanol were carried out each at 320.degree. to 360.degree.
C., 18 Kg/cm.sup.2 G and SV 1,000 to 3,000 liters/hour thereby to obtain
methylamine mixtures of the compositions indicated in Table 5.
EXAMPLE 2
Various mordenites having the alkali metal contents within the ranges as
specified in the present invention were prepared by treating the natural
mordenite according to the method of Comparative Example 3. For example,
by maintaining 100 g of H-type natural mordenite in 1 liter of a solution
of 0.5N NaNO.sub.3 and 1N KNO.sub.3 in admixture at 10.degree. C. for 10
hours, a mordenite containing 0.3% Na and 0.8% K was obtained.
These mordenites were extruded into cylinders of 3-mm diameter and provided
for use as catalysts. According to the same procedure as in Example 1,
reactions between ammonia and methanol were carried out each at
270.degree. to 360.degree. C., 18 Kg/cm.sup.2, SV 1,000 to 4,200
liters/hour and N/C 1.2 to 1.9 thereby to obtain methylamine mixtures of
the compositions indicated in Table 6.
TABLE 1
__________________________________________________________________________
Equilibrium Composition
Feeding
ammonia/
Equilibrium
Respective methylamines in
Tempera-
methanol
methanol
all methylamines under
DMA yield
ture (.degree.C.)
N/C (molar ratio)
conversion (%)
equilibrium (wt. %) MMADMATMA
##STR1##
__________________________________________________________________________
400 1.9 99.6 28.5 28.1
43.4 20.0
" 2.8 99.7 36.0 28.5
35.5 21.0
360 1.9 99.8 24.9 25.9
49.1 18.1
350 " " 24.0 25.3
50.7 17.6
340 " " 23.1 24.7
52.2 17.1
330 " " 22.2 24.0
53.8 16.6
320 " " 21.2 23.3
55.4 16.0
" 2.8 99.9 27.2 24.6
48.1 17.4
" 1.2 99.8 15.0 21.1
64.0 14.1
310 1.9 99.9 20.3 22.6
57.1 15.5
__________________________________________________________________________
(*1) Methylamine yield (%) =- -
##STR2##
- -
(*2) DMA yield = DMA formed [g]/Methanol fed 100 [g] (Calculated with
methylamine yield as 100%)
TABLE 2
__________________________________________________________________________
Comparative Example 1
Mole ratio Proportions of respec-
Methyl-
Reaction N/C of
Space
Methanol
tive methylamines in
amine
DMA
Temper- ammonia
velocity
conver-
total methylamines
yield
yield
ature and meth-
SV sion formed (wt. %)
(%) (g/100 g)
Run
Catalyst
(.degree.C.)
anol fed
(hr.sup.-1)
(%) MMA DMA TMA (*1) (*2) No.
__________________________________________________________________________
.gamma.-alumina
400 1.9 1610 99.3 26.3
26.2
47.5 18.4 1
" " 2040 98.8 25.3
25.3
49.4
96.1 17.6 2
" " 3120 97.1 23.7
23.6
52.7 15.9 3
" " 5820 87.9 22.5
21.5
56.0 13.0 4
" 2.8 2220 98.6 32.1
26.0
41.9
96.9 18.5 5
" " 4230 95.1 31.1
25.2
43.7 17.2 6
360 1.9 1020 91.2 25.6
22.1
52.3
97.2 14.1 7
340 " 1000 77.1 25.2
21.8
53.0 11.7 8
Silica
400 1.9 1700 98.7 27.2
26.3
46.5
96.4 18.4 9
alumina
" " 2480 96.2 27.0
25.7
47.3 17.5 10
" " 3450 89.8 26.7
24.1
49.2 15.3 11
" 2.8 2020 98.3 29.8
27.1
43.1
97.1 19.1 12
" " 4000 94.6 29.3
26.8
43.9 18.1 13
350 1.9 1110 76.8 26.5
21.2
52.3 11.4 14
" " 1750 61.7 27.0
18.9
54.1 8.2 15
320 " 500 88.4 26.9
20.2
52.8 12.5 16
" " 710 79.2 27.5
18.5
54.0 10.3 17
" " 1130 71.4 29.8
17.7
52.5 8.9 18
" " 1590 47.9 35.9
16.0
48.1 5.6 19
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
Comparative Example 2
__________________________________________________________________________
Contents of alkali metals in mordenite
Total of
Contents of
Reaction
Mole ratio
Na, K, Li
other metals
tempera-
N/C of ammonia
Na (wt. %)
K (wt. %)
Li (wt. %)
(mol/100 g)
(wt. %)
ture (.degree.C.)
and methanol fed
__________________________________________________________________________
5.3 -- -- 0.23 -- 400 1.9
" -- -- " -- " "
4.8 -- -- 0.21 -- 360 "
4.1 -- -- 0.17 -- 350 "
2.4 4.0 -- 0.21 -- " "
0.7 7.0 -- " -- " "
3.8 -- 0.3 " -- " "
0.1 7.1 -- 0.10 -- " "
" 3.8 -- 0.19 -- " "
" -- -- 0.01 -- 360 "
" -- -- " -- 310 "
" -- -- " -- " "
" -- -- " -- " "
" -- -- " -- " "
" -- 0.3 0.05 -- 320 "
" -- " " -- " "
" 0.8 -- 0.02 -- " "
" " -- " -- " "
" -- -- 0.01 Ca 1.5 330 "
" -- -- " Mg 0.3 " "
__________________________________________________________________________
Respective methylamines in
Space Methanol
total methylamines formed
velocity
conver-
MMA DMA TMA Methylamine
DMA yield
SV (hr.sup.-1)
sion (%)
(wt. %)
(wt. %)
(wt. %)
yield (%)
(g/100 g)
Run No.
__________________________________________________________________________
2380 29.2 80.1 13.7 6.3 3.6 20
4620 10.8 91.5 6.8 1.8 96.7 0.7 21
2010 47.2 72.1 16.2 11.7 6.6 22
1000 83.7 51.2 32.8 16.0 21.9 23
2020 58.3 50.1 32.1 17.8 14.8 24
1410 71.1 42.7 29.3 28.0 15.9 25
1050 79.2 49.2 33.3 17.5 97.8 20.8 26
1980 70.3 43.8 27.5 28.7 14.8 27
2020 87.6 42.0 28.2 29.8 18.7 28
4000 99.7 23.6 25.3 51.1 96.9 17.6 29
1530 96.1 21.5 22.6 55.9 97.9 15.0 30
2010 95.1 23.7 23.9 52.5 15.8 31
3080 87.6 26.8 26.3 46.8 16.3 32
4000 73.0 34.1 29.3 36.6 15.7 33
1600 93.2 22.9 28.0 49.1 18.2 34
2130 76.3 24.8 31.7 43.5 17.1 35
1520 95.2 24.2 26.1 49.7 97.4 17.4 36
3010 68.3 27.6 28.3 44.1 13.8 37
1510 89.1 26.1 30.3 43.6 19.2 38
1500 86.9 28.5 31.2 40.3 19.5 39
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
Comparative Example 3
__________________________________________________________________________
Contents of alkali metals in mordenite
Total of
Contents of
Reaction
Mole ratio
Na, K, Li
other metals
tempera-
N/C of ammonia
Na (wt. %)
K (wt. %)
Li (wt. %)
(mol/100 g)
(wt. %)
ture (.degree.C.)
and methanol fed
__________________________________________________________________________
4.2 0.2 -- 0.19 360 1.9
" " -- " " "
3.3 2.9 -- 0.22 " "
2.1 4.7 -- 0.21 " "
" " -- " " "
2.4 -- 0.8 0.22 " "
0.1 0.1 -- 0.01 310 "
" " -- " " "
" 3.1 -- 0.08 330 "
" 0.1 -- 0.01 Ca 1.0 " "
__________________________________________________________________________
Respective methylamines in
Space Methanol
total methylamines formed
velocity
conver-
MMA DMA TMA Methylamine
DMA yield
SV (hr.sup.-1)
sion (%)
(wt. %)
(wt. %)
(wt. %)
yield (%)
(g/100 g)
Run No.
__________________________________________________________________________
1520 70.1 54.1 31.8 14.1 18.0 40
2400 58.5 62.3 26.7 11.0 13.0 41
1510 65.2 49.7 33.1 17.2 17.1 42
1490 70.3 44.6 32.3 23.1 17.5 43
2400 58.5 48.8 29.7 21.5 13.6 44
1510 71.2 43.8 34.1 22.1 18.7 45
" 97.5 24.1 24.0 51.9 97.7 16.3 46
2410 92.8 25.8 26.3 47.9 17.2 47
2400 88.3 26.4 27.5 46.1 17.2 48
" 90.7 29.0 28.7 42.3 18.7 49
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
Example 1
__________________________________________________________________________
Contents of alkali metals in mordenite
Total of
Contents of
Reaction
Mole ratio
Na, K, Li
other metals
tempera-
N/C of ammonia
Na (wt. %)
K (wt. %)
Li (wt. %)
(mol/100 g)
(wt. %)
ture (.degree.C.)
and methanol fed
__________________________________________________________________________
3.8 -- -- 0.16 -- 360 1.9
" -- -- " -- " "
" -- -- " -- " "
2.1 -- -- 0.09 -- " "
" -- -- " -- " "
0.4 -- -- 0.02 -- " "
" -- -- " -- " "
2.0 3.7 -- 0.18 -- 340 "
1.8 -- 0.7 " -- " "
0.3 0.4 -- 0.02 -- 320 "
" " -- " -- " "
0.7 -- -- -- Ca 1.0 " "
__________________________________________________________________________
Respective methylamines in
Space Methanol
total methylamines formed
velocity
conver-
MMA DMA TMA Methylamine
DMA yield
SV (hr.sup.-1)
sion (%)
(wt. %)
(wt. %)
(wt. %)
yield (%)
(g/100 g)
Run No.
__________________________________________________________________________
1050 96.6 35.7 37.1 27.2 98.6 26.8 50
2020 80.3 44.5 43.0 12.5 27.1 51
3030 67.1 41.2 39.8 19.0 20.5 52
1010 89.2 37.0 49.3 13.7 99.2 33.7 53
1420 81.5 41.1 50.5 8.4 32.2 54
1400 96.8 30.7 34.1 35.2 99.0 24.0 55
2020 90.3 34.1 39.5 26.4 26.6 56
1400 82.2 39.0 54.1 6.9 34.6 57
" 86.3 43.5 42.1 14.4 98.8 28.4 58
1420 97.8 29.0 34.4 36.6 24.3 59
3100 85.8 34.1 37.5 28.4 23.9 60
1010 90.3 40.2 41.5 18.3 28.9 61
__________________________________________________________________________
TABLE 6
__________________________________________________________________________
Example 2
__________________________________________________________________________
Contents of alkali metals in mordenite
Total of
Contents of
Reaction
Mole ratio
Na, K, Li
other metals
tempera-
N/C of ammonia
Na (wt. %)
K (wt. %)
Li (wt. %)
(mol/100 g)
(wt. %)
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