Melamine quality by reactivation of the melamine synthesis catalyst

In the synthesis of melamine by conversion of urea in a fluidized catalyst bed, the melamine quality is improved by reactivating the catalyst by treating it, in the fluidized bed, with gases containing steam, in the absence of oxygen, at from 250.degree. to 450.degree. C.

The present invention relates to a process for improving the quality of the 
melamine, obtained by chemical catalytic conversion of urea, through 
reactivation of the catalyst. 
It is known that in the synthesis of melamine from urea, carried out in the 
presence of a catalyst at from 300.degree. to 450.degree. C. under a 
pressure of from 1 to 10 bar, in the presence of ammonia or gases 
containing ammonia, for example a mixture of ammonia and carbon dioxide 
such as that which is obtained by freeing the reaction gas from melamine 
and which consists essentially of 2 parts by volume of ammonia and 1 part 
by volume of carbon dioxide, as a carrier gas, less volatile by-products, 
such as melem, melamine cyanurate and cyameluric acid, are also formed. 
The catalyst pores and surface become increasingly clogged with these 
non-volatile products, so that in sustained operation the activity of the 
catalyst decreases progressively, and the gas mixture leaving the reactor 
contains ever-increasing proportions of isocyanic acid, which, when the 
reaction gases are cooled to deposit the melamine, reacts with the latter 
to form melamine cyanurate etc. These impurities in melamine interfere 
with the production of finishes from melamine-formaldehyde resins. Since 
they (for example in the case of melamine cyanurate) are present in an 
insoluble very finely divided form, they can be removed from the 
melamine-formaldehyde solutions only at great expense, if at all. 
It is true that by bringing the pH to an alkaline value, for example by 
adding sodium hydroxide solution, the organic impurities which are present 
in the melamine and are insoluble in pure formaldehyde can be brought into 
solution, but in some recipes for the preparation of melamine-formaldehyde 
resins it is not possible to employ an alkaline pH. 
A catalyst whose activity has dropped can be reactivated by flushing it in 
a known manner with ammonia at the reaction temperature for a prolonged 
period (German Pat. No. 1,209,570). It is true that melem can thereby be 
converted to melamine, but the remaining substances which also reduce the 
activity of the catalyst cannot be removed completely, and moreover this 
method entails an economically unacceptable consumption of ammonia. 
According to German Pat. No. 1,209,570 this disadvantage can be avoided by 
carrying out the reaction in two stages and interchanging the catalysts 
periodically between the first and second stages. However, this procedure 
is relatively expensive. 
According to Japanese Patent Application No. 22,385/79, the catalysts are 
freed from impurities by bringing them into contact, at from 380.degree. 
to 800.degree. C., with oxygen, or oxygen-containing gas, which contains 
steam, thereby burning away the adhering organic substances. This process 
has the great disadvantage that the oxygen treatment of the catalyst, 
which may be pyrophoric, has to be carried out under strictly controlled 
conditions in order to avoid a runaway reaction, ie. an uncontrolled rise 
in temperature, since at higher temperatures there is a danger of the 
catalyst being damaged through a change in its lattice structure. A 
further disadvantage is that the burning off of the impurities cannot be 
carried out in the reactor itself, since the reactors employed for the 
synthesis of melamine are not designed for the high temperatures which may 
arise in such burning off. To carry out this process, the catalyst must 
therefore be removed from the reactor and treated in a special oven. This 
means an enormous expense in the case of an industrial plant, and hence 
the process is also not useful in practice. 
It is an object of the present invention to provide a process for improving 
the quality of melamine by reactivating the catalysts, which have been 
employed in the synthesis of melamine by thermal conversion of urea in a 
fluidized catalyst bed, through treatment with gases containing steam, 
which process can be carried out safely, and without major expense, in 
industrial operation, reactivation being carried out without removing the 
catalyst from the synthesis reactor. 
We have found that this object is achieved if the catalyst in the fluidized 
bed is treated with gases which contain steam, in the absence of oxygen, 
at from 250.degree. to 450.degree. C. 
Surprisingly, the treatment of the catalysts, in accordance with the 
invention, can be carried out during the synthesis of the melamine, ie. 
the steam or water can be introduced into the reaction zone without 
interrupting the feed of urea. Though, in this procedure, urea or its 
conversion products are hydrolyzed, the catalysts resume their original 
activity. Of course, the treatment according to the invention can also be 
effected after stopping the urea feed. The novel treatment achieves 
complete reactivation of the catalyst, ie. immediately after stopping the 
supply of water or steam, melamine is again produced in the original yield 
and purity. 
The process according to the invention can be carried out by introducing 
either steam or liquid water into the fluidized bed, since liquid water in 
any case vaporizes immediately at the temperatures to be maintained in the 
process according to the invention, namely from 250.degree. to 450.degree. 
C., preferably from 350.degree. to 450.degree. C. The steam is diluted 
with the gas used to fluidize the catalyst. In practice, it has proved 
advantageous to feed into the fluidizied bed an amount of water or steam 
which is such that the gases have a steam content of from 0.5 to 15% by 
volume; of course, the reactivation takes place more rapidly at higher 
steam contents than at lower contents. Equally, higher temperatures within 
the stated range accelerate the reactivation. 
The catalysts employed in the synthesis of melamine are usually oxidic 
compounds, such as silica gel, aluminum silicates, oxides of titanium, 
zirconium or thorium, and also kaolin, bentonite, bauxite, diatomaceous 
earth and fuller's earth, but especially aluminum oxide. 
The duration of the treatment according to the invention is from 1 to 24 
hours depending on the degree of clogging of the catalyst, the temperature 
employed and the steam concentration. The required amount of water is 
preferably introduced into the fluidized bed via the urea injection 
nozzles, whilst if steam is employed it is advantageously admixed to the 
fluidizing gas. 
The fluidizing gas used in the treatment according to the invention and 
during the synthesis itself is, in particular, a gas consisting of ammonia 
and carbon dioxide, expecially the synthesis waste gas, ie. the gas which 
has been freed from melamine and urea and contains ammonia and carbon 
dioxide in a volume ratio of about 2:1. 
The process according to the invention has the advantage, over the prior 
processes for regenerating a melamine synthesis catalyst, that the 
regeneration can be carried out in the synthesis reactor, ie. without 
removing and reinstalling the catalyst, and that all which is necessary 
when there is a drop in the catalyst activity, which, as mentioned, can be 
detected through the quality of the product, is that in place of urea 
water or steam is introduced into the reactor under otherwise unchanged 
conditions, or that during the synthesis water or steam is introduced into 
the reactor.

The Examples which follow illustrate the advantages of the novel process. 
EXAMPLE 1 
(A) Per hour, 2.1 t of melamine are produced in a fluidized bed reactor, 
charged with a .gamma.-Al.sub.2 O.sub.3 catalyst, by injecting 6 t of 
molten urea at a reaction temperature of 390.degree. C. The catalyst is 
fluidized by means of a gas consisting of 70% by volume of ammonia and 30% 
by volume of carbon dioxide. The vaporous melamine obtained after removing 
by-products and abraded catalyst is desublimed by supplying cooled 
reaction gas, and is separated out by means of downstream cyclones and 
then discharged. 
The quality of this melamine is examined by dissolving 63 g of melamine in 
a mixture of 100 ml of 30% strength by weight formaldehyde and 9 g of 
distilled water by heating at 90.degree.-95.degree. C., with stirring. The 
solution is assessed as to whether it is clear, opalescent or cloudy. If 
it is cloudy or opalescent, the product quality of the melamine is 
improved by injecting water instead of liquid urea into the reaction zone 
of the fluidized bed reactor under the above reaction conditions. The 
amount of water added corresponds, after vaporization, to 5.9% by volume 
of the fluidizing gas. After 20 hours, the feed of water is stopped and 
the introduction of urea into the reactor resumed. The melamine formed is 
again examined. The melamine-formaldehyde solution now proves completely 
clear and the product quality is maintained for at least 8 weeks. 
(B) If the melamine prepared as described in Example 1 does not give a 
clear solution in formaldehyde unless NaOH solution is added, gaseous 
ammonia is additionally introduced into the fluidizing gas which normally 
consists of about 70% by volume of NH.sub.3 and about 30% by volume of 
CO.sub.2. The amount of added ammonia is 7.3% by volume of the fluidizing 
gas, and this additional ammonia is introduced for 48 hours. During this 
time, the injection of liquid urea into the reactor is stopped. The 
temperature in the fluidized bed reactor is set to 395.degree. C. 
After 48 hours, the reaction temperature of the fluidized bed reactor is 
returned to 390.degree. C. and the production of melamine from 6 t/h of 
liquid urea is continued in the normal manner. 
The quality of the malamine now produced is examined. The product still 
does not give a clear solution in formaldehyde. 
EXAMPLE 2 
If the melamine prepared as in section (A) of Example 1 does not give a 
clear solution in formaldehyde without addition of NaOH solution, but does 
so if 1 N NaOH solution is added until the pH is 8-9, the product quality 
can also be improved more quickly by injecting water for 5 hours into the 
reaction zone of the fluidized bed reactor, at a reaction temperature of 
395.degree. C., the amount of water being so chosen that the steam content 
of the fluidizing gas is 11.2% by volume. The feed of liquid urea is 
stopped at the same time. Thereafter, the reaction temperature of the 
fluidized bed reactor is restored to 390.degree. C. and the production of 
melamine from liquid urea is continued. The melamine formed is again 
investigated. It gives a clear solution in formaldehyde without addition 
of NaOH solution. The product quality is maintained for at least 6 weeks. 
EXAMPLE 3 
The product quality of the melamine prepared as in Example 2 can also be 
improved by injecting steam for 24 hours into the reaction zone over the 
fluidized bed reactor at a reaction temperature of 395.degree. C. and 
choosing the amount of steam to be such that the fluidizing gas contains 
3.8% by volume of steam. In other respects, the procedure of Example 2 is 
followed. The improved product quality is maintained for about 5 weeks. 
EXAMPLE 4 
If the melamine prepared in section (A) of Example 1 gives opalescent or 
cloudy resin solutions with formaldehyde, which clear if the pH of the 
resin solution is brought to 8-9, the product quality can also be 
improved, without stopping the feed of 6 t/h of liquid urea to the 
reactor, by blowing steam into the fluidizing gas, consisting of 70% by 
volume of NH.sub.3 and 30% by volume of CO.sub.2, in an amount such that 
the fluidizing gas contains 0.8% by volume of steam. 
If the steam is introduced for 1 hour at a reaction temperature of 
395.degree. C., the improved melamine quality is maintained for about 10 
days.