Organic compounds -- part of the class 532-570 series – Organic compounds – Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
2001-09-25
2003-03-11
Berch, Mark L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitrogen attached directly or indirectly to the purine ring...
C502S064000, C502S071000
Reexamination Certificate
active
06531601
ABSTRACT:
The present invention relates to a molded catalyst for production of triethylenediamine, a method for its production, and a method for producing triethylenediamine employing such a catalyst. More particularly, the present invention relates to an improved crystalline aluminosilicate molded catalyst which is capable of producing triethylenediamine effectively and efficiently from an amine compound.
Triethylenediamine is a useful compound which is used in a large amount as e.g. a foaming catalyst in production of polyurethanes or a curing accelerator for epoxy resins.
Such triethylenediamine can be obtained usually by cyclization of an amine compound by using a catalyst. As such a catalyst, zeolite is well known. For example, {circle around (1)} JP-A-62-228079 and {circle around (2)} JP-A-63-122654 disclose a method of using a crystalline metal silicate subjected to calcination treatment in an air atmosphere at a temperature of from 400 to 600° C. and having a molar ratio of silica to alumina of at least 12, as a catalyst; {circle around (3)} JP-A-1-132587 discloses a method of using a pentasyl-type zeolite as a catalyst; {circle around (4)} JP-A-1-143864 discloses a method of using a pentasyl-type zeolite as a catalyst and contacting ethylenediamine, diethylenetriamine or 2-aminoethanol with such a catalyst at a temperature of from 250 to 550° C. to obtain triethylenediamiine; {circle around (5)} JP-A-3-133971 discloses a method of employing a pentasyl-type zeolite containing an alkali metal or having aluminum in the zeolite framework isomorphically substituted by iron, as a catalyst, and contacting ethylenediamine with the catalyst at a temperature of from 270 to 420° C. to obtain triethylenediamine; {circle around (6)} JP-A-5-17460 discloses a method for producing triethylenediamine from an amine compound and a catalyst composed of a crystalline aluminosilicate subjected to calcination treatment at a temperature of from 500 to 950° C. in a steam atmosphere; {circle around (7)} JP-A-5-17461 discloses a method for producing triethylenediamine from an amine compound and a catalyst composed of a crystalline aluminosilicate subjected to calcination treatment at a temperature of from 610 to 950° C. in an air atmosphere; {circle around (8)} JP-A-5-17462 discloses a method for producing triethylenediamine from an amine compound and a crystalline aluminosilicate catalyst having an inorganic salt supported thereon; {circle around (9)} JP-A-10-109964 discloses a method for producing triethylenediamine from an amine compound and a zeolite catalyst subjected to basic treatment; {circle around (10)} JP-A-10-182562 discloses a method for producing triethylenediamine from an amine compound and a surface acidity-deactivated zeolite catalyst; and {circle around (11)} JP-A-10-195029 discloses a method for producing triethylenediamine from a triethylenediamine reaction solution having an ethylated compound and a zeolite having a shape selectivity for a condensation reaction and a cyclic reaction added.
As mentioned above, many methods employing zeolite catalysts have been disclosed for the production of triethylenediamine. However, such zeolite catalysts had the following problems when used as industrial catalysts.
In the methods for producing triethylenediamine, the reaction system may be either a batch system, a semibatch system or a continuous system, and the reaction can be carried out in a suspension bed system (a fluidized bed system in the case of a gas phase reaction) or a fixed bed flow system. However, industrially, the fixed bed flow system is advantageous from the viewpoints of operation, apparatus and economical efficiency. In all of Working Examples of the above-mentioned prior art, the reaction is carried out by a fixed bed flow system. In the case of a fixed bed flow system, not only the yield of triethylenediamine, but also the mechanical strength of the molded catalyst and the catalyst life, are very important. With respect to the preparation of the molded catalyst, the prior art gives little specific description of e.g. the molding method, the binder, etc., and has not yet reached a level which is applicable to an industrial fixed bed flow system continuous reactor.
Only {circle around (6)} JP-A-5-17460, {circle around (7)} JP-A-5-17461 and {circle around (8)} JP-A-5-17462 disclose molding methods. These publications mention about extrusion molding, tableting and granulation, but in all Working Examples, tableting is employed.
With respect to the description of a binder, {circle around (2)} JP-A-63-122654 discloses silica, alumina, silica-alumina, etc., {circle around (5)} JP-A-3-133971 discloses alumina oxide, silicon dioxide or a clay such as bentonite or montmorillonite, {circle around (6)} JP-A-5-17460, {circle around (7)} JP-A-5-17461 and {circle around (8)} JP-A-5-17462 disclose silica, alumina, silica-alumina, clay, etc., and {circle around (9)} JP-A-10-109964, {circle around (10)} JP-A-10-182562 and {circle around (11)} JP-A-10-195029 disclose silica, alumina, titania, zirconia and natural clay, but no specific disclosure is made in Working Examples. {circle around (3)} JP-A-1-132587 and {circle around (4)} JP-A-1-143864 mention about an inert binder in Working Examples, but no name of the material is disclosed. Further, {circle around (9)} JP-A-10-109964, {circle around (10)} JP-A-10-182562 and {circle around (11)} JP-A-10-195029 disclose that a material having a low acidity such as silica or zirconia is preferred, since an undesirable side reaction caused by a more active material such as alumina, can be prevented. However, no specific operation or effects are described.
Further, with respect to the yield of triethylenediamine and the catalyst life when triethylenediamine is prepared by means of such a catalyst, for example, by the method disclosed in {circle around (1)} JP-A-62-228079 or {circle around (2)} JP-A-63-122654, the selectivity of triethylenediamine can be increased if the conversion of the starting material is made low, but the selectivity decreases as the conversion increases, and thus, it is not possible to obtain triethylenediamine in good yield, and the decrease in activity of the catalyst with time is significant. By the method disclosed in {circle around (3)} JP-A-1-132587 or {circle around (4)} JP-A-1-143864, the selectivity for triethylenediamine is high, but the conversion of the starting material at that time is low, whereby the yield of triethylenediamine is low, and deterioration with time of the catalytic activity is substantial. By the method of employing an alkali metal ion-containing pentasyl type zeolite as disclosed in {circle around (5)} JP-A-3-133971, the selectivity is high, but the conversion of the starting material is low, and the yield of triethylenediamine is low. On the other hand, with the pentasyl-type zeolite having aluminum in the zeolite framework substituted by iron, the selectivity is high, and as a result, the yield is improved, but the catalyst is a special zeolite, and the method for its production is complex, and the production conditions are severe, the production costs are high, such being not practical from the industrial viewpoint. Although the deterioration with time of the catalytic activity is lower than other conventional catalysts, the improvement is not yet of a level satisfactory from the industrial point of view.
By the method disclosed in {circle around (6)} JP-A-5-17460, {circle around (7)} JP-A-5-17461 or {circle around (8)} JP-A-5-17462, the yield of triethylenediamine is improved, but deterioration with time of the catalytic activity is substantial.
By the method disclosed in {circle around (9)} JP-A-10-109964 or {circle around (10)} JP-A-10-182562, the yield of triethylenediamine is low, and deterioration with time of the catalytic activity is substantial, and such a method is not useful as an industrial production method.
Further, the method disclosed in {circle around (11)} JP-A-10-195029 is a two step reaction, whereby the operation is cumbersome, the installation cost tends to be high, and deter
Berch Mark L.
Tosoh Corporation
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