Organic compounds -- part of the class 532-570 series – Organic compounds – Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
2000-07-05
2003-04-29
Shah, Mukund J. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
active
06555688
ABSTRACT:
The object of the invention is a method for production of triethylene diamine (1,4-diazabicyclo [2.2.2]octane,hereinafter called TEDA) with use of ethylene diamine (1,2-Diaminoethan, hereinafter called EDPA) and zeolite catalysts of the Pentasil type.
Triethylene diamine is an important base material, being used, inter alia, in the production of pharmaceutics and plastics, in particular as a catalyst in the production of polyurethanes.
The known methods for the production of TEDA basically differ by the nature of the initial products and the catalysts. As a matter of principle, it is beneficial to use favourable base chemicals such as ethanolamine or ethylene diamine (EDA) as educts. Conventional methods have however proven to be not very selective, in particular toward the educt EDA. In addition, a separation of the contaminations resulting from the cycling reaction is difficult, with the result that this method was not able to assert itself technically.
Methods for the production of TEDA using EDA have already been suggested.
The method described in U.S. Pat. No. 3,285,920 (H. G. Muhlbauer et al., Jefferson Chemical Co.) for simultaneous production of TEDA and piperazin (hereinafter called PIP) is a 2-step process, according to which one firstly converts ethylene diamine, ethanolamine and/or their oligomers in the presence of ammonia, hydrogen to a mixture of piperazin and N-(beta-aminoethyl)-piperazin in a reductive amination process making use of metal-oxidic hydrogenating catalysts and then cycles the residue—after separating the piperazin—in the presence of cycling catalysts such as phosphate salts and alumo-silicates. The amounts of TEDA gained are about 25%, those of piperazin about 12%.
In EP 0 158 319 (Union Carbide Corp.), zeolitic catalysts such as ZSM-5 are suggested for the production of TEDA. Basically, EP 0 158 319 has cyclic amine compounds as educts as its object.
From DE 37 35 212-A1 (corresponds to EP 0 313 753) and DE 37 35 214-A1 (corresponds to EP 0 313 734, both Huils AG) a method for production of a PIP/TEDA mixture by conversion of ethanolamines and/or ethylene diamine in the presence of a zeolite of the Pentasil type is known. According to this method, the chemicals are guided to a reaction at 280 to 380° C., an LHSV (liquid hourly space velocity) of 0.1 to 10 h
−1
and at an absolute pressure of 0.1 to 10 bar in a gaseous form via a packetbed catalyst. It is also suggested that the initial compounds be used together with a diluting agent, e.g. water.
According to EP 0 382 055-A1 (corresponds to DE 39 036 22, BASF AG) 1,2-diaminoethane and 0 to 200 mol% piperazin are converted to TEDA on aluminium, boron, gallium and/or iron silicate zeolites at the following preferred reaction conditions in the case of a liquid phase reaction: reaction temperature 100 to 300° C., pressure 1 to 5 bar and WHSV 1 to 10 h
−1
. If the reaction is conducted in the gaseous phase, temperatures of 200 to 400° C. are preferred. A solvent or diluting agent such as water can be used.
DE 39 34 459-A1 (Bayer AG) describes a method for the production of TEDA and piperazin (PIP) by conversion of EDA on zeolites of the Pentasil type with weakened acidity. According to DE 39 34 459-A1, such zeolites are available by replacement of at least 50% of all the replaceable cations with alkali metal cations or are zeolites in which the aluminium of the zeolite framework has been replaced isomorphally by iron. ZSM-5 catalysts not treated with this method have proven to be less suitable according to DE 39 34 459-A1. The conversion is conducted at a temperature of 300 to 400° C. and with a catalyst load of 0.03 to 2.0 kg/kg EDA/kg zeolite/h, with EDA/water mixtures with 2 to 25 Mol, preferably 5 to 15 Mol, water per Mol EDA being used.
In newer U.S. patent literature (U.S. Pat. No. 5,731,449 and U.S. Pat. No. 5,741,906; Air Products and Chemicals Inc. and U.S. Pat. No. 5,041,548 Idemitsu Kosan Ltd.) methods for the production of TEDA from EDA making use of modified Pentasil catalysts are suggested. According to U.S. Pat. No. 5,041,548 (Idemitsu Kosan Ltd.) there is, for example, the suggestion of using zeolite catalysts of the ZSM-5 type produced in the presence of organic cycling agents such as tetraalkyl ammonium compounds.
In U.S. Pat. No. 5,756,741 (Air Products and Chemicals Inc.), a two-phased method is described, in which an interim phase rich with piperazin is firstly produced from an amino-compound through cyclization reaction, this then being converted to TEDA by adding, for example, EDA.
The methods according to the state of the art have a low selectivity with regard to the formation of TEDA, a large amount of water as a diluting agent and, if applicable, an additional extensive catalyst production/modification in common. The objective of the invention is to develop a method for the production of TEDA from easily accessible initial compounds containing N which is simple to execute and above all is to guarantee an increased selectivity compared with the state of the art. The object of the invention is thus a method for the conversion of ethylene diamine (EDA) making use of zeolite catalysts which avoids the disadvantages of the state of the art, in particular low selectivity and a large production of piperazin, and leads to large yields of high-purity TEDA.
The object is achieved according to the invention by a method for production of triethylene diamine from ethylene diamine making use of zeolite catalysts, wherein
the educt flow in continuous operation contains 5 to 80% by weight of ethylene diamine, preferably 20 to 70% by weight and particularly preferably 35 to 60% by weight,
the zeolite catalysts are zeolite catalysts of the Pentasil type with Si: Al atom ratios of 100:1 to 700:1, preferably 100:1 to 350:1, particularly preferably 100:1 to 250:1 and in particular from 150:1 to 250:1, and exist or are used at least partly in the H+ and/or NH
4
+ form, preferably in the H+ form,
the educt flow has a water content of 2 to 60% by weight, preferably 10 to 40% by weight, particularly preferably 10 to 30% by weight, relative to the educt flow and
the reaction temperature is between 290 and 400° C., preferably 310 and 370° C., particularly preferably 310 and 350° C.
Preferred embodiments of the invention are the objects of the sub-claims.
The zeolite catalyst of the Pentasil type used as a catalyst in the method in the invention for the production of triethylene diamine has a crystalline skeleton structure of silicone dioxide and aluminium dioxide. To the extent that the zeolite catalyst of the Pentasil type has the Si:Al atom ratio as stated above, there are essentially no additional requirements either with regard to the zeolite material as such or with regard to the method according to which this can be obtained.
For example, the following types of zeolite catalysts of the Pentasil type are suitable for use in the invention in question: ZSM-5, ZSM-11, ZSM-23, ZSM-53, NU-87, ZSM-35, ZSM-48 and mixed structures of at least two of the above mentioned zeolites, in particular ZSM-5 and ZSM-11 as well as their mixed structures.
If the zeolite catalyst of the Pentasil type according to the invention is not available in the required acid H form due to the kind of production, but, for example, in the Na form (or any other salt form), then it can be completely or partially transferred into the required H+ or NH
4
+ form by an exchange of ions, e.g. with ammonium ions with subsequent calcination or by treatment with acids. In order to achieve the highest possible selectivity, high turnovers and long service lives, it can be a benefit if the zeolites are modified. A suitable modification of the catalysts comprises the zeolitic material—deformed or undeformed—being subjected to a treatment according to the state of the art with protonic acids—such as hydrochloric acid, sulphuric acid, hydrofluoric acid, phosphoric acid, a carbonic acid or dicarbonic acid and/or complex-formers and/or water vapour.
Further, the following reaction conditions have pro
Frauendorfer Erich
Frauenkron Matthias
Klockemann Werner
Stein Bernd
BASF - Aktiengesellschaft
Keil & Weinkauf
McKenzie Thomas C
Shah Mukund J.
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