Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure

Abstract

The present invention relates to a process for the conversion of 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines of the formula H.sub.2N—[CH.sub.2CH.sub.2NH].sub.n—CH.sub.2CH.sub.2NH.sub.2 wherein n≥1 comprising: (i) providing a catalyst comprising a zeolitic material having the MOR framework structure comprising YO.sub.2 and X.sub.2O.sub.3, wherein Y is a tetravalent element and X is a trivalent element, said zeolitic material containing copper as extra-framework ions; (ii) providing a gas stream comprising 2-aminoethanol and ammonia; (iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) for converting 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines.

Claims

1. A process for the conversion of 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines of the formula H.sub.2N—[CH.sub.2CH.sub.2NH].sub.n—CH.sub.2CH.sub.2NH.sub.2 wherein n≥1 comprising (i) providing a catalyst comprising a zeolitic material having the MOR framework structure comprising YO.sub.2 and X.sub.2O.sub.3, wherein Y is Si and X is Al, said zeolitic material containing copper as extra-framework ions; (ii) providing a gas stream comprising 2-aminoethanol and ammonia; (iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) for converting 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines, wherein the zeolitic material having the MOR framework structure is prepared by a process comprising (1) preparing a mixture comprising at least one source of YO.sub.2, at least one source of X.sub.2O.sub.3, and comprising one or more organotemplates as structure directing agent and/or comprising seed crystals; (2) crystallizing the mixture prepared in (i) for obtaining a zeolitic material having the MOR framework structure; and (7) subjecting the zeolitic material obtained in (2) to an ion-exchange procedure, wherein extra-framework ions contained in the zeolitic material are ion-exchanged against Cu.sup.2+ and/or Cu.sup.+.

2. The process of claim 1, wherein the gas stream provided in (ii) and contacted with the catalyst in (iii) contains 2-aminoethanol in an amount in the range of from 0.1 to 10 vol.-%.

3. The process of claim 1, wherein the gas stream provided in (ii) and contacted with the catalyst in (iii) contains ammonia in an amount in the range of from 5 to 90 vol.-%.

4. The process of claim 1, wherein the gas stream provided in (ii) and contacted with the catalyst in (iii) contains 1 vol.-% or less of hydrogen.

5. The process of claim 1, wherein the gas stream provided in (ii) and contacted with the catalyst in (iii) further contains hydrogen in an amount in the range of from 0.1 to 70 vol.-%.

6. The process of claim 1, wherein the gas stream provided in (ii) and contacted with the catalyst in (iii) contains H.sub.2O in an amount of 5 vol.-% or less.

7. The process of claim 1, wherein the gas stream provided in (ii) is heated to a temperature in the range of from 120 to 600° C., prior to contacting with the catalyst in (iii) at that temperature.

8. The process of claim 1, wherein the zeolitic material contains from 0.5 to 15 wt.-% of copper as extra-framework ions calculated as the element and based on 100 wt-% of YO.sub.2 contained in the zeolitic material having the MOR framework structure.

9. The process of claim 1, wherein the Cu:X.sub.2O.sub.3 molar ratio of the zeolitic material is in the range of from 0.01 to 2.

10. The process of claim 1, wherein the zeolitic material contains substantially no Na.

11. The process of claim 1, wherein the zeolitic material having the MOR framework structure is prepared by a process further comprising (3) isolating the zeolitic material obtained in (2); (4) optionally washing the zeolitic material obtained in (2) or (3); (5) optionally drying and/or calcining the zeolitic material obtained in (2), (3), or (4); (6) optionally subjecting the zeolitic material obtained in (2), (3), (4), or (5) to an ion-exchange procedure, wherein extra-framework ions contained in the zeolitic material are ion-exchanged against H.sup.+; (7) subjecting the zeolitic material obtained in (3), (4), (5), or (6) to an ion-exchange procedure, wherein extra-framework ions contained in the zeolitic material are ion-exchanged against Cu.sup.2+ and/or Cu.sup.+; (8) optionally drying and/or calcining the zeolitic material obtained in (7).

12. The process of claim 11, wherein in (6) the step of subjecting the zeolitic material to an ion-exchange procedure includes the steps of (6.a) subjecting the zeolitic material obtained in (2), (3), (4), or (5) to an ion-exchange procedure, wherein extra-framework ions contained in the zeolitic material are ion-exchanged against NH.sub.4.sup.+; (6.b) calcining the ion-exchanged zeolitic material obtained in (6.a) for obtaining the H-form of the zeolitic material.

13. The process of claim 1, wherein 2-aminoethanol comprised in the gas stream obtained in (iii) is separated from said gas stream and recycled to (ii).

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the powder X-ray diffraction pattern of the Na-Mordenite obtained in Example 2, wherein the line pattern of sodium Mordenite from a crystallographic database has been included for comparative purposes. The X-ray diffraction pattern shown in the figure was measured using Cu K alpha-1 radiation. In the respective diffractogram, the diffraction angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate.

EXAMPLES

(2) The crystallite size of the samples was determined using X-ray diffraction by fitting the diffracted peak width using the software TOPAS 4.2. Instrumental broadening was considered during the peak fitting using the fundamental parameter approach as described in TOPAS 4.2 Users Manual (Bilker AXS GmbH, Östliche Rheinbrückenstr. 49, 76187 Karlsruhe, Germany). This leads to a separation of the instrumental from the sample broadening. The sample contribution was determined using a single Lorentzian profile function that is defined in the following equation:
β=λ/(L.Math.cos θ)
where β is the Lorentzian full width at half maximum (FWHM), λ is the X-ray wavelength of the CuKα radiation used, L is the crystallite size, and θ is the half the scattering angle of the peak position.

(3) The crystallite size of the 002 reflection in samples having the MOR framework type was determined in a refinement of the local data surrounding the 002 reflection, from 21° to 24.2° (2θ). Single peaks with varying crystallite sizes model the surrounding reflections.

(4) The data was collected in the Bragg-Brentano geometry from 2° to 70° (2θ), using a step size of 0.02° (2θ).

Reference Example 1

Synthesis of H-Mordenite

(5) In a 5 l plastic beaker 120 g fumed silica (CAB-O-SIL M5, Sigma-Aldrich) are suspended in 900 g deionized water. To this suspension a mixture of 52.04 g tetraethylammonium bromide (TEABr, Aldrich) in 161.7 g deionized water is added. The resulting mixture is agitated for 1 h at a stirring speed of 200 rpm. Then, a mixture of 36.5 g sodium hydroxide flakes (NaOH, Sigma-Aldrich) in 161.7 g deionized water is added. The resulting mixture is then agitated for 1.5 hat a stirring speed of 300 rpm. Subsequently, 188.6 g deionized water are added and then a mixture of 15.66 g sodium aluminate (NaAlO.sub.2, Sigma-Aldrich) in 188.6 g deionized water. The resulting mixture is then agitated for 1 h at a stirring speed of 200 rpm. The pH value of the mixture was determined to be 12.5. A gel is formed which aged over night.

(6) The synthetic gel displaying a molar composition of 0.28 Na.sub.2O:0.048 Al.sub.2O.sub.3:SiO.sub.2:44.5 H.sub.2O:0.13 TEABr is then crystallized in a pressure tight vessel for 84 h at 170° C. under agitating at a stirring speed of 250 rpm. Then, the resulting product is filtered off as a solid and washed with deionized water until the electrical conductance of the washing water reaches a value lower than 150 μS. The solids are then dried in air at 90° C. for 12 h. Subsequently, the solids are heated in air to 90° C. with a heating rate of 3.5° C. per minute and then left at said temperature for 2 h. Then the solids are heated to 120° C. with a heating rate of 1.5° C. per minute and then left at said temperature for 2 h. Then the solids are heated to 550° C. with a heating rate of 4.5° C./min and left at said temperature for 12 h. The yield was 66 g.

(7) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of 0.1 g carbon, 5.0 g aluminum, 3.2 g sodium and 37 g silicon.

(8) The BET surface area was determined to be 382 m.sup.2/g. The crystallinity of the product was measured to be 86%.

(9) As taken from the X-ray diffraction pattern of the resulting product, the zeolitic material obtained displays the MOR framework structure as the single crystalline phase, wherein the average crystal size along the 002 axis of the crystallites as calculated from the X-ray diffraction data was determined to be 58 nm.

(10) In a 2 liter stirring apparatus, 50 g of ammonium nitrate dissolved in 450 g of distilled water were placed as an aqueous solution (10 wt.-% NH.sub.4NO.sub.3), 50 g of the zeolitic material were added, and the resulting mixture was stirred for 2 h at 80° C. The zeolitic material was then filtered off and a new 10-wt.% aqueous solution containing 50 g of ammonium nitrate dissolved in 450 g of distilled water was then placed in the stirring apparatus to which the filtered off zeolitic material was added and the resulting mixture again stirred for 2 h at 80° C. The zeolitic material was then filtered off and washed with distilled water until the wash water was free of nitrate. The washed material was then dried for 5 h at 120° C. and subsequently calcined at 500° C. for 5 h with a heating rate of 2° C./min. The entire procedure was then repeated, affording 43.7 g of the H-form of the zeolitic material.

(11) According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 4.9 g aluminum, 0.06 g sodium and 38 g silicon.

(12) The BET surface area was determined to be 432 m.sup.2/g.

Reference Example 2

Synthesis of H-Mordenite

(13) In a 5 l plastic beaker 120 g fumed silica (CAB-O-SIL M5, Sigma-Aldrich) are suspended in 900 g deionized water. To this suspension a mixture of 52.04 g tetraethylammonium bromide (TEABr, Aldrich) in 161.7 g deionized water is added. The resulting mixture is agitated for 1 h at a stirring speed of 200 rpm. Then, a mixture of 36.5 g sodium hydroxide flakes (NaOH, Sigma-Aldrich) in 161.7 g deionized water is added. The resulting mixture is then agitated for 1.5 hat a stirring speed of 300 rpm. Subsequently, 188.6 g deionized water are added and then a mixture of 15.66 g sodium aluminate (NaAlO.sub.2, Sigma-Aldrich) in 188.6 g deionized water. The resulting mixture is then agitated for 1 h at a stirring speed of 200 rpm. The pH value of the mixture was determined to be 12.2. A gel is formed which aged over night.

(14) The synthetic gel displaying a molar composition of 0.28 Na.sub.2O:0.048 Al.sub.2O.sub.3:SiO.sub.2:44.5 H.sub.2O:0.13 TEABr is then crystallized in a pressure tight vessel for 72 h at 170° C. under agitating at a stirring speed of 250 rpm. Then, the resulting product is filtered off as a solid and washed with deionized water until the electrical conductance of the washing water reaches a value lower than 150 μS. The solids are then dried in air at 90° C. for 12 h. Subsequently, the solids are heated in air to 90° C. with a heating rate of 3.5° C. per minute and then left at said temperature for 2 h. Then the solids are heated to 120° C. with a heating rate of 1.5° C. per minute and then left at said temperature for 2 h. Then the solids are heated to 550° C. with a heating rate of 4.5° C./min and left at said temperature for 12 h. The yield was 82 g.

(15) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of <0.1 g carbon, 4.9 g aluminum, 3.2 g sodium and 37 g silicon.

(16) The BET surface area was determined to be 404 m.sup.2/g. The crystallinity of the product was measured to be 90%.

(17) As taken from the X-ray diffraction pattern of the resulting product, the zeolitic material obtained displays the MOR framework structure as the single crystalline phase, wherein the average crystal size as calculated from calculated from the X-ray diffraction data was determined to be 59 nm, and the average crystal size along the 002 axis of the crystallites was determined to be 46 nm.

(18) In a 2 liter stirring apparatus, 70 g of ammonium nitrate dissolved in 630 g of distilled water were placed as an aqueous solution (10 wt.-% NH.sub.4NO.sub.3), 70 g of the zeolitic material were added, and the resulting mixture was stirred for 2 h at 80° C. The zeolitic material was then filtered off and washed with distilled water until the wash water was free of nitrate. The filtrate was discarded and a new 10-wt.% aqueous solution containing 70 g of ammonium nitrate dissolved in 630 g of distilled water was then placed in the stirring apparatus to which the washed zeolitic material was added and the resulting mixture again stirred for 2 h at 80° C. The zeolitic material was then filtered off and washed anew with distilled water until the wash water was free of nitrate. The washed material was then dried for 5 h at 120° C. and subsequently calcined at 500° C. for 5 h with a heating rate of 2° C./min. The entire procedure was then repeated, affording 63.4 g of the H-form of the zeolitic material.

(19) According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 5.0 g aluminum, 0.01 g sodium and 38 g silicon.

(20) The BET surface area was determined to be 474 m.sup.2/g.

Example 1

Synthesis of Copper-Exchanged Mordenite

(21) 1.5 liters of a 0.01 molar aqueous solution of copper(II) acetate (3 grams in 1.5 liters) were placed in a 2 liter stirring apparatus and 25 g of the product from Reference Example 2 were then added and the mixture stirred at room temperature for 20 h. The zeolitic material was then filtered off, and the filtrate was discarded. A new solution of 1.5 liters of a 0.01 molar aqueous solution of copper(II) acetate (3 grams in 1.5 liters) was then placed in the 2 liter stirring apparatus and the zeolitic material was added thereto and the mixture stirred at room temperature for 20 h. The zeolitic material was then filtered off, the filtrate discarded, and the zeolitic material was again added to a new solution of 1.5 liters of a 0.01 molar aqueous solution of copper(II) acetate (3 grams in 1.5 liters) and stirred for 20 h at room temperature. The resulting product was then separated from the solution by centrifugation, the solution discarded, and the zeolitic material subsequently suspended in 1.25 liters of distilled water. The zeolitic material was then separated from the solution by centrifugation, the washwater was discarded, and the washing procedure with distilled water was repeated 3 times for washing the zeolitic material. The zeolitic material was then dried for 24 h at 110° C., thus affording 24.4 g of a copper-exchanged zeolitic material.

(22) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of <0.1 g carbon, 4.8 g aluminum, 2.6 g copper and 35 g silicon.

(23) The BET surface area was determined to be 371 m.sup.2/g.

Example 2

Synthesis of Copper-Exchanged Mordenite

(24) In a stirring apparatus, 2.4 kg fumed silica (CAB-O-SIL M5, Sigma-Aldrich) are suspended in 18 kg deionized water. To this suspension an solution of 1.04 kg tetraethylammonium bromide (TEABr, Aldrich) in 1.04 kg deionized water is added. The resulting mixture is agitated for 1 h at a stirring speed of 150 rpm. Then, a solution of 0.73 kg sodium hydroxide flakes (NaOH, Sigma-Aldrich) in 3.5 kg deionized water is added. The resulting mixture is then agitated for 1.5 h at a stirring speed of 180 rpm. Subsequently, a solution of 0.31 kg sodium aluminate (NaAlO.sub.2, Sigma-Aldrich) in 4 kg deionized water are added, together with 3 kg of deionized water with which the receptacle containing the previous solution was washed out. The resulting mixture is then agitated for 1 h at a stirring speed of 180 rpm. The pH value of the resulting gel was determined to be 13.1. The gel was then aged over night.

(25) The synthetic gel displaying a molar composition of 0.5 Na.sub.2O:0.0475 Al.sub.2O.sub.3:SiO.sub.2:44.5 H.sub.2O:0.125 TEABr is then heated under stirring at 200 rpm to 170° C. in a pressure tight vessel and held at that temperature for 84 h under further stirring at the same speed. Then, the resulting product displaying a pH of 12.5 is filtered off as a solid and washed five times with 50 liters of deionized water, respectively, until the electrical conductance of the washing water reaches a value of 85 μS. The filter cake is then heated to 100° C. and a nitrogen stream is conducted over the filter cake for 16 h for drying at that temperature. 1.667 kg of a crystalline material was thus obtained, which is then calcined for 12 h at 550° C., thus obtaining 1.533 kg of a white powder.

(26) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of <0.1 g carbon, 5.3 g aluminum, 3.2 g sodium and 35 g silicon.

(27) The BET surface area was determined to be 400 m.sup.2/g. The crystallinity of the product was measured to be 93%.

(28) As taken from the X-ray diffraction pattern of the resulting product displayed in FIG. 1, the zeolitic material obtained displays the MOR framework structure as the single crystalline phase. The average crystal size of the crystallites as calculated from the X-ray diffraction data was determined to be 57.5 nm.

(29) 325 g of distilled water were placed in a stirring apparatus and 50 g of the crystallization product having the MOR type framework structure were then added and the heated to 60° C. 7.15 g of copper(II) acetate and a solution of 0.39 g acetic acid in 0.17 g distilled water (70% acetic acid solution) were then added to the mixture which was then stirred at 60° C. for 1 h. 243.75 g of distilled water (having room temperature) were then added to the hot mixture, after which the zeolitic material was immediately filtered off. The filter cake was then dried for 12 h at 110° C. and subsequently heated to 500° C. using a heating ramp of 2° C./min and calcined at that temperature for 5 h, thus affording 51.5 g of a copper-exchanged zeolitic material.

(30) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of <0.1 g carbon, 4.7 g aluminum, 0.08 g copper, 0.07 g Na, and 35 g silicon.

(31) The BET surface area was determined to be 377 m.sup.2/g.

Example 3

Synthesis of Copper-Exchanged Mordenite

(32) In a stirring apparatus, 650 g of ammonium nitrate were placed as a solution in 5.85 kg of distilled water (10 wt.-% NH.sub.4NO.sub.3), 650 g of the non copper ion-exchanged zeolitic material having the MOR framework structure as obtained from crystallization and after washing, drying and calcining in Example 2 were added to the solution, and the resulting mixture was heated to 80° C. under stirring and held at that temperature for 2 h. The zeolitic material was then filtered off, the filtrate was discarded, and a new 10-wt.% aqueous solution containing 650 g of ammonium nitrate was then placed in the stirring apparatus to which the filtered-off zeolitic material was added and the resulting mixture again stirred for 2 h at 80° C. The zeolitic material was then filtered off and washed with 12 liters of distilled water. The washed material was then dried for 5 h at 120° C. and subsequently calcined at 500° C. for 5 h to afford 1.196 kg of a white powder.

(33) According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 5.4 g aluminum, 0.1 g sodium and 40 g silicon.

(34) A new 10-wt.% aqueous solution containing 650 g of ammonium nitrate was then placed in the stirring apparatus, and the calcined powder was added to the solution, after which the resulting mixture was heated to 80° C. under stirring and held at that temperature for 2 h. The zeolitic material was then filtered off and washed with 12 liters of distilled water. The washed material was then dried for 5 h at 120° C. and subsequently calcined at 500° C. for 5 h to afford 1.172 kg of the H-form of the zeolitic material.

(35) According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of 4.6 g aluminum, 0.01 g sodium and 38 g silicon.

(36) According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 5.0 g aluminum, 0.01 g sodium and 38 g silicon.

(37) The BET surface area was determined to be 438 m.sup.2/g.

(38) 1.8 liters of a 0.01 molar aqueous solution of copper(II) acetate (3.6 grams in 1.8 liters) were placed in a 2 liter stirring apparatus and 30 g of the H-form of the zeolitic material were then added and the mixture stirred at room temperature for 20 h. The zeolitic material was then filtered off, and the filtrate was discarded. A new solution of 1.8 liters of a 0.01 molar aqueous solution of copper(II) acetate (3.6 grams in 1.8 liters) was then placed in the 2 liter stirring apparatus and the zeolitic material was added thereto and the mixture stirred at room temperature for 20 h. The zeolitic material was then filtered off, the filtrate discarded, and the zeolitic material was again added to a new solution of 1.8 liters of a 0.01 molar aqueous solution of copper(II) acetate (3.6 grams in 1.8 liters) and stirred for 20 h at room temperature. The resulting product was then separated from the solution by centrifugation, the solution discarded, and the zeolitic material subsequently suspended in 1.5 liters of distilled water. The zeolitic material was then separated from the solution by centrifugation, the washwater was discarded, and the washing procedure with distilled water was repeated 3 times for washing the zeolitic material. The zeolitic material was then dried for 24 h at 110° C., thus affording 22 g of a copper-exchanged zeolitic material.

(39) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of 0.17 g carbon, 4.4 g aluminum, 2.6 g copper and 36 g silicon.

(40) The BET surface area was determined to be 425 m.sup.2/g.

Example 4

Synthesis of Copper-Exchanged Mordenite

(41) 50 g of the H-form of the zeolitic material obtained in Example 3 which has not been subject to copper ion exchange were placed in a beaker and an aqueous solution of 4.03 copper(II) acetate monohydrate dissolved in 50 ml of distilled water were added thereto and the resulting mixture stirred with a spatula. The zeolitic material was then filtered off and the filter cake was dried in a drying oven at 110° C. for 12 h, and subsequently heated at a rate of 2° C./min to 500° C. and calcined at that temperature for 5 h, thus affording 49 g of a copper ion-exchanged zeolitic material.

(42) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of <0.1 g carbon, 4.7 g aluminum, 2.6 g copper and 38 g silicon.

(43) The BET surface area was determined to be 444 m.sup.2/g.

Example 5

Synthesis of Copper-Exchanged Mordenite

(44) 325 g of distilled water were placed in a round bottom flask and 50 g of the H-form of the zeolitic material obtained in Example 3 which has not been subject to copper ion exchange is added thereto under stirring, after which the mixture is then heated under stirring to 60° C. 7.15 g of copper(II) acetate and a solution of 0.39 g acetic acid in 0.17 g distilled water (70% acetic acid solution) were then added to the mixture which was then stirred at 60° C. for 1 h. 243.75 g of distilled water (having room temperature) were then added to the hot mixture for cooling, after which the zeolitic material was filtered off. The filter cake was then washed twice with 600 ml of distilled water to obtain a value of 10 μS in the filtrate. The filter cake was then dried for 12 h at 110° C. and subsequently heated to 500° C. using a heating ramp of 2° C./min and calcined at that temperature for 5 h, thus affording 49.5 g of a copper-exchanged zeolitic material.

(45) According to the elemental analysis the resulting product had the following contents determined per 100 g substance of 4.4 g aluminum, 1.9 g copper, and 37 g silicon.

(46) The BET surface area was determined to be 477 m.sup.2/g.

Example 6

Catalyst Testing

(47) Into a carrier gas stream consisting of nitrogen and specific amounts of methane (as internal standard), hydrogen, ammonia, and monoethanolamine (MEOA) are evaporated at a temperature according to their partial pressures. Ammonia is evaporated in a first evaporator whereas MEOA is evaporated in a second evaporator downstream. Afterwards the resultant gas vapor stream is heated to 200° C.

(48) The zeolitic materials to be tested were respectively admixed with 3 wt.-% graphite and homogenized by shaking and mixing, if necessary using a mortar and pestle. The homogenized mixture is then pelletized using a 13 mm diameter pelletizing tool set applying 10-40 kN of force depending on the zeolite in order to obtain stable pellets and thus a stable target fraction, wherein the pellets obtained are 2-3 mm in height and have a diameter of 13 mm. The pellets thus obtained were then precrushed with mortar and pestle and sieved through a 1000 μm analytical sieve. Crushing and sieving was repeated for obtaining the desired target fraction having a particle diameter in the range of from 315-500 μm using suitable analytical sieves and a pestle, and wherein the fines (<315 μm) were removed by sieving on a sieving tool (e.g. Retsch AS 200) or by sieving manually.

(49) This gas vapor stream is fed to a reactor filled with 1 cm.sup.3 of catalyst particles that are of the size in the range of 315-500 μm. The catalyst bed has a diameter of 4 mm and a length of 80 mm. Due to the low diameter of the catalyst bed it is isothermal. Before the catalyst bed the gas vapor stream is heated to the reaction temperature by passing it through an inert bed. Both the catalyst bed and the inert bed are heated externally to the reaction temperature. Downstream to the catalyst bed the product stream is diluted and cooled to 250° C. Further downstream its composition is measured by an online-GC.

(50) Results were calculated by referencing the ratio of educt to internal standard (IS) to the same ratio as obtained by analyzing the gas vapor stream from a by-pass tubing. Thus undetected products (high-boilers, coke) are taken into account as well. The following formulas give the detailed procedure:
Conversion: X(educt)=1-c(educt)/c(IS)/(c(educt_by-pass)/c(IS-by-pass))
Yields: Y(product)=c(product)/c(IS)/(c(educt_by-pass)/c(IS-by-pass))
Selectivities: S(product)=Y(product)/X(educt)
For the standard experiment the following testing conditions were chosen: gas hourly space velocity (GHSV) of 5000 h.sup.−1 with MEOA-concentration of 1 vol-%. Apart from the main educt MEOA the gas stream consisted of 40 vol.-% ammonia, 20 vol.-% hydrogen and 1 vol.-% methane as internal standard with nitrogen as balance. The catalysts were heated in nitrogen to the reaction temperature of 300° C. and then the gas feed was switched to testing conditions. The results obtained from catalytic testing performed on Examples 1-5 and Reference Examples 1 and 2 are displayed in Table 1 below, wherein the yield of ethylene diamine and the conversion rate of MEOA are respectively shown in %, as well as the amounts of diethylenetriamine (DETA), aminoethylethanolamine (AEEA), piperazine (PIP), 1-(2-aminoethyl)piperazine (AE-PIP), and 1,4-diazabicyclo[2.2.2]octane (DABCO) generated in the reaction in %. As regards the results obtained for Example 1 and Reference Example 2, values are indicated from 2 different runs, respectively.

(51) TABLE-US-00001 TABLE 1 Results from catalytic testing of Examples 1-5 and Reference Examples 1 and 2. EDA DETA AEEA PIP AE-PIP DABCO MEOA Cu Yield Yield Yield Yield Yield Yield conversion Example [wt.-%] [%] [%] [%] [%] [%] [%] [%] Ex. 1 2.6 35.2 0.7 1.8 1.7 2.8 1.5 52.5 Ref. Ex. 2 — 31.6 0.6 1.9 1.9 3.3 2.0 51.0 Ex. 5 1.9 27.1 0.2 2.0 1.3 2.2 1.0 42.2 Ex. 3 2.6 35.9 0.8 1.8 2.1 3.1 1.9 58.9 Ex. 4 2.6 25.0 0.2 1.7 1.2 2.1 0.9 39.5 Ref. Ex. 1 — 20.8 <0.1 2.4 0.7 1.4 0.8 34.3 Ex. 2 0.08 9.4 <0.1 1.6 0.7 1.3 0.7 20.3

(52) Thus, as may be taken from the results displayed in Table 1, all of the inventive samples display a superior performance in the catalytic amination of MEOA to EDA when the zeolitic material of the reference examples having the MOR framework structure are ion exchanged with copper. Thus, said effect may be observed when comparing the results obtained for reference example 2 compared to the results for example 1 after having subjected a sample from reference example 2 to ion exchange. Same applies accordingly when comparing the results obtained for reference example 1 compared to the results for examples 3, 4, and 5 after having respectively subjected samples as obtained according to reference example 1 to ion exchange with copper.

(53) As regards the results of obtained for example 2, these may not be directly compared to the other examples and reference examples which were all obtained using the H-form of the zeolitic materials having the MOR framework structure, respectively. In particular, it is noted that example to was obtained from the sodium-form of a zeolitic material having the MOR framework structure, which was subsequently subject to partial ion exchange of the sodium ions against copper (II) ions. Consequently, a comparison of the sample from example 2 would necessarily require that a sample of the zeolitic material containing the same amount of sodium yet which has not been ion exchanged with copper be tested in the catalytic amination of MEOA.

(54) Therefore, as demonstrated in the foregoing, it has surprisingly been found that a zeolitic material having the MOR framework structure and which has been ion exchanged with copper not only displays a considerably improved catalytic activity in the amination of MEOA, but furthermore displays a highly improved selectivity as may be observed from the results for the yield in EDA achieved by the inventive samples. Consequently, it has quite unexpectedly been found that a highly improved process for the amination of MEOA to EDA may be obtained by using a copper ion exchanged zeolitic material having the MOR framework structure.

LIST OF THE CITED PRIOR ART REFERENCES

(55) WO 2014/135662 A U.S. Pat. No. 7,605,295 U.S. Pat. No. 7,687,423 B2 Grundner, Sebastian et al. in Nat. Commun. 2015, Vol. 6article number 7546 U.S. Pat. No. 4,918,233 CN 1962058 A JP H0687797 A JP H07247245 A CN 101215239 B CN 101406845 A CN 102974393 A CN 103007984 A CN102233272A CN102190588A inaugural thesis “Heterogeneous Transition Metal Catalyzed Amination of Aliphatic Diols” from Achim Fischer, Diss. ETH No 12978, 1998 WO 2009/083580 A1 U.S. Pat. No. 4,918,233 CN 101215239 A DE 10 2005 047464 A1