PROCESS FOR THE CONVERSION OF MONOETHANOLAMINE TO ETHYLENEDIAMINE EMPLOYING A NANOCRYSTALLINE 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.nCH.sub.2CH.sub.2NH.sub.2 wherein n1 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; (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 average particle size of the zeolitic material along the 002 axis of the crystallites is in the range of from 51 nm to 558 nm as determined by powder X-ray diffraction.

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.nCH.sub.2CH.sub.2NH.sub.2 wherein n1 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; (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 average particle size of the zeolitic material along the 002 axis of the crystallites is in the range of from 51 nm to 558 nm as determined by powder X-ray diffraction.

2. The process of claim 1, wherein the average particle size of the primary crystallites of the zeolitic material as determined by powder X-ray diffraction is in the range of from 51 nm to 10015 nm.

3. 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.-%.

4. 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.-%.

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 1 vol.-% or less of hydrogen.

7. 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.

8. 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.

9. The process of claim 1, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and mixtures of two or more thereof.

10. The process of claim 1, wherein X is selected from the group consisting of Al, B, In, Ga, and mixtures of two or more thereof.

11. The process of claim 1, wherein the zeolitic material having the MOR framework structure is in the H-form and contains protons as extra-framework ions, wherein 0.1 wt.-% or less of the extra-framework ions are metal cations, calculated as the element and based on 100 wt.-% of YO.sub.2 contained in the zeolitic material.

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

13. The process of claim 1, 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; (3) optionally 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) optionally subjecting the zeolitic material obtained in (2), (3), (4), (5), or (6) to an ion-exchange procedure, wherein extra-framework ions contained in the zeolitic material are ion-exchanged against one or more metal ions M selected from the group consisting of alkaline earth metals and/or transition metals; (8) optionally drying and/or calcining the zeolitic material obtained in (7).

14. The process of claim 13, 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.

15. 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

[0156] FIG. 1 shows the powder X-ray diffraction pattern of the UZM-14-B according to U.S. Pat. No. 7,687,423 B2 obtained in Example 3, 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

[0157] 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 (Bruker AXS GmbH, stliche Rheinbrckenstr. 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:

=/(L.Math.cos )

where is the Lorentzian full width at half maximum (FWHM), is the X-ray wavelength of the CuK radiation used, L is the crystallite size, and is the half the scattering angle of the peak position.

[0158] 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 (20). Single peaks with varying crystallite sizes model the surrounding reflections.

[0159] The data was collected in the Bragg-Brentano geometry from 2 to 70 (2), using a step size of 0.02 (2).

Example 1: Synthesis of H-Mordenite

[0160] 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 h at 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.

[0161] 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 S. 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.

[0162] 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.

[0163] The BET surface area was determined to be 404 m.sup.2/g. The crystallinity of the product was measured to be 90%.

[0164] 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.

[0165] In a 2 liter stirring apparatus, 70 g of ammonium nitrate 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 630 g of distilled water. The filtrate was discarded and a new 10-wt. % aqueous solution containing 70 g of ammonium nitrate 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 630 g of distilled water. 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.

[0166] 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.

[0167] The BET surface area was determined to be 474 m.sup.2/g.

Example 2: Synthesis of Copper-Exchanged Mordenite

[0168] 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 Example 1 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.

[0169] 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.

[0170] The BET surface area was determined to be 371 m.sup.2/g.

Example 3: Synthesis of UZM-14-B According to U.S. Pat. No. 7,687,423 B2

[0171] In a 2 l plastic beaker 91 g fumed silica (CAB-O-SIL M5, Sigma-Aldrich) are provided. In a separate plastic beaker, 960 g of deionized water are weighed in, and 15.63 g of sodium hydroxide (NaOH, Sigma-Aldrich), 11.28 g of sodium aluminate (NaAlO.sub.2, Sigma-Aldrich), and 12.65 g tetraethylammonium bromide (TEABr, Aldrich) are added and stirring and the mixture is further stirred until complete dissolution thereof is achieved. The solution is then added to the beaker containing the fumed silica under stirring for providing a viscous gel, which is further stirred for 2 h. The synthesis gel thus obtained (1.07 kg) displaying a molar composition of 0.2 Na.sub.2O:0.051 Al.sub.2O.sub.3:SiO.sub.2:39.5 H.sub.2O:0.045 TEABr is then distributed among several pressure tight vessels and then crystallized for 76 h at 150 C. under agitating at a stirring speed of 300 rpm. The resulting product is then filtered off as a solid, washed with deionized water, and dried, followed by a step of heating the solids under a nitrogen atmosphere with a heating rate of 2 C. per minute to 540 C. and calcining the material at said temperature for 2 h, after which calcination at that temperature is continued in air for an additional 5 h. The yield was 59.1 g.

[0172] 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, 2.8 g sodium and 38 g silicon.

[0173] The BET surface area was determined to be 416 m.sup.2/g. The crystallinity of the product was measured to be 80%.

[0174] 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 as calculated from calculated from the X-ray diffraction data was determined to be 47.5 nm, and the average crystal size along the 002 axis of the crystallites was determined to be 33 nm.

[0175] 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 4 h at 120 C. and subsequently calcined at 500 C. in air for 5 h. The entire procedure was then repeated, affording 40.8 g of the H-form of the zeolitic material.

[0176] According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of 4.2 g aluminum, <0.01 g sodium and 38 g silicon.

[0177] The BET surface area was determined to be 486 m.sup.2/g. The crystallinity of the product was measured to be 71%, and the average crystal size as calculated from calculated from the X-ray diffraction data was determined to be 47 nm, and the average crystal size along the 002 axis of the crystallites was determined to be 33 nm.

Comparative Example 1: Synthesis of H-Mordenite

[0178] 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 h at 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.

[0179] 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 S. 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.

[0180] 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.

[0181] The BET surface area was determined to be 382 m.sup.2/g. The crystallinity of the product was measured to be 86%.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] The BET surface area was determined to be 432 m.sup.2/g.

Comparative Example 2: Synthesis of H-Mordenite

[0186] In a 5 l plastic beaker 90 g fumed silica (CAB-O-SIL M5, Sigma-Aldrich) are suspended in 675 g deionized water. To this suspension a mixture of 39.03 g tetraethylammonium bromide (TEABr, Aldrich) in 121.3 g deionized water is added. The resulting mixture is agitated for 1 h at a stirring speed of 200 rpm. Then, a mixture of 27.88 g sodium hydroxide flakes (NaOH, Sigma-Aldrich) in 121.3 g deionized water is added. The resulting mixture is then agitated for 1.5 h at a stirring speed of 300 rpm. Subsequently, a mixture of 11.75 g sodium aluminate (NaAlO.sub.2, Sigma-Aldrich) in 141.45 g deionized water are added and then 33.86 g of 1,6-hexanediol. The resulting mixture is then agitated for 1 h at a stirring speed of 200 rpm. Finally, 150 g of n-decane were added and the pH value of the mixture was determined to be 10.2. A gel is formed which aged over night.

[0187] The synthetic gel displaying a molar composition of 0.28 Na.sub.2O:0.048 Al.sub.2O.sub.3:SiO.sub.2:39.2 H.sub.2O:0.19 1,6-hexanediol:0.7 n-decane:0.124 TEABr is then crystallized in a pressure tight vessel for 120 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 S. 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 56 g.

[0188] 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, 3.3 g sodium and 37 g silicon.

[0189] The BET surface area was determined to be 398 m.sup.2/g. The crystallinity of the product was measured to be 89%.

[0190] 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 washed with distilled water until the wash water was free of nitrate. 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 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 45.7 g of the H-form of the zeolitic material.

[0191] According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 5.3 g aluminum, <0.01 g sodium and 39 g silicon.

[0192] The BET surface area was determined to be 440 m.sup.2/g.

[0193] 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 60 nm.

Comparative Example 3: Synthesis of H-Mordenite from Commercial Na-MOR

[0194] In a 2 liter stirring apparatus, 200 g of ammonium chloride dissolved in 800 ml of distilled water were placed as an aqueous solution (20 wt.-% NH.sub.4Cl), 100 g of Na-Mordenite (FM-8, Zeochem) were added, and the resulting mixture was stirred for 2 h at 100 C. The zeolitic material was then filtered off and washed with distilled water until the wash water was free of chloride. The washed material was then dried for 12 h at 120 C. and subsequently calcined at 500 C. for 5 h with a heating rate of 2 C./min. The procedure afforded 97.8 g of the H-form of the commercial zeolitic material.

[0195] According to the elemental analysis, the resulting sample had the following contents determined per 100 g substance of <0.1 g carbon, 2.8 g aluminum, <0.01 g sodium and 38 g silicon.

[0196] As calculated from the X-ray diffraction data of the commercial sample, the average crystal size along the 002 axis of the crystallites was determined to be 77 nm.

Comparative Example 4: Commercial Mordenite in the H-Form

[0197] A commercial sample of H-Mordenite (TZM-1013, Tricat) was directly employed as Comparative Example 4.

[0198] According to the elemental analysis, the sample had the following contents determined per 100 g substance of <0.1 g carbon, 5.4 g aluminum, 0.03 g sodium and 36 g silicon.

[0199] As calculated from the X-ray diffraction data of the commercial sample, the average crystal size was determined to be 71 nm, and the average crystal size along the 002 axis of the crystallites was determined to be 99 nm.

Comparative Example 5: Commercial Mordenite in the H-Form

[0200] A further commercial sample of H-Mordenite (MOR-1501, Novel) was directly employed as Comparative Example 5.

[0201] According to the elemental analysis, the sample had the following contents determined per 100 g substance of 5.1 g aluminum and 40 g silicon.

[0202] As calculated from the X-ray diffraction data of the commercial sample, the average crystal size was determined to be 91.5 nm, and the average crystal size along the 002 axis of the crystallites was determined to be 83 nm.

Example 4: Catalyst Testing

[0203] 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.

[0204] 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 m analytical sieve. Crushing and sieving was repeated for obtaining the desired target fraction having a particle diameter in the range of from 315-500 m using suitable analytical sieves and a pestle, and wherein the fines (<315 m) were removed by sieving on a sieving tool (e.g. Retsch AS 200) or by sieving manually.

[0205] 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 m. 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.

[0206] 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:

X(educt)=1c(educt)/c(IS)/(c(educt_by-pass)/c(IS-by-pass))Conversion:

Y(product)=c(product)/c(IS)/(c(educt_by-pass)/c(IS-by-pass))Yields:

S(product)=Y(product)/X(educt)Selectivities:

[0207] 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 1-3 and Comparative Examples 1-5 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 (AEPIP), and 1,4-diazabicyclo[2.2.2]octane (DABCO) generated in the reaction in %. As regards the results obtained for Examples 1-3, values are indicated as obtained from 2 different runs, respectively.

TABLE-US-00001 TABLE 1 Results from catalytic testing of Examples 1-3 and Comparative Examples 1-5. average 002 crystal plane EDA DETA AEEA PIP AE-PIP DABCO MEOA dimension Yield Yield Yield Yield Yield Yield conversion Example [nm] [%] [%] [%] [%] [%] [%] [%] Ex. 3 33 31.9 0.4 1.6 2.2 3.2 1.8 53.0 Ex. 1 46 32.1 0.5 2.1 1.1 2.1 1.2 48.3 Ex. 2 46 35.2 0.7 1.8 1.7 2.8 1.5 52.5 Comp. Ex. 1 58 20.8 <0.1 2.4 0.7 1.4 0.8 34.3 Comp. Ex. 2 60 4.0 1.1 1.2 5.3 7.2 3.7 52.6 Comp. Ex. 5 83 28.4 0.7 2.5 1.3 2.7 1.2 47.4 Comp. Ex. 3 77 6.9 <0.1 1.8 0.6 1.3 0.6 14.6 Comp. Ex. 4 99 9.6 <0.1 1.4 0.6 1.4 0.5 15.5

[0208] Thus, as may be taken from the results displayed in Table 1, all of the inventive samples having an average 002 crystal plane dimension of less than 55 nm display a clearly superior performance in the catalytic amination of MEOA to EDA, both in view of MEOA conversion, as well as with respect to the yield in EDA which may be realized. As may be taken from the results obtained for Example 2 compared to those obtained for Example 1, the superior performance may be further increased by ion exchange of the H-form with copper.

[0209] Therefore, as demonstrated in the foregoing, it has surprisingly been found that a zeolitic material having the MOR framework structure and which displays an average 002 crystal plane dimension of less than 55 nm 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 zeolitic material having the MOR framework structure displaying an average 002 crystal plane dimension of less than 55 nm, wherein said effect may be further increased by ion exchange of the H-form with copper.

LIST OF THE CITED PRIOR ART REFERENCES

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