PROCESS FOR THE ALKYLATION OF ALIPHATIC ORGANIC COMPOUNDS

Abstract

Disclosed is a process for the alkylation of an aliphatic organic compound comprising: (a) providing a catalyst comprising one or more zeolitic materials having a BEA framework structure, wherein the BEA framework structure comprises YO.sub.2 and optionally comprises X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element, (b) contacting the catalyst with one or more aliphatic organic compounds in the presence of one or more alkylating agents in one or more reactors for obtaining one or more alkylated organic compounds, wherein the one or more zeolitic materials are obtainable from a synthetic process which does not employ an organotemplate as structure directing agent.

Claims

1. A process for the alkylation of an aliphatic organic compound, the process comprising: providing a catalyst comprising one or more zeolitic materials having a BEA framework structure, wherein the BEA framework structure comprises YO.sub.2 and optionally comprises X.sub.2O.sub.3, wherein Y is a tetravalent element, and X is a trivalent element; and contacting the catalyst with one or more aliphatic organic compounds in the presence of one or more alkylating agents in one or more reactors for obtaining one or more alkylated organic compounds, wherein the one or more zeolitic materials are obtained from a synthetic process which does not employ an organotemplate as a structure directing agent.

2. The process of claim 1, wherein the one or more zeolitic materials are non-calcined.

3. The process of claim 1, wherein Y is at least one selected from the group consisting of Si, Sn, Ti, Zr, and Ge.

4. The process of claim 1, wherein the BEA framework structure comprises X.sub.2O.sub.3; and wherein X is at least one selected from the group consisting of Al, B, In, and Ga.

5. The process of claim 1, wherein the BEA framework structure comprises X.sub.2O.sub.3; and wherein a Y:X molar ratio of the one or more zeolitic materials is in a range of from 1 to 100.

6. The process of claim 1, wherein the one or more zeolitic materials comprise H.sup.+ as a counterion to the BEA framework structure of the one or more zeolitic materials.

7. The process of claim 1, wherein the one or more zeolitic materials have an X-ray diffraction pattern comprising the following reflections: 9-29% intensity at a diffraction angle of 21.06-21.26; 100% intensity at a diffraction angle of 22.11-22.31; 10-30% intensity at a diffraction angle of 25.01-25.21; 8-28% intensity at a diffraction angle of 26.77-26.97; 12-32% intensity at a diffraction angle of 28.38-28.58; 27-47% intensity at a diffraction angle of 29.22-29.42; 7-27% intensity at a diffraction angle of 29.99-30.19; 9-29% intensity at a diffraction angle of 32.85-33.25; and 11-31% intensity at a diffraction angle of 42.86-43.26; wherein 100% relates to the intensity of the maximum peak in the X-ray powder diffraction pattern, and wherein the diffraction angles are in terms of 2 [Cu K(alpha 1)].

8. The process of claim 7, wherein the X-ray diffraction pattern further comprises the following reflection: 6-26% intensity at a diffraction angle of 25.54-25.74.

9. The process of claim 1, wherein the one or more zeolitic materials comprise zeolite beta.

10. The process of claim 1, wherein the one or more aliphatic organic compounds are at least one selected from the group consisting of a substituted (C2-C20)hydrocarbon, a cyclic (C2-C20)hydrocarbon, and a branched (C2-C20)hydrocarbon.

11. The process of claim 10, wherein the one or more aliphatic organic compounds are branched and have the formula ##STR00007## wherein R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of a substituted (C1-C8)alkyl, a cyclic (C1-C8)alkyl, and a branched (C1-C8)alkyl.

12. The process of claim 10, wherein the one or more aliphatic organic compounds are unsubstituted hydrocarbons.

13. The process of claim 1, wherein the one or more alkylating agents comprise at least one compound selected from the group consisting of an olefin, an alcohol, an aldehyde, and an alkyl halide.

14. The process of claim 1, wherein a molar ratio of the one or more aliphatic organic compounds to the one or more alkylating agents ranges from 10 to 250.

15. The process of claim 1, wherein the process is conducted in a batch or in a continuous mode.

Description

DESCRIPTION OF THE FIGURES

[0176] FIG. 1 schematically displays the reaction of isobutane with linear butenes and their direct reaction products.

[0177] FIG. 2 shows the X-ray diffraction (XRD) pattern (measured using Cu K alpha-1 radiation) of the zeolitic material obtained from organotemplate-free synthesis according to Reference Example 2. In the figure, the diffraction angle 2 theta in is shown along the abscissa and the intensities are plotted along the ordinate. FIG. 2 further includes the respective line patterns of zeolite beta obtained from template mediated synthesis and of mordenite for comparison.

[0178] FIG. 3 shows the nitrogen adsorption isotherm of the zeolitic material obtained according to Reference Example 2. In the figure, the relative pressure p/p is plotted along the abscissa and the pore volume in cm.sup.3/g STP (standard pressure and temperature), determined according to DIN 66134 at 77 K, is plotted along the ordinate. The values for the adsorption are indicated by the symbols (.diamond-solid.) and the values for the desorption are indicated by the symbols (.box-tangle-solidup.).

[0179] FIG. 4 shows the results from experimental testing of the catalyst samples from Reference Examples 2, 4, 5, 7, and 9 in the alkylation of isobutane with but-1-ene as obtained according to Example 1. In the figure, the Si:Al molar ratio of the respective sample is plotted along the abscissa and the yield in alkylation product in mg relative to the amount of catalyst in g (mg.sub.product/g.sub.cat), is plotted along the ordinate. The values obtained for Reference Examples 2, 4, and 5 are indicated by the symbols (.diamond-solid.), those obtained for the dealuminated samples of Reference Examples 7 and 9 are indicated by the symbols (.circle-solid.), and those obtained for the commercial zeolite beta samples are indicated by the symbols (.box-tangle-solidup.).

[0180] FIG. 5 shows the results from experimental testing of the catalyst samples from Reference Examples 2, 4, 5, 7, and 9 in the alkylation of isobutane with but-1-ene as obtained according to Example 1. In the figure, the Si:Al molar ratio of the respective sample is plotted along the abscissa and the selectivity of the respective catalyst samples towards the C.sub.8-alkylation products expressed in % relative to 100% of the alkylation product is plotted along the ordinate. The values obtained for Reference Examples 2, 4, and 5 are indicated by the symbols (.diamond-solid.), those obtained for the dealuminated samples of Reference Examples 7 and 9 are indicated by the symbols (.circle-solid.), and those obtained for the commercial zeolite beta samples are indicated by the symbols (.box-tangle-solidup.).

[0181] FIG. 6 shows the X-ray diffraction (XRD) pattern (measured using Cu K alpha-1 radiation) of the zeolitic material obtained according to Reference Example 10. In the figure, the diffraction angle 2 theta in is shown along the abscissa and the intensities are plotted along the ordinate. FIG. 6 further includes the respective line patterns of zeolite beta and chabazite.

EXAMPLES

Reference Example 1: Preparation of Zeolite Beta from Organotemplate-Free Synthesis

[0182] 23.95 g of NaAlO.sub.2 were dissolved in 812.35 g of H.sub.2O, followed by addition of 9.01 g of Al-beta zeolite seed crystals (CP814C zeolite beta from Zeolyst International; calcined 5 h at 500 C. for obtaining H-form prior to use). 1154.69 g of sodium-water glass solution (26 wt.-% SiO.sub.2 and 8 wt.-% Na.sub.2O from Fa. Woellner) were then slowly added to the mixture while stirring, wherein a gel is first produced which is then dissolved after further addition of the solution.

[0183] The mixture was then transferred into a 2.5 L autoclave and heated without stirring to 120 C. over a period of 3 h and then crystallized at that temperature for 117 h. After having let the reaction mixture cool to room temperature, it was filtered and the solid residue repeatedly washed with distilled water to neutralization, after which it was dried at 120 C. for 16 h thus affording 85 g of a white crystalline product. The product displayed a crystallinity grade of 90% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0184] In FIG. 2, the XRD of the crystalline product is displayed. In particular, the XRD pattern is typical for a BEA framework structure as obtained from organotemplate-free synthesis in view of the 2 characteristic reflections observed in the 25 to 26 2 theta range.

[0185] Elemental analysis of the crystalline product afforded an Si:Al molar ratio of 4.8:1. Energy dispersive X-Ray (EDX) composition analysis of the sample afforded an Si:Al molar ratio of 4.9:1.

[0186] 1 g of the crystalline product was then subject to two subsequent ion exchange steps using a 10 wt. % aqueous ammonium nitrate solution at 80 C., wherein the ion-exchanged material was the calcined at 350 C. for 5 h.

[0187] In FIG. 3, the nitrogen isotherm obtained using the ion-exchanged product is shown. In particular, the step-like curve of a type I adsorption isotherm typical of microporous solids is evident (cf. DIN 66135), indicating that the as-synthesized zeolitic material has open micropores. The evaluation of the data gave an equivalent surface of 681 m.sup.2/g according to the Langmuir method, and a BET surface area of 521 m.sup.2/g.

Reference Example 2: Preparation of the H-Form of Zeolite Beta from the Product of Reference Example 1

[0188] The non-ion exchanged crystalline product of Reference Example 1 was subject to three subsequent ion exchange steps with a 0.5 M ammonium nitrate solution, respectively, after which is was calcined for 6 h at 450 C.

Reference Example 3: Preparation of Zeolite Beta from Organotemplate-Free Synthesis

[0189] 332.1 g of NaAlO.sub.2 were dissolved in 7578.8 g of H.sub.2O, followed by addition of 62.8 g of Al-beta zeolite seed crystals (CP814C zeolite beta from Zeolyst International; H-form), after which 363.6 g of fumed silica (Aerosil 200 from Degussa) were slowly added while stirring at 200 rpm. The mixture was then transferred into a 20 L autoclave and 8062.6 g of sodium-water glass solution (26 wt.-% SiO.sub.2 and 8 wt.-% Na.sub.2O from Fa. Woellner) were then slowly added to the mixture while stirring, wherein a gel is first produced which is then dissolved after further addition of the solution.

[0190] The mixture was then heated without stirring to 120 C. over a period of 3 h and then crystallized at that temperature for 117 h. After having let the reaction mixture cool to room temperature, it was filtered and the solid residue repeatedly washed with distilled water to neutralization, after which it was dried at 120 C. for 16 h thus affording 1330 g of a white crystalline product. The product displayed a crystallinity grade of 90% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0191] Elemental analysis of the crystalline product afforded an Si:Al molar ratio of 4.5:1.

[0192] As for Reference Example 1, the XRD of the crystalline product displayed an XRD pattern which is typical for a BEA framework structure as obtained from organotemplate-free synthesis in view of 2 characteristic reflections observed in the 25 to 26 2 theta range.

Reference Example 4: Preparation of the H-Form of Zeolite Beta from the Product of Reference Example 3

[0193] The crystalline product of Reference Example 3 was subject to three subsequent ion exchange steps with a 0.5 M ammonium nitrate solution, respectively, after which is was calcined for 6 h at 450 C.

Reference Example 5: Preparation of Zeolite Beta from Organotemplate-Free Synthesis

[0194] 18.28 kg of Al-beta zeolite seed crystals (CP814C zeolite beta from Zeolyst International; calcined prior to use for obtaining H from thereof) were suspended in 100 kg of distilled water, and the solution was then further stirred for 30 min at 100 rpm. In a separate vessel, 24.75 kg of NaAlO.sub.2 were dissolved in 399.6 kg of distilled water, and the solution was then further stirred for 30 min at 50 rpm. The aqueous suspension of the seed crystals was then added to the sodium aluminate solution under stirring, and the empty vessel then rinsed with 20 L distilled water, wherein the rinsing solution was then added to the mixture. 555.27 kg g of sodium-water glass solution (26 wt.-% SiO.sub.2 and 8 wt.-% Na.sub.2O from Fa. Woellner) were then continuously added over 1 h to the mixture under stirring at 25 rpm, and the empty vessel then rinsed with 10 L distilled water, wherein the rinsing solution was then added to the mixture. 96.21 kg of an aqueous solution of colloidal silica (40%; Ludox AS 40 from Grace) was then added to mixture under stirring, and the empty vessel then rinsed with 5 L distilled water, wherein the rinsing solution was then added to the mixture.

[0195] The mixture was then heated to 120 C. over a period of 3 h while stirring at 25 rpm and then crystallized at that temperature for 84 h. After having let the reaction mixture cool to room temperature, it was filtered and the solid residue repeatedly washed with distilled water to neutralization, after which it was dried at 120 C. thus affording 122.523 kg of a white crystalline product. The product displayed a crystallinity grade of 71% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0196] As for Reference Examples 1 and 3, the XRD of the crystalline product displayed an

[0197] XRD pattern which is typical for a BEA framework structure as obtained from organotemplate-free synthesis in view of 2 characteristic reflections observed in the 25 to 26 2 theta range.

[0198] Elemental analysis of the crystalline product afforded an Si:Al:Na molar ratio of 0.9:0.2:0.2. The Si:Al molar ratio of the product was thus 4.5:1.

[0199] The nitrogen isotherm in accordance with DIN 66135 was determined, wherein the evaluation of the data gave an equivalent surface of 643 m.sup.2/g according to the Langmuir method, and a BET surface area of 471 m.sup.2/g.

[0200] 100 g of the crystalline product was then added to 1 kg of a 10 wt. % aqueous ammonium nitrate solution in which it was stirred for 2 h at 80 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate. The ion exchange step was then repeated, after which the product was dried at 120 C. overnight, for affording 90 g of the ion-exchanged crystalline product.

[0201] Elemental analysis of the ion-exchanged product afforded an Si:Al:Na molar ratio of 1.17:0.22:0.002. The Si:Al molar ratio of the product was thus 5.3:1.

Reference Example 6: Preparation of Zeolite Beta from Organotemplate-Free Synthesis

[0202] 332.1 g of NaAlO.sub.2 were dissolved in 7578.8 g of H.sub.2O, followed by addition of 62.8 g of Al-beta zeolite seed crystals (CP814C zeolite beta from Zeolyst International; H-form), after which 363.6 g of fumed silica (Aerosil 200 from Degussa) were slowly added while stirring at 200 rpm. The mixture was then transferred into a 20 L autoclave and 8062.6 g of sodium-water glass solution (26 wt.-% SiO.sub.2 and 8 wt.-% Na.sub.2O from Fa. Woellner) were then slowly added to the mixture while stirring at 200 rpm, wherein a gel is first produced which is then dissolved after further addition of the solution.

[0203] The mixture was then heated without stirring to 120 C. over a period of 3 h and then crystallized at that temperature for 117 h. After having let the reaction mixture cool to room temperature, it was filtered and the solid residue repeatedly washed with distilled water to neutralization, after which it was dried at 120 C. for 16 h thus affording 1370 g of a white crystalline product. The product displayed a crystallinity grade of 82% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0204] Elemental analysis of the ion-exchanged product afforded an Si:Al:Na molar ratio of 1.07:0.24:0.23. The Si:Al molar ratio of the product was thus 4.5:1.

[0205] As for Reference Examples 1, 3, and 5, the XRD of the crystalline product displayed an XRD pattern which is typical for a BEA framework structure as obtained from organotemplate-free synthesis in view of 2 characteristic reflections observed in the 25 to 26 2 theta range.

[0206] 650 g of the crystalline product was then added to 6.5 kg of a 10 wt. % aqueous ammonium nitrate solution in which it was stirred for 2 h at 80 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate. The ion exchange step was then repeated, after which the product was dried at 120 C. for 16 h. The product was then heated to 450 C. using a ramp of 1 C./min and then calcined at that temperature for 5 h, thus affording 575 g of the calcined ion-exchanged crystalline product.

[0207] Elemental analysis of the calcined ion-exchanged product afforded an Si:Al:Na molar ratio of 1.1:0.25:0.004. The Si:Al molar ratio of the product was thus 4.4:1.

[0208] The calcined ion-exchanged product displayed a crystallinity grade of 86% compared to the crystallinity of the seed crystals employed in the initial synthesis in the 2 theta rage of 18 to 25.

[0209] 60 g of the calcined ion-exchanged crystalline product was then added to 300 g of a 2% HNO.sub.3 solution in which it was stirred for 2 h at 60 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate. The product was then dried at 120 C. for 16 h, and then heated to 450 C. using a ramp of 1 C./min and calcined at that temperature for 5 h, thus affording a white crystalline product.

[0210] Elemental analysis of the final product afforded an Si:Al:Na molar ratio of 1.25:0.19:0.01. The Si:Al molar ratio of the product was thus 6.6:1.

[0211] The calcined ion-exchanged product displayed a crystallinity grade of 52% compared to the crystallinity of the seed crystals employed in the initial synthesis in the 2 theta rage of 18 to 25.

Reference Example 7: Dealumination of Zeolite Beta from Reference Example 6 by Acid Treatment

[0212] 45 g of the zeolite beta obtained from Reference Example 6 was then added to 225 mL of a 2% HNO.sub.3 solution in which it was stirred for 2 h at 60 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate. The product was then dried at 120 C. for 16 h, and then heated to 450 C. using a ramp of 1 C./min and calcined at that temperature for 5 h, thus affording 44 g of a white crystalline product.

[0213] Elemental analysis of the final product afforded an Si:Al:Na molar ratio of 1.35:0.16:0.001. The Si:Al molar ratio of the product was thus 8.4:1.

[0214] The calcined ion-exchanged product displayed a crystallinity grade of 52% compared to the crystallinity of the seed crystals employed in the initial synthesis in the 2 theta rage of 18 to 25.

Reference Example 8: Preparation of Zeolite Beta from Organotemplate-Free Synthesis

[0215] 19.91 kg of Al-beta zeolite seed crystals (CP814C zeolite beta from Zeolyst International; calcined) were suspended in 100 kg of distilled water, and the solution was then further stirred for 30 min at 100 rpm. In a separate vessel, 26.96 kg of NaAlO.sub.2 were dissolved in 443.15 kg of distilled water, and the solution was then further stirred for 30 min at 50 rpm. The aqueous suspension of the seed crystals was then added to the sodium aluminate solution under stirring, and the empty vessel then rinsed with 20 L distilled water, wherein the rinsing solution was then added to the mixture. 620.15 kg g of sodium-water glass solution (26 wt.-% SiO.sub.2 and 8 wt.-% Na.sub.2O from Fa. Woellner) were then continuously added over 1 h to the mixture under stirring at 25 rpm, and the empty vessel then rinsed with 10 L distilled water, wherein the rinsing solution was then added to the mixture. 94.78 kg of an aqueous solution of colloidal silica (40%; Ludox AS 40 from Grace) was then added to mixture under stirring, and the empty vessel then rinsed with 5 L distilled water, wherein the rinsing solution was then added to the mixture.

[0216] The mixture was then heated to 120 C. over a period of 3 h while stirring at 25 rpm and then crystallized at that temperature for 79 h. After having let the reaction mixture cool to room temperature, it was filtered and the solid residue repeatedly washed with distilled water to neutralization, after which it was dried at 120 C. thus affording 117 kg of a white crystalline product. The product displayed a crystallinity grade of 72% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0217] As for Reference Examples 1, 3, 5, and 6, the XRD of the crystalline product displayed an XRD pattern which is typical for a BEA framework structure as obtained from organotemplate-free synthesis in view of 2 characteristic reflections observed in the 25 to 26 2 theta range.

[0218] Elemental analysis of the product afforded an Si:Al:Na molar ratio of 1.07:0.23:0.22. The Si:Al molar ratio of the product was thus 4.7:1.

[0219] The nitrogen isotherm in accordance with DIN 66135 was determined, wherein the evaluation of the data gave an equivalent surface of 611 m.sup.2/g according to the Langmuir method.

[0220] 25 kg of the crystalline product was then added to 250 kg of a 10 wt. % aqueous ammonium nitrate solution in which it was stirred for 2 h at 80 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate. The ion exchange step was then repeated, after which the product was dried at 120 C. for 16 h. The dried product was then heated to 500 C. using a ramp of 1 C./min and calcined at that temperature for 5 h. The product displayed a crystallinity grade of 74% compared to the crystallinity of the seed crystals employed in the synthesis in the 2 theta rage of 18 to 25.

[0221] Elemental analysis of the ion-exchanged product afforded an Si:Al:Na molar ratio of 1.28:0.22:0.001. The Si:Al molar ratio of the product was thus 5.8:1.

[0222] The nitrogen isotherm of the ion-exchanged product was determined in accordance with DIN 66135, wherein the evaluation of the data gave an equivalent surface of 636 m.sup.2/g according to the Langmuir method.

Reference Example 9: Dealumination of Zeolite Beta from Reference Example 8 by Steam and Acid Treatment

[0223] The product of Reference Example 8 was subject to a steam treatment for 1 h at 700 C. in a nitrogen atmosphere containing 10% H.sub.2O. The steam treated material was then subject to three subsequent acid treatment steps with a 2% HNO.sub.3 solution in which it was stirred for 2 h at 60 C., the solid then filtered off and washed with distilled water until the filtrate was free of nitrate, respectively. The product was then dried at 120 C. for 16 h, and then heated to 450 C. using a ramp of 1 C./min and calcined at that temperature for 5 h, thus affording a white crystalline product displaying an Si:Al molar ratio of 17.9:1.

Reference Example 10: Synthesis of Zeolite Beta According to U.S. Pat. No. 5,824,835 A

[0224] 513.23 grams of colloidal silica (30 wt.-%, Ludox SM-30), 574.77 grams of tetraethylammonium hydroxide (35 wt.-%), 24.61 grams of aluminum hydroxide and 0.68 grams of water were added to a vessel and stirred at 700 rpm for 1 hour. The resulting mixture was transferred to an autoclave and heated at a rate of 2 C./minute to 100 C. The mixture was stirred at 100 C. and 60 rpm for 48 hours. The autoclave was allowed to cool to room temperature, opened and 538.9 grams of aqueous barium hydroxide (5 wt.-%) was added followed by addition of 47.94 grams of aqueous potassium hydroxide (10 wt.-%). The autoclave was then sealed and the resulting mixture was heated at a rate of 2 C./minute to 150 C. The mixture was stirred at 150 C. and 60 rpm for 168 hours. The product was then filtered and dried at 110 C. overnight.

[0225] The dried zeolitic material was treated with 1M ammonium chloride whose pH was adjusted to 8 over 1 hour at 60 C. The ion exchange was repeated twice. The product was then collected by centrifugation, washed with water and collected again by centrifugation. The washing/centrifugation were repeated once. The resulting zeolitic material was dried for 16 hours at 110 C. The dry exchanged product was heated up to 538 C. in a stream of dry nitrogen at 2 C. per minute and held for 3 hours. The temperature was lowered to 250 C. and the atmosphere was switched to air after which the temperature was raised again to 538 C. at 2 C. per minute and held for three hours. The crystallinity of the obtained calcined material was found to be 76% and the product contained minor amounts of CHA zeolitic material as evidenced in the XRD (see FIG. 6 for the XRD of Reference Example 10).

[0226] Elemental analysis of the ion-exchanged product afforded an Si:Al:K:Ba:C molar ratio of 1:0.123:0.00378:0.0014:0.006. The Si:Al molar ratio of the product was thus 8.1:1.

Example 1: Alkylation of Isobutane with but-1-Ene

[0227] The catalysts (500 mg) from Reference Examples 2, 4, 5, 7, and 9 were respectively activated at 250 C. and subsequently placed in a 100 mL Parr reactor that was closed immediately and purged with nitrogen. As comparative examples, two commercial zeolite beta samples were employed, both obtained from a synthesis methodology employing an organotemplate, wherein the first displayed an Si:Al molar ratio of 12.5 (CP811 from PQ Corporation), and the second an Si:Al molar ratio of 30 (H-beta from Sdchemie). The reactor was cooled on ice and liquid isobutane was added via a 31.4 mL compressed air driven plunger that was cooled at 15 C. to ensure that isobutane is in its liquid state. Subsequently gaseous 1-butene was added using a 49.1 mL plunger that was not cooled. The lines were subsequently purged with nitrogen to ensure that the entire olefin was transferred to the reactor. Reactions were carried out at 70 C. to 100 C. while stirring the slurry. After completion of the reaction, the reactor was cooled on ice and the gases were released. Subsequently n-decane was added to the reactor to dilute the reaction products. Reactions were analyzed using a GC-FID instrument with tetradecane as standard.

[0228] The alkylation of isobutane with 1-butene was tested with an olefin/paraffin ratio of 1/50. Initially, the commercial zeolite beta samples were tested, where the best catalyst provided 149 mg.sub.product/g.sub.cat at 42% C.sub.8 selectivity. As may be taken from FIG. 4, zeolite beta from organotemplate-free synthesis as obtained from Reference Examples 2, 4, and 5 displaying Si/AI ratios ranging from 4.5 to 5.3 provided significantly higher activity with up to 407 mg.sub.product/g.sub.cat compared to the commercial samples from templated synthesis. Furthermore, as may be taken from FIG. 5, zeolite beta from organotemplate-free synthesis as obtained from Reference Examples 2, 4, and 5 further provided the highest C.sub.8 selectivites. Dealumination of zeolites from organotemplate-free synthesis as achieved in Reference Example 7 and 9 resulted in both lower activity and lower C.sub.8 selectivity than for the untreated zeolites from Reference Examples 2, 4, and 5.

[0229] As may be further taken from the results in FIG. 4, a clear relationship between the Si:Al ratio and the activity of the zeolite beta catalyst may be observed, wherein the activity decreases with decreasing Si:Al ratio, independently as to whether the zeolite was obtained from templated or from organotemplate-free synthesis, or whether the Si:Al ratio was achieved by subsequent dealumination of the zeolite beta after synthesis thereof. However, it has quite surprisingly been found that although a similar relationship is observed in the results in FIG. 5 for the C.sub.8-selectivity of the respective catalysts, zeolite beta as obtained from organotemplate-free synthesis displays a substantially higher selectivity than the catalysts obtained from templated synthesis at comparable Si:Al ratios, in particular for those samples displaying low Si:Al molar ratios. In particular, it has quite unexpectedly been found that compared to the commercial zeolite beta samples obtained from templated synthesis, which are practically insensitive to variations in the C.sub.8-selectivity, the catalyst samples obtained from organotemplate-free synthesis do not only display a substantially higher selectivity, but also show a strong relationship between the Si:Al molar ratio and the C.sub.5-selectivity of the samples. In particular, the samples from Reference Examples 2 and 4 with Si:Al molar ratios in the range of 4 to 5 afford C.sub.8-selectivities which are almost twice as high as observed for commercial zeolite beta which is obtained from templated synthesis.

[0230] Furthermore, Reference Example 10, which represents the teaching of prior art document U.S. Pat. No. 5,824,835 A, was also evaluated in the alkylation of isobutane with but-1-ene according to Example 1, the results of which are given in Table 1 below, together with the results obtained using the zeolite from organotemplate-free synthesis according Reference Example 2.

TABLE-US-00009 TABLE 1 Comparison of alkylation of isobutane with but-1-ene with zeolites from Reference Examples 10 and 2. selectivity [%] yield [mg/g catalyst] C.sub.7 C.sub.8 C.sub.9 Reference Ex. 10 154 7.9 52 40.1 Reference Ex. 2 407 10 69.4 20.6

[0231] Thus, as may be taken from the results in Table 1 the results of the present invention are also confirmed in view of prior art document U.S. Pat. No. 5,824,835 A, which specifically teaches the use of zeolite beta from conventional (templated) synthesis in the alkylation of isobutane with butene-2. In particular, as may be taken from the results with regard to the C.sub.8-selectivity, the inventive process using Reference Example 2 which is a zeolite beta obtained from organotemplate-free synthesis achieves a considerably higher selectivity compared to the C.sub.8 selectivity achieved with Reference Example 10, which confirms the results and general tendencies displayed in FIG. 5.

[0232] Accordingly, it has surprisingly been found that the use of zeolite beta from organotemplate-free synthesis in a process for the alkylation of isobutane with 1-butene affords considerably better results than with commercial zeolite beta with regard to both activity and selectivity, in particular towards C.sub.8-alkane products. Furthermore, it has quite unexpectedly been found that this is not only dependent on the lower Si:Al molar ratios which may be afforded using the organotemplate-free synthetic methodology, but is further due to the unique structure of the zeolite beta materials obtained from said method, in particular in view of the outstanding and completely unexpected selectivities which may be achieved with regard to the desired C.sub.8-alkane products.

CITED PRIOR ART DOCUMENTS

[0233] Feller, A. et al. in Journal of Catalysis, 2004, Vol. 224, pp. 80-93 [0234] Dalla Costa, B. O. et al. in Applied Catalysis A 2010, Vol. 385, pp. 144-152 [0235] Corma, A. et al. in Applied Catalysis A 1994, Vol. 119, pp. 83-96 [0236] WO 2012/137133 A [0237] Xiao et al., Chem. Mater. 2008, 20, pp. 4533-4535 [0238] WO 2010/146156 A [0239] Majano et al., Chem. Mater. 2009, 21, pp. 4184-4191 [0240] U.S. Pat. No. 4,992,616 A [0241] U.S. Pat. No. 5,824,835 A [0242] Nivarthy, G. S. et al. in Microporous and Mesoporous Materials 2000, vol. 35-36, pages 75-87 [0243] Nivarthy, G. S. et al. in Microporous and Mesoporous Materials 1998. vol. 22, no. 1-3, pages 379-388 [0244] Yuki Kato et al. in Journal of the Japan Petroleum Institute 2013, vol. 56, no. 5, pages 349-355