Method for oligomerising alkenes using the ITQ-39 zeolite

Abstract

The invention relates to a heterogeneous method for oligomerising alkenes in order to produce hydricarbons within a diesel fraction in the present of a catalyst based on the ITQ-39 zeolite. The oligomerisation method described in the present invention includes at least: a. feeding a catalyst containing at least the ITQ-39 zeolitic material into the reactor; b. supplying the reactor with a stream that includes at least one olefinic compound; and c. enabling the catalyst containing at least the ITQ-39 material and the organic compound to remain in contact during the time required for the reaction to take place.

Claims

1. A process of oligomerization of olefinic compound for producing hydrocarbons, comprising at least: a. introducing a catalyst containing at least a zeolitic material ITQ-39 in a reactor; b. feeding the reactor with a stream comprising at least one olefinic compound; c. allowing the catalyst containing at least the zeolitic material ITQ-39 and the at least one olefinic compound to remain in contact the time necessary for the oligomerization to take place.

2. The process according to claim 1, wherein the olefinic compound is selected from the group consisting of ethylene, propene, butenes, pentenes, hexenes or mixtures of same.

3. The process according to claim 1, wherein the olefinic compound is present in the stream at a concentration between 10 and 100% by weight.

4. The process according to claim 1, wherein the zeolitic material ITQ-39 is in its acid form.

5. The process according to claim 1, wherein the zeolitic material ITQ-39 has been modified to generate additional mesoporosity.

6. The process according to claim 1, wherein the zeolitic material ITQ-39 has a external surface that has been deactivated through selectivation processes.

7. The process according to claim 1, wherein the zeolitic material ITQ-39 has been selectivated through treatments with oxalic acid.

8. The process according to claim 1, wherein the zeolitic material ITQ-39 has been selectivated through treatments with ethylenediaminetetraacetic acid (EDTA).

9. The process according to claim 1, wherein the catalyst comprises a matrix formed by, at least, one oxide selected from the group consisting of amorphous oxide, low crystallinity oxide and combinations thereof.

10. The process according to claim 1, wherein the catalyst comprises a matrix formed by, at least, one oxide selected from the group consisting of alumina, silica-alumina, silica, clays, magnesium oxide, titanium oxide, boron oxide, zirconium oxide, and combinations thereof.

11. The process according to claim 1, wherein the catalyst comprises a matrix formed by gamma-alumina.

12. The process according to claim 1, wherein the catalyst comprises a matrix that comprises at least aluminum phosphates, zirconium phosphates, coal, aluminates and combinations thereof.

13. The process according to claim 1 wherein the catalyst comprises at least one hydrogenating Group VIII metal and combinations thereof.

14. The process according to claim 1, wherein the catalyst comprises at least one metal selected from the group consisting of iridium, ruthenium, rhodium, rhenium, palladium, platinum, iron, cobalt, nickel and combinations thereof.

15. The process according to claim 1 wherein the catalyst comprises at least, a promoter agent selected from phosphorus, boron and combinations thereof.

16. The process according to claim 1 wherein the catalyst comprises at least, a promoter that is phophorus.

17. The process according to claim 1, wherein the catalyst comprises at least, an element of Group VIIB.

18. The process according to claim 1 that it is carried out at a temperature between 100 and 500 C., at a pressure between 0, 1 and 200 bar and at a spatial rate (WHSV) between 0.1-100 h.sup.1.

19. The process according to claim 1, that it is carried out in the presence of hydrogen.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1: Conversion of olefin in function of reaction time (Time on Stream, TOS) obtained with zeolite ITQ-39 and ZSM-5 with a commercial origin, in the oligomerization of propylene present in a mixture propylene:propane of 60:40 (molar ratio), at 200 C., 40 bar and a contact time, , of 0.08 h.

(2) FIG. 2: Selectivity in the C5+ liquid fraction accumulated (TOS=0-3 h and TOS=3-6 h) obtained with the ITQ-39 zeolite and with a ZSM-5 zeolite from commercial sources, in the oligomerization of propylene present in a mixture propylene:propane of 60:40 (molar ratio), at 200 C., 40 bar and at a contact time, , of 0.08 h.

EXAMPLES

Example 1

Preparation of a Dication in a Dihydroxide Form

(3) The organic dication SDA is synthesized following the general process depicted in the following scheme:

(4) ##STR00002##

(5) In a general process a reaction of reductive amination of 1-propyl-4-piperidone (compound A) with pyrrolidine (compound B) is performed, leading to the corresponding diamine (compound C). The diamine is quaternized through an ethyl halide being converted into the SDA dication (compound D).

(6) More specifically, the organic dication is prepared as follows:

(7) 21.600 g of pyrrolidine are dissolved in 250 ml of methanol and this solution is acidified with HCl (5 M in methanol) to a pH=7.2, cooling the mixture continuously in an external bath at 0 C. Then, 14.30 g of 1-propyl-piperidone, followed by 5.14 g of NaBH.sub.3CN are added. The resulting mixture is kept under stirring at room temperature for 72 hours.

(8) HCl (5 M in methane) is slowly added to this mixture, until a pH lower than 2 is achieved by moving the HCN by means of a continuous stream of nitrogen. The resulting solution is concentrated by rotatory evaporation and a solution of KOH (25 wt %) is added until a pH greater than 12 is achieved. At this stage, a white precipitate appears. The resulting mixture was saturated with NaCl and added to water. Finally, the diamine, 1-propyl-4-pyrroline-1-yl-piperidine, is extracted with diethyl ether and dried over anhydrous MgSO.sub.4 while stirring.

(9) Quaternization of the diamine is carried out as follows: 65.68 g of ethyl iodide are added to a solution of 19.11 g of diamine in 150 ml of ethanol. 48 hours later, additional 30.80 g of ethyl iodide are added. The mixture is kept stirred at reflux and heated to 85 C. by an external bath. The solution is concentrated by rotatory evaporator.

(10) Several hours later a semi-solid phase is formed. 20 ml of methanol are added to dissolve it and diethyl ether is used for the precipitation of the solid, which is filtered under vacuum.

(11) The iodide of the cation is exchanged with a hydroxide using an ion exchange resin according to the following process: 61.13 mmol of the cationic iodide are dissolved in water. 165 g of Amberlite IRN-78 resin are added to the obtained solution and the mixture is kept under stirring until the next day. The sample is then filtered, washed with ultrapure water and the dihydroxide solution is obtained. The dihydroxide is titrated with aqueous HCl using phenolphthalein as indicator, obtaining an exchange efficiency greater than 60%. The final solution contains 0.47 equivalents of hydroxide per 1000 g of solution.

Example 2

Synthesis of Zeolitic Material ITQ-39

(12) 1883 g of aluminum isopropoxide are added to 28,753 g of tetraethyl orthosilicate (TEOS). Then 146.910 g of the solution obtained in the previous example are added. The mixture is left to evaporate with stirring until complete elimination of the ethanol formed from the hydrolysis of TEOS. At this point 2.92 g of HF (48 wt %) are added. The water is removed by stirring and heating in an external bath to obtain the final composition of the gel, which is: SiO.sub.2:0.033Al.sub.2O.sub.3:0.25[SDA](OH).sub.2:0.5HF:2H.sub.2O

(13) wherein the SDA is the dication described in Example 1.

(14) The gel is introduced into a stainless steel autoclave with an internal teflon jacket and heated statically for 35 days at 135 C. The solid obtained after separation by filtration, is washed with distilled water and acetone.

(15) The XRD pattern of the synthesized material is shown in Table III

(16) TABLE-US-00003 TABLE III 2 (degrees) 0.5 Intensity (I/I.sub.0) 7.8198 49.56 8.6885 13.82 15.7045 4.51 19.2097 7.54 21.3591 32.59 22.0000 45.40 22.7964 100.00 25.0561 9.92 26.2576 13.17 27.4230 7.01 28.7596 6.87 29.4369 5.87 31.9616 5.07 34.1133 1.72 36.1252 1.17 36.7736 2.03 42.6035 1.28 43.4655 5.76

Example 3

Activation by Calcination of the Zeolitic Material ITQ-39

(17) The zeolitic material ITQ-39 obtained as described in example 2 is calcined in an air flow at 580 C. for 3 hours. The DRX pattern of the calcined material is shown in table IV.

(18) TABLE-US-00004 TABLE IV 2 (degrees) 0.5 Intensity (I/I.sub.0) 7.8461 100.00 8.7039 37.71 11.0092 1.47 13.6688 2.40 14.7903 5.20 15.7731 5.95 19.2573 5.47 21.4378 28.77 22.1339 44.61 22.973.9 95.99 25.1759 15.59 26.3257 20.77 27.6284 12.92 29.1717 12.52 32.1493 7.69 34.3923 2.64 36.4259 1.95 43.9105 4.31

Example 4

Use of Zeolite ITQ-39 as Catalyst for the Oligomerization of Propylene

(19) A zeolitic material ITQ-39 calcined as described in Example 3 is converted into pills, milled and sieved to a particle size of 0.2-0.4 mm. 0.5 g of this sample in the form of pills, are diluted with SiC (0.4-0.6 mm) to obtain a bed volume of 4.0 cm.sup.3. The mixture is loaded into a fixed bed reactor of stainless steel, a stream of feed C3=:C3 (60:40 molar ratio) is fed to the reactor in liquid phase through a Gilson piston pump. During the reaction the pressure is controlled by a pneumatic valve electronic Badger. The temperature in the catalytic bed is controlled by two independent heating zones with their corresponding thermocouples placed inside the catalytic bed.

(20) Before starting the oligomerization experiment, the catalyst is activated in situ by calcination by increasing the temperature to 520 C. in a flow of 20 ml/min of N.sub.2, and calcination for 5 hours at 520 C. in an air flow of 200 ml/min.

(21) Oligomerization experiments are conducted at T=473 K, P=40 bar and a contact time, , of 0.08 h, referred to the olefin.

(22) Variation of propylene conversion with reaction time (TOS) obtained with the ITQ-39 zeolitic material, described in this patent is compared in FIG. 1 with the one of a commercial ZSM-5 (Si/Al=11, supplied as ammonium form by TRICAT) tested in the same conditions as the ITQ-39. It can clearly be seen how ITQ-39 is initially more active, and deactivates at lower deactivation speed with TOS than commercial ZSM-5.

(23) The selectivity to the different fractions in the liquid product, collected at the outlet of the reactor, accumulated at reaction times between 0 and 3 hours and between 3 and 6 hours TOS, is shown in FIG. 2. The results show that the catalyst based on zeolite ITQ-39 is more selective to the desired diesel fraction than the commercial ZSM-5.