Preparation of a catalyst for normal paraffin isomerization.

<⁵⁴) Process for obtaining a catalyst used for normal paraffin isomerization

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The present invention relates to a process for obtaining a catalyst used for normal paraffin isomerization.

It is known that, prepared by depositing one or more noble metals of group VIII on mordenite, the catalysts have high selectivity and activity for the normal isomerization of paraffins.

For the preparation of catalysts suitable for this purpose, the metal exchange cations, initially present in mordenite, are almost completely replaced by hydrogen ions. This substitution can be effected by treating the mordenite with an aqueous solution of an acid or by treating the mordenite with an aqueous solution of an ammonium compound, followed by calcination. Catalysts prepared in this way do not have a proper activity in the processes of isomerization of normal paraffins.

The catalyst according to the invention eliminates these disadvantages by executing the treatment of mordenite with a saturated solution of sodium chloride in hydrochloric acid with a normality of between 0.5 ... 3.0, preferably 1.0 ... 2, 0, in an amount which, expressed in g / 1, is at least ten times higher than the norm.83320 lity of the aqueous acid solution, mordenite being subsequently treated with an aqueous solution of ammonium nitrate having a molarity of 0.1 ... 10 and then mixed with 5 ...

50% of an amorphous alumina based material on which platinum was previously deposited, in such proportions that in the finished catalyst there is 0.1 ... 1.5% by weight platinum, the material obtained being subjected to final formation at high pressure /

Following are examples of embodiments of the invention.

Example 1. Boil at reflux for one hour a mixture of 20 g of sodium mordenite and 200 ml of 1.5 N HCl. The solid material is filtered and washed with water. Thereafter, the solid material was boiled at reflux for one hour with 200 ml of 1 M ammonium nitrate solution. This treatment with ammonium nitrate is repeated twice, each time with a fresh solution of ammonium nitrate. After each treatment, the solid material is filtered and washed with water. Platinum is eventually deposited on the ammonium mordenite thus obtained, by treating it with an aqueous solution of a platinum compound. The solid material is filtered and dried at 120 ° C. Platinum / ammonium mordenitis

THE PRICE OF LEI 11,51 thus obtained is tabled and plucked, pi »,« tatiji ^ lul, .iflapiqșt, hare.

pìțl .'eeriȚgfe p jțrpgțiuițe ςμ diaipetrpj? particles between 0.2 and 0.6 mm. This fraction is converted to a catalyst rated by 1 by calcination at 500 ° C.

Example 2. The catalyst is prepared in the same manner as the catalyst in Example 1, except that in this case the platinum / ammonium mordenite is intensely mixed with alumina sprayed in a 4: 1 weight ratio, before being pelleted. .

Example 3. This catalyst is prepared in the same way as the catalyst in Example 1, except that in this case 1.5 N HCl is used to which 400 g / sodium chloride was added.

Example 4. This catalyst is prepared in the same manner as the catalyst in Example 3, with the exception that in this case the muffin gives platinum / ammonium mixed intensely in a 4: 1 weight ratio with the same alumina powder as in the case of the catalyst. of Example 2, before being tableted.

Example 5. Is a platinum / alumina composition containing 1.2 parts by weight platinum to 100 parts by weight alumina prepared by treating the garlic powder? mine used in the preparation of the catalysts of Examples 2 and 4 with an aqueous solution g cppipps ge platinum, followed gp i! Ș6 «fe and cplciiifirQ at 50P''C. I am dying? deuitft dp amgpiu held as a hypothermic pad for the preparation of the catalysts dip examples 3 and 4, dry} g and scepăptă ippepște iptr in relation to grpptte dP 4: you can apply the platinum / glue and the cap. pip the xnea material? the eipat is plated through Q by the small fraction of the puprips, about 0.2 and -0.6 mm. This fraction is FFPPfonjiă in cationglizophores from Example 5 preheated calcination at 500 ° C.

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''^: WScent'ele'l 'in' isopentane weight in product are the averages realized between 10 and 05 hours (¹ k

<td>The experience</td><td>Catalyst no.</td><td>% by weight isopentane</td>

<td> 1</td><td> 1</td><td> 044</td>

<td> 2</td><td> 2</td><td> 61,0</td>

<td> 3,</td><td> 3</td><td> 07,3</td>

<td> 4</td><td> 4</td><td>f} 3.5</td>

<td> 5</td><td> 5</td><td> 66,9</td>

From experiences 1-5 only experience no. 5 is an isomerization experiment, according to the present invention. In this experience, a catalyst prepared according to the invention was used. The other experiences are outside the scope of the invention and are included in the patent application for comparison only.

Comparison of the results of experiences 1 and 2 shows that mixing platinum / hydrogen bond with A1 binder₂A₃ Prior to the formation of high pressure cube does not influence the behavior of ready-made catalyst particles.

The behavior of the results of experiments 3 and 4 shows that the improvement in the behavior of H-mordenite as a result of the incorporation of sodium ions into acid solution is completely lost when platinum / H-mordenite is mixed with the aluminum binder A1.₂A₃ Prior to the formation of high heels.

According to the present invention, in the preparation of the ge catalyst particles, according to the present invention, the enhancement of the H? Imprdenite pumps as a result of the incorporation of the gp §pgiu ion into its acid solution was found to be integral in the ge catalyst particles.

From the base material of the catalyst obtained in the manner described above, can the catalyst particles be prepared? rates through high pressure formation. To confer the catalyst particles? Sufficient crushing resistance for commercial evening use, in the current practice, is the base material of the catalyst evenly mixed with an amorphous bonding material that contains? it mainly consists of one or more oxides of the metals of groups II, III and IV, before being subjected to high pressure formation.

Is the catalytic activity for normal paraffin isomerization improving? is it by replacing cla treatment? sic in one phase of mordenite I two-phase treatment, using an aqueous acid solution in which alkali metal ions were incorporated. The particles like? talizator' can be prepared by depositing the noble metals of group VIII, not usually on the treated mordenite, but on the li5 the apiorf pointing, tp egcnenza, from ppul şş, p more oxides of mgtpfelpr t | ip group li, IU and IV . Welcome to the intense appearance of the pigvclenitis treated and the H4îlț asfprf mafmiplif, carp qqnțipe the middle you can) dtp group VIII and the granulation of the mixture thus obtained under high pressure, catalysts can be prepared that satisfy the two abovementioned requirements.

The process of preparing a catalyst suitable for the paraffin isomerization of paraffins according to the invention consists in the fact that the inheritance is treated with a solution prepared by the incorporation of ions. their potassium and / or sodium in an aqueous acidic solution with a normality of at least 0.5 cpl and 3.0 cgl more, in an amount which, expressed in g / 1, is at least ten. times greater than the normality of the aqueous acid solution. The mordenil is assigned and subsequently treated with an aqueous solution of a coipp, an ammonium gate, after which the mordenil thus treated is mixed with an amorphous material consisting essentially of one or more oxides of the metals of group I, III and IV. on which they have deposited the uu or more inub te pobile metals for the group VJli, qpieg-. the tee obtained as a foil for high pressure formation. As acids in the above-mentioned aqueous acid solution, according to the invention, both organic acids and inorganic acids can be used. Preferably, hydrochloric acid is used. The preferred normality of the acidic solution is between Ϊ, Q and 2.0. For the incorporation of. potassium and / or sodium in the aqueous acid solution both organic and inorganic salts can be used. - Satisfactory results can be obtained by performing the treatment with aqueous acid solutions in which potassium and / or sodium ions have been incorporated with an aqueous solution of one breast of several acids, saturated with one or more potassium salts and / or sodium. For acid treatment, preference is given to an aqueous acid solution containing sodium ions. It is also preferable to use potassium and / or sodium salts derived from the same acid used for acid treatment. The acid treatment is preferably carried out at high temperature, in particular, near the boiling point of the aqueous acid solution.

For the treatment of mordenitis with an aqueous solution of an ammonium compound, organic or inorganic compounds can be used. The term "ammonium compound" refers to any compound that can form ammonium ions. It is preferable to use simple, inorganic ammonium compounds, especially ammonium nitrate. The preferred molar concentration of the aqueous solution of the ammonium compound is QȚ-W &amp; TpâUmfep.lul cp. ρ solution, aqueous of the poinpps and citronium ions can be tealised at room temperature or at high temperature, .......

Time for each one, spherical treatment depends on concentration? temperature and the degree of contact, Usually, the gluing of the tripod lasts at least '30 mip, '4β preferably almost a pra. And it would be advantageous to repeat or continue the treatment of an aqueous solution of the ammonium compound until the mordgnite no longer yields alkaline metal in detectable quantities by analysis.

After treatment with an ammonium compound, mordenite is in the form of ammonium. By calcining the ammonium mordenite, the nitrogen atoms incorporated by the treatment are removed and the mordenite is obtained in the form of hydrogen. The conversion of ammonium mordenite into hydrogen may occur before or after mixing with the amorphous material containing noble VIII in group VIII.

When preparing the catalyst, according to the invention, the treated mordepitp is mixed with an amorphous material consisting, essentially, (I know more oxides of the elements of groups II, ITI and IV, where more noble metals have been deposited group VIII · Examples of oxides, developed as noble carriers of the VIIT group, are alumina, silica, magnesium oxide, zifconium oxide or rimri. Preferably, ρίμηπηρ is used, the noble petals dip group VIII which could be present on the oxides of the dip elements group II, III and IV scepter; platinum, palladium, pomegranates, ruthenium, iridium and osmi, of which the preferred metal is platinum. The catalyst may contain two or more noble metals in Group VIII. The amount of noble group VIII metal present in the prepared catalyst is preferably 0.01 ... 5% by weight and, in particular, 0.1 ... 1.5% by weight. The prepared catalyst preferably contains 5 ... 50% by weight of amorphous material, which contains a noble group VIII metal. The noble metal of group VIII is preferably deposited on oxides by impregnation. The formation of the high pressure catalyst can be accomplished, for example, by tablet or extrusion.

The catalysts according to the invention are suitable for the normal isomerization of paraffins in the presence of hydrogen. Normal paraffins which are subjected to isomerization treatment preferably contain 4-10, especially 4-7 carbon atoms in a molecule. The normal isomerization of paraffins with molecular structure mentioned in the presence of hydrogen is usually performed at a temperature of, Q ptsesfepg: dp,: 3-, 30.-, a,_KSpatial velocity P of H-mordenite 0.5 - 10 kg kg^_1h^_1 and a molar ratio of hydrogen to a charge of 0.5: 1–10: 1. Isomerization is preferably carried out under the following conditions: temperature of 230–280 ° C, pressure of 10–40 at and a spatial velocity of H-morderitis of 1.0-5.0 kg kg ~¹f^_1.

Compared to isoparaffins having the same number of carbon atoms, paraffins normally have a low octane number; their presence in light gasoline fractions is therefore undesirable. By the normal conversion of the paraffins present in the respective fractions into isoparaffins, the octane number is increased. Isoparaffins also present in fractions of gasoline can be eliminated before isomerization, for example by distillation or by molecular sieves. Because normal paraffin isomerization is a equilibrium reaction, the product leaving the isomerization reactor still contains an amount of unprocessed paraffin. These paraffins can be separated from the isomerization product, for example, by distillation or by means of molecular sieves and recycled in an isomerization process. It is also possible to add the isomerization product to the Original mixture of normal paraffins and isoparaffins to remove the isoparaffins from this mixture, for example by distillation, breast with molecular sieves and to isomerise the rest of the mixture of normal paraffin according to the invention.

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The process according to the invention has the advantage of obtaining in a simple way a catalyst for the normal isomerization of the paraffins with activity and mechanical resistance 5 higher than the known catalysts.