DD225671B1 - MANUFACTURE OF MECHANICAL SOLID HYDROSPECT CATALYSTS BASED ON ROENTGENAMORPHER ALUMOSILICATES - Google Patents

Description

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VEB Leuna-Werke Merseburg, May 10, 1984

"Walter Ulbricht"

LP 8435

Title of the invention

Production of mechanically strong hydrosoluble catalysts based on X-ray amorphous aluminosilicates

Field of application of the invention

The invention relates to a preparation process for a hydrosolating catalyst for heavy hydrocarbon fractions.

Characteristic of the known technical solutions

Hydrocolumn catalysts for the preferential recovery of middle distillates from, in particular, unrefined high boiling hydrocarbon fractions consisting of elements of the Periodic Table 6 and 8 * Feet Groups and an X-ray amorphous aluminosilicate are known per se. However, there are technical difficulties in making moldings of catalysts of the type described which are highly active and at the same time mechanically strong.

For this purpose, various production methods have been described, e.g. by applying the active components to the carrier from common solution (US Pat. No. 3,956,104) or by consecutive impregnation (DE-AS 1,152,213). In all cases, the manufacturing processes are characterized by annealing stages during catalyst production. These annealing stages in the production process not only represent a considerable expenditure of energy, but also require a considerable reduction in the production capacity or an increase in capital expenditure, since the technical annealing times including heating and cooling period between 4 and about 10 hours. In addition, they have an adverse effect on the catalytic behavior of the catalysts produced.

In DD-PS 157 159 a highly active hydrocracking catalyst is described in whose preparation no annealing stage is required. Such a catalyst is obtained by using all components in the form of their unannealed compounds. The disadvantage is that a catalyst produced in this way has no satisfactory mechanical strength.

Object of the invention

The aim of the invention is a process for the preparation of hydrocracking catalysts for heavy hydrocarbon fractions, which provides catalyst moldings which have a particularly good mechanical strength in addition to a high catalytic activity.

Explanation of the essence of the invention

The object is to develop a production process for mechanically strong hydrocracking catalysts based on X-ray amorphous aluminosilicates, which is technologically simple and energy-economical.

Fiese problem is solved by the present invention thermally pretreated the deformed catalysts at 333 to 373 K, then stored for 15 minutes to 3 hours in flowing air at 273 to 328 K and then post-treated at 453 to 553 K.

It is favorable when the catalysts are flowed through during the intermediate storage of ambient air at a flow rate of 1 to 3 v / vh.

Advantageously, the catalysts are stored for 15 minutes to 1 hour at 278 to 328 E.

It is important that before this interruption already at least 60 % of the total weight loss associated with the drying occurred, contrary to expectations it was found that such an intermediate treatment, the mechanical strength of the catalyst moldings is increased.

By the Yortrocknung a mass loss, which corresponds to 60 to 90 % of the total by the drying mass reduction corresponds to !fach the intermediate storage, the catalyst at 453 to 553 K nachzubehandeln to remove more water and decompose thermally unstable compounds, the solidification process progresses until the weight constancy is reached.

The catalyst prepared according to the invention is characterized by an up to 40 % higher mechanical strength than hydrosoluble catalysts of the type described produced by the customary processes and achieves the strength values achieved by the known annealing technologies. A further advantage of the production method according to the invention is thus that it can be carried out in an energy-saving manner.

Exemplary embodiments Example 1

5.3 kg of an X-ray amorphous aluminosilicate (SiO ₂ content 18.8% by mass) are mixed with 1.8 kg of a nickel-containing X-ray amorphous aluminosilicate (9.5% by mass of Ui, 17.9% by mass of SiO ₂ ) and 1.35 kg MoOo (all raw materials milled to a fineness of O % residue on the S3 pm-Trüf sieve) in a kneader initially intimately mixed dry and then with the addition of water and 1.4% by mass oxyethyl cellulose, based on the total mixture, as plasticizer and dissolved in water, plasticized. The plastic material is then deformed on a single-screw extruder into cylindrical moldings with a diameter of 8 mm. All composition values given in this example relate to the anhydrous material.

Example 2 (catalyst according to the invention)

A catalyst sample according to Example 1 was dried for 5 hours at 333 K in a drying oven, then flowed through for 1 hour in a weak air stream of ambient air at 295 K and then further dried 553 K for 2 hours. The total mass loss was 51.3% by mass based on the wet starting sample. A 31.8 % mass loss had occurred until storage. Random selection of 30 moldings of the catalyst sample thus treated was subjected to a strength test wherein each mold was loaded to break between two plane-parallel steel plates in a universal strength testing machine. The mean value of the breaking load was 62.2 Newton, the mean error of the mean 3.7 % ·

Example 3 (Comparative Catalyst)

A sample of the catalyst according to Example 1 was heated in a drying oven to 553 K and dried for 2 hours at this temperature. The weight loss occurred within the weighing error was the same as the total mass loss in Example 2. The strength test of 30 moldings according to Example 2 gave an average breaking load of 44.5 Newtons with a mean error of the mean value of 3.0 %.

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Example 4 (comparison)

A sample of the catalyst according to Example 1 was heated in a drying oven to 473 K and dried for 4 hours at this temperature. The mass loss occurred was 49.7% by mass. The strength test analogous to Example 2 yielded 41 »7 Newton with an error of 4> 3 % · (complies with 03.03 89)

Example 5 (according to the invention)

A catalyst sample according to Example 1 was predried for 4 hours at 353 K, then temporarily stored for 3 hours in a weak stream of air and then further dried for 3 hours at 453 K. The total mass loss was 49.8% by volume based on the moist initial sample. Until interim storage, a mass loss of 33.5 mass% had occurred. The strength test analogous to Example 2 gave 60.9 Newton with an error of 5.0 %,

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Example 6 (according to the invention)

A catalyst sample according to Example 1 was pretreated for 2 hours at 373 K, then temporarily stored for 15 minutes at 328 K and then further dried for 4 hours at 500 K. The total mass loss was 52.8% by mass, the mass loss to intermediate storage was 33.0% by mass (ie 62.5 % of the seed mass loss). The strength test as in Example 2 gave 56.4 Newton with a defect of 4.7 %.

(nachpereicht 03.03.59)

Claims (4)

-7- ΖΖ5 & Ϊ1 claims 1. Preparation of mechanically strong hydrosoluble catalysts based on X-ray amorphous aluminosilicates containing elements of the 6th and 8th lifting groups of the Periodic Table and an X-ray amorphous aluminosilicate, the ITebengruppenelemente in the catalyst in the form of ungrafted compounds, characterized in that the deformed catalysts at 333 to 373 K thermally pretreated to a loss of at least 60 % of the total weight loss associated with the thermal treatment, then intermediately stored for 15 minutes to 3 hours in flowing air at 273 to 328 K and then post-treated at up to 553 K. 2. Preparation according to item 1, characterized in that the catalysts are flowed through during the intermediate storage of ambient air at a flow rate of 1 to 3 v / vh. 3. Preparation according to item 1, characterized in that the catalysts are stored for 15 minutes to 1 hour. 4. Preparation according to item 1 and 3 », characterized in that the intermediate storage is carried out at 278 to 328 K.