DD160297A3 - CATALYST SYSTEMS FOR COLLECTING HOEHERSYLING HYDROCARBON FRACTIONS - Google Patents

Abstract

The invention relates to catalyst systems for cracking higher boiling hydrocarbon fractions to fuel components. The object of the invention is to produce cracking catalysts with improved selectivity of the formation of fuel components in the cracking of higher boiling hydrocarbon fractions. The task of developing a catalyst system of corresponding composition, thereby a catalyst system is solved, the zeolitic aluminosilicates, preferably of the NaY type, their Na + cations to 60 to 95 Aequ .-% by hydrogen or ammonium cations and / or cations of the 2 Main group and / or 3rd main group and / or subgroup of the PSE, in an amount of 1 to 50% by mass, a roentgenamorphic aluminosilicate having a Na 2 O content of <- 0.03 Ma. % and a SiO 2 deep content of 1 to 90% by weight, in an amount of 5 to 90% by mass, optionally a peptizable binder, in an amount of 1 to 30% by mass, one or more Heavy metal compounds on an oxidic carrier comprising 1 to 10% by mass of one or more compounds of the 1st to 2nd main groups of the PSE, in an amount of 0.1 to 20% by mass.

Description

£. i, J \ J \ J

VEB Leuna-Werke Leuna, the 4.3 »1981

"Walter Ulbricht"

LP 80121 Title of the invention:

Catalyst systems for cracking higher boiling hydrocarbons of ffract ions

Field of application of the invention:

The invention relates to catalyst systems for cracking higher boiling hydrocarbon fractions to fuel components which are in a catalytic. Cleavage method can be used with moving catalyst bed.

Characteristic of the known technical solutions

Catalytic fission processes can be designed in a technologically different way ». A distinction is made between processes carried out on a fixed catalyst and on a moving catalyst bed. The most advanced method of the latter type is the ⁿ riser method in which the splitting operation takes place in a so-called plug dust cloud.This method requires microspherical, abrasion-resistant catalysts which exhibit high activity and good thermal and hydrothermal stability during the pretreatment, reaction and In addition, good resistance to poisoning against nitrogen, sulfur and rJetallver -

U55

Impurities required ..

Catalysts meeting these requirements are preferably blends of activated crystalline aluminosilicates and X-ray amorphous aluminosilicates and, in some cases, alumina. However, these catalysts do have some significant pest parts.

1. They form, for example, relatively much coke and gas at the expense of the formation of liquid products.

2. They decompose compounds containing sulfur and nitrogen only in an insufficient amount, so that the cracked gas formed has to be aftertreated and / or a hydrorefined raw material must be used.

2. There are relatively many naphthenic linking compounds cleaved which are no longer available for aromatization.

The above-mentioned limitations limit the economic efficiency of the catalytic Grackverfahrene.

Ziiei the .ariinaung

The aim of the invention is the development of catalyst systems for catalytic! Splitting hydrocarbon fractions into fuel components that have improved selectivity to form liquid reaction products, particularly fuel components and aromatics, and exhibit higher activity for degrading organic heteroatoms.

Presentation of the, Vesens of the invention

The object of the invention is to develop a catalyst system for splitting higher boiling hydrocarbon fractions of corresponding composition, the use of which, with improved selectivity, leads to higher fuel yields. This object is achieved by catalyst systems for splitting higher boiling hydrocarbon fractions into fuel components which are zeolitic zeolitic aluminosilicates, preferably of the ITaY type, whose iia ⁺ cations are hydrogenated to 60-95 Aqu .-> ä by hydrogen or ammonium cations and / or nations of the 2 . Head-

229055 7

and / or lifting group of the PSE, in an amount of 1 to 50% by mass, an X-ray amorphous aluminosilicate having an ITa ₂ O content of .mu.m , 0.03 mass% and an SiO.sub.2 content of 1 to 90 Ma. ~% Based on the material calcined at 1073 K, in an amount of 5 to 90 wt.%, Optionally a repulpable binder in an amount of 1-30 wt.% »One or more heavy metal compounds of 6 Seep group of the PSE on an oxidic support comprising 1 to 10% by mass of one to several compounds of the elements of the 1st to 2nd main groups of the PSE in an amount of 0.1 to 20% by mass.

The catalyst systems preferably contain 5 to 25 Ma. % zeolitic aluminosilicates, 10 to 50% by mass X-ray amorphous aluminosilicate, 10 to 25 Ma. - Böhmithydrogel as a peptizable binder and 1 to 10 Ma. -% heavy metal compounds on an oxide carrier. It is favorable if the oxidic support contains alumina, silica or aluminosilicate and if potassium, cesium, calcium or magnesium are used as elements of groups 1 and 2 of the PSE. As heavy metal compounds are advantageously the oxides and / or sulfides of molybdenum and / or V / o If rams, in an amount of 0.1 to 20 Ma. -% used.

The heavy metal compounds can be introduced into the catalyst system in various ways. The preferred variant is that different catalyst systems from the alumina, which may be stabilized by silica, together with the heavy metal compound and the remaining o.g. Compounds are prepared separately by dispersion and spray drying microspherical particles with diameters of 10 to 15Oy ^ m, preferably 30 to 120 / ^ m, the mechanical mixtures thereof in the ratio of 0.01 to 1, preferably from 0.05 to 0 , 2, can be used as catalyst systems in the context of this invention. A possible variant also consists in producing an aqueous or mineral-acid dispersion from all components indicated, which is sprayed in the spray dryer to form microspherical particles with a diameter of 10 to 150 μm4.m, preferably 30 to 120 μm.

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It is surprising that a catalyst system which additionally contains heavy metal compounds is superior to the conventional ones in terms of activity and selectivity.

The examples below are intended to illustrate the nature of the invention.

Example 1: Catalyst A (Catalyst of the Prior Art) is a microspherical PCC catalyst made from a mixture of 20 Ma .-><? Boehmite, 60 IvIa .-; ό aluminosilicate with an SiQ ₉ content of 85 Ma. -% and 20 Ka .-% of a 90 eq .-% xnit_ 1'ΙΉ _£ ions and an SS ^ -lonengemisch HaY exchanged zeolite prepared and after Galcinierung at 873 K for 8 hours at 1023 K hydrothermally treated v / urde ,

Example 2:

The catalyst system B (catalyst according to the invention) consists of a mixture of 5 parts of catalyst A and 1 part of a spray-dried aluminum oxide, which contains 1.8 1.10% of CaO and 10% of Ia. -% UoQ ^ contains.

Example 3 '· (Comparing

These catalysts became an L ^; likro-CAT-A-test.

Conditions: Kataiysatormenge 5 g of dry matter

Grain size>. G3yU.ni catalyst / oil ratio 2.8

Ti

Temperature 7i? 3K

Pressure 0.1 MPa

Load 20 g / gh

Raw material vacuum distillate

(623 to 773 K boil with 0.33% ash sulfur)

DEND,

.229055

catalyst Ma "-% A Total sales in ti 80.5 liquid products 74.1 tt Boiling 453 K) It 54.6 Crack gas η 16.8 coke 9.1 gasoline selectivity 0.68

72.1

84.1

56.2 7.9 '8.0 0.78

Benzine selectivity is the ratio of gasoline content to total sales. The data in ila «-% refer to the enforced raw material.

Catalysts A and B are compared for sulfur reduction capacity and liquid product composition. The reaction conditions correspond to those of the example

Catalyst Total conversion into fusible products thereof: aromatics i - paraffinic olefins residual sulfur

it

ti

it

80.5

74.1

50.8

28.6

3.8

0.32

72.1 84.1 49.8

34.9 6.0 0.21

From the examples given it is apparent that an inventive catalyst system over a conventional PCC catalyst by

- An improved selectivity of the formation of fuel components at almost the same activity

- a significantly reduced gas and a small coke formation

- a significantly better yield of aromatics as well

- characterized a much improved sulfur degradation.

Claims (6)

-229055 7 Invention claim 1. Catalyst systems for cracking higher boiling hydrocarbon fractions containing as main components a mixture of an ion-exchanged modified crystalline and a substantially alkali-free X-ray amorphous aluminosilicate »characterized in that the catalyst systems zeolitic aluminosilicates, preferably of the HaY type, whose Ua ⁺ ions contain from 60 to 95 equiv. by hydrogen or, ammonium cations and / or cations of the main and / or main groups of the PSE in an amount of 1 to 50! "la" - jo j an X-ray amorphous aluminosilicate having an ITapO content of 0.03 mass % and a SiO 2 content of 1 to 90 mass%, in an amount of 5 to 90 mass%, optionally a peptisable binder, in an amount of 1 to 30% by mass, - One or more heavy metal compounds of the 6th lifting group of the PSE on an oxidic support comprising 1 to 10 Mao% of one or more compounds of an element of the 1st to 2nd main group of the PSE, in an amount of 0.1 to 20 Ma .-%, contain. Catalyst system according to item 1, characterized in that it contains 5 to 25% zeolitic aluminosilicates, 10 to 80 Ma. % X-ray amorphous aluminosilicate, 10 to 25% by weight of boehmite hydrogel as a peptizable binder and 1 to 10 Ma. -% heavy metal compounds contained on an oxidic support. 3. Catalyst system according to item 1 and 2, characterized in that the oxidic support contains alumina, silica or aluminosilicate and that as 229055 7 Elements of the 1st to 2nd main group of the PSB Potassium, cesium, 00.62? jiicigne3j.üiü TSaTWGnCvS u ν »* 3χΌ, 3ϋ · 4. Catalyst systems according to item 1 and 2, characterized in that are used as Seawermetallverbindungen the oxides and / or sulfides of molybdenum and / or tungsten in amounts of 1 to 10 Ma .- ^. The catalyst system according to items 1 to 4 is characterized by the fact that they consist of particles of diameter 10 to 150 μm in diameter. 6. Catalyst system according to item 1 to 4, characterized in that from the oxidisehen carrier and the heavy metal compound and the o.g. Components are manufactured separately by microspherical particles with a diameter of 10 to 120 microns, the mechanical mixtures can be used in the ratio of 0.01 to 1 for splitting higher boiling hydrocarbon fractions to fuel components.