DD151557A3 - Preparation of aluminum oxide-containing erionite catalysts with selective cold characteristics - Google Patents

Preparation of aluminum oxide-containing erionite catalysts with selective cold characteristics Download PDF

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Publication number
DD151557A3
DD151557A3 DD21553879A DD21553879A DD151557A3 DD 151557 A3 DD151557 A3 DD 151557A3 DD 21553879 A DD21553879 A DD 21553879A DD 21553879 A DD21553879 A DD 21553879A DD 151557 A3 DD151557 A3 DD 151557A3
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DD
German Democratic Republic
Prior art keywords
hydrosol
erionite
characterized
hydrogel
alumina
Prior art date
Application number
DD21553879A
Other languages
German (de)
Inventor
Karl Becker
Karl-Hermann Steinberg
Josef Hille
Manfred Prag
Dieter Pape
Hans-Dieter Berrouschot
Waltraut Weinhold
Ralf Merk
Renate Strauss
Heiner Klotzsche
Karl-Heinz Nestler
Dieter Sachse
Christian Szkibik
Helmut Fuertig
Wolfgang Krueger
Original Assignee
Karl Becker
Steinberg Karl Hermann
Josef Hille
Manfred Prag
Dieter Pape
Berrouschot Hans Dieter
Waltraut Weinhold
Ralf Merk
Renate Strauss
Heiner Klotzsche
Nestler Karl Heinz
Dieter Sachse
Christian Szkibik
Helmut Fuertig
Wolfgang Krueger
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Karl Becker, Steinberg Karl Hermann, Josef Hille, Manfred Prag, Dieter Pape, Berrouschot Hans Dieter, Waltraut Weinhold, Ralf Merk, Renate Strauss, Heiner Klotzsche, Nestler Karl Heinz, Dieter Sachse, Christian Szkibik, Helmut Fuertig, Wolfgang Krueger filed Critical Karl Becker
Priority to DD21553879A priority Critical patent/DD151557A3/en
Publication of DD151557A3 publication Critical patent/DD151557A3/en

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Abstract

Preparation of alumina-containing erionite-based catalysts for shape-selective cleavage of n-paraffins. Through the use of the form-selectively acting Spaltkatalysartor it is possible to split out the octane-neutral n-paraffins from reformate mines. This makes it possible to increase either reformates with higher octane number or using milder reforming the throughput at a constant octane number. The aim is a process for the preparation of erionithaltigen catalysts. The object of the invention is to find such a deformation method for Erionitkatalysatorenmassen, with it is possible to produce mechanically stable and specifically lightweight moldings of any shape and high macroporosity. The object is achieved by converting in the first stage a boehmite-containing alumina hydrogel with a basic salt-forming acid in the molar ratio acidic / hydrogel of 0.05 to 0.20 at room temperature into a hydrosol I low dispersity, in the second stage this hydrogel I. by heating to 323 to 423 K in a hydrosol II and treated until the desired degree of dispersity is reached, the Hydrosol II optionally forms in combination with other components with the addition of finely ground ion-exchanged erionite under reaction with a coagulant to formates, which in known Be thermally treated and processed further. The catalysts prepared according to the invention can be used in hydrocarbon conversion processes for the production of knock-resistant gasoline components.

Description

-wf-

VEBLeuna-Werke Merseburg, 5. 12, 1979

"Walter Ulbricht" DC.Do/Sch

LP 78115 Title of the invention

Preparation of alumina-containing erionite catalysts with selective splitting properties

Field of application of the invention

The invention relates to the production of highly porous and mechanically solid alumina-containing erionite catalysts which can be used in the chemical industry for the selective cracking of η-paraffins from hydrocarbon mixtures.

Characteristic of the known technical solutions

By employing molecular cleavage-selective cleavage catalysts, it is possible to cleave n-affines from hydrocarbon mixtures and, for example, to produce higher octane reformates in the reforming process or to maintain the same level of octane at comparatively milder reforming conditions and thus extend the reformer's operating periods Purely this process, which was introduced under the name "Selektoforming", contains noble metal-containing ion-exchanged catalysts on molecular sieve, preferential

wise erionite base used.

These catalysts can be used in different geometric forms. The suitability of certain forms of catalyst is decisive, i.a. the geometry of the technical reactor used. If it is possible to ensure a sufficiently high catalytic activity, it is expedient to keep the specific bulk density as low as possible, because the catalysts contain very expensive constituents. On the other hand, the catalyst moldings have to cope with the mechanical stresses of practical operation. For the preparation of zeolite catalyst moldings, several methods have already become known, wherein as zeolites mordenite, erionite, X, Y and A zeolites are used. Zeolithformlinge should by tableting after mixing the zeolite powder without binder (DE-AS 1 667 314) or by tabletting after mixing of the zeolite powder with suitable binders (DE-AS 1,249,834, DD-PS 130 531) or by extrusion to full-strand moldings (DD- PS 96 642, DD-PS 116 008) or by agglomeration to Agglomerierkugeln (DD-PS 100 403) to be produced.

All of these methods have some disadvantages that cause a reduction in the utility properties of the catalyst moldings. Thus, when tableting and agglomeration due to the strong compression moldings with an unfavorable pore structure and a high bulk density. The full-strand blanks produced by blending and extruding have, in most cases, too low a strength to be used in larger reactors. This is especially true when the porosity is high. Another solution to the problem of mordenite deformation is the co-dripping of suspensions of mordenite and a binder into an organic agent and subsequent curing (DE-AS 1 215 660, DE-AS 1 259 853, DE-AS 1 442 856, DE -AS 1 442 858, DE-AS 1 442 859, DE-AS 1 442 880, DE-AS 1 442 882, DE-AS 1 545 288, DE-AS 1 545 418). The binders used are predominantly aluminum oxides or oxide hydrates and / or aluminosilicates (DD-PS 116 008, DE-AS 1 946 187) or partially hydrolyzed aluminum salts (SU-PS 484 183). The Nach-

Part of this type of deformation is that the mixture in most cases thixotropic and thus are not or only very limited stability. Pure large-scale use of such a method thus results in considerable problems. Furthermore, very difficult to reproduce properties are obtained. This method is not known at all for the dropping of erionite-containing catalyst masses, since erionite in particular exhibits a strong tendency to thixotropy in such suspensions. A process has also been proposed for producing mechanically strong, porous hollow-strand moldings from erionite catalyst trains, according to which it is possible to produce mechanically sufficiently stable hollow-strand moldings by using binder mixtures and by applying specific thermal treatment (V / P B 01 J / 205 236). The disadvantage of this method is the complicated technology and the high technical complexity of manufacturing. Furthermore, the thermal aftertreatment can not always be made reproducible.

Object of the invention

The aim of the invention is a technologically simple process for the preparation of highly active Erionitkatalysatorformlinge for selectively cleaving η-paraffins, which have a high porosity and low bulk density with high mechanical stability.

Presentation of the veson of the invention

The object of the invention is to produce such alumina hydrosols by conversion of böhmithaltigen alumina hydrogels of any Provinienz, with which it is possible to deform highly active Erionitkatalysatormassen to mechanically stable, specific light forms of any shape and high macroporosity. According to the invention, the object is achieved by carrying out the peptization of the alumina hydrogel in two stages, wherein in the first stage a predominantly boehmite-containing hydrogel with a basic Sal ~

ze acid forming in acid / hydrogel molar ratio of 0.05 to 0.20 at room temperature in a hydrosol I low dispersity and viscosity and in the second stage, the hydrosol I by kneading or stirring, optionally by heating to temperatures of 323 to 423 K. , transferred to a hydrosol II and treated until the desired degree of dispersity is reached, the Hydrosol II optionally in combination with other components with the addition of finely ground ion-exchanged erionite, optionally formed under reaction with a coagulant to formations which are thermally treated in a known manner and From the viewpoint of peptizability, the use of an alumina hydrogel precipitated above pH 7.5 is particularly useful in the form of a wet cake or in the form of finely ground, dried aluminum trihydroxide or mixtures of filter cake and dried product advantageous ,

An adjustment of the water content of the hydrosol I formed in the first stage proves to be favorable from 50 to 90% by mass.

Advantageously, acids which form as basic salts are nitric acid.

The desired high degree of dispersity of the hydrosol II can be achieved by heating the hydrosol I in the second stage at temperatures of 323 to 423 K for 0.1 to 24 h. Hydrosol I and / or alumina hydrogel and / or alumina and ion-exchanged erionite, which is optionally ground and thermally pretreated, are advantageously admixed in amounts of from 1 to 80 % , the solids content in the hydrosol to be deformed being from 150 to 400 g / l is.

For the process according to the invention, it is possible to use erionite which has been ion-exchanged by a variety of methods, i.e. ion exchange is carried out in one or more stages with or without heat treatment between optionally several exchange cycles in both solutions and salts melts.

Advantageously, the moldings are thermally treated, optionally subjected to one or more further ion exchange processes and impregnated with platinum and / or palladium in the form of their amine complexes in an amount of 0.1 to 1.0 mass of the noble metal,

embodiments

Example 1 (comparative example)

In a commercial erionite, by repeated ion exchange with ammonium nitrate solution and intermediate heating, the sodium content was reduced to 0.02% Na 2 O and the potassium content to 1.1% by weight KpO. After filtration and washing, the filter cake was dried at 385 K and then ground (catalyst mass A). Of these, 1000 g (based on the Glückückstand at 1070 K) with 170 g of a kaolinithaltigen clay (based on a Glückrückstand at 1070 K) and 170 ml of an alkali-free 30 $ silica and 1.0 1 of a 6% aqueous Äthylzelluloselösung in one Kneading machine kneaded and extruded into hollow strands with 5 mm outer diameter and 1.5 mm inner diameter. After standing in air, the hollow strands are heated at 5 degrees / minute to 723 K, 2 hours at 723 K in the air stream, cooled to 423 K, purged with dry nitrogen, heated in the dried hydrogen stream at 5 degrees / minute to 723 K and cooled down again. On the thus treated hollow strands were applied with Piatintetramminchloridlösung by impregnation 0.6 mass% platinum. It was then dried at 385K. The moldings had a bursting pressure of 165 N / molding, an edge strength of 52 N / molding and a bulk density of 570 g / l (Catalyst 1).

Example 2

From a nitrate of aluminum nitrate (100 g AlgO ^ / l and 25 g HN0 ~ / l) is precipitated with ammonia water (25% by mass №Ц) Aluminiumhydrogelgel at a pH of 8.0 and a temperature of 330 K. After filtration and washing was

a filter cake with 21.8 mass # AIpO- received. In a mixer, 20 kg of the filter cake were converted into an aluminum hydrosol I by addition of 340 ml of nitric acid at room temperature.

By stirring in an autoclave (4 hours at 370 K), the Hydrosol I in the Hydros! II transferred. 17.8 kg (based on the ignition residue at 1070 K) of the catalyst composition A (of Example 1) and 10 kg of Hydrosol II are mixed in a kneading machine. The mixture is gelled with 750 ml of ammonia water and extruded to 3 mm extrudates. The moldings were dried at 375 K and annealed at 800 K. A platinum content of 0.6 meq% was applied to the whole-strand blanks by impregnation with a platinum tetrammine chloride solution.

The full-strand blanks had a bursting pressure of 206 N / molded article, an edge strength of 75 N / molded article and a bulk density of 560 g / l (Catalyst 2),

Example 3 μ °> I

On a commercial erionite 95 % of sodium and 70 l % dex ^ potassium ions are replaced by ion exchange with ammonium nitrate solution. It is filtered and washed, the filter cake dried at 385 K, then ground and calcined at 800 K (catalyst mass B).

18.0 kg (based on the ignition residue at 1070 K) of the catalyst mass B and 10 kg of hydrosol II (of Example 2) are mixed in a kneading machine. The mixture is gelled with 750 ml of ammonia water and extruded to 2 mm full strands. The molds are dried at 375 K and annealed at 800 K. With AmmoniumnitrratlÖ3ung took place at the formations a renewed ion exchange in the course of which the sodium content to 0.02% Na 2 O and the potassium content to 0.84 % K 2 O sank. The moldings were washed, dried at 275 K and annealed at 800 K.

A platinum content of 0.6% by mass was applied to the moldings with platinum tetrammine chloride solution. The full-strand blanks had an initial print of 220 N / blank, an edge

strength of 76 N / molded articles and a bulk density of 565 g / l (Catalyst 3).

Example 4

From a nitric acid AluminiumnitraUösung (100 g Al ^ O ^ / l and 25 g HNO ^ / l) is precipitated with ammonia water (25% by mass ЖЦ) at a pH of 8.5 and 330 K an alumina hydrogel. After filtration and washing, a filter cake with 22.0% by mass Al 2 Oo was obtained. In a mixing container, 20 kg of the filter cake are mixed with 370 ml of nitric acid (50% strength) and transferred by stirring to the aluminum hydrosol I at room temperature. »

Hydrosol II was obtained by treatment of Hydrosol I in a stirred autoclave (5 hours at 370 K). 2.8 kg (based on the Glübrückstand at 1070 K) of the catalyst composition A (of Example 1) are mixed with 5 kg of the hydrosol II and 2 1 of water until the viscosity reached 0.07 cP. By dropping into ammonia water, the mixture was coagulated. The resulting dripping balls have after drying a very smooth surface, a strength of 120 N / ball and a bulk density of 380 g / l. A platinum content of 0.6% by mass was applied to the dripping balls by impregnation with a platinum tetrammine chloride solution (catalyst 4).

Examples 2, 3 and 4 correspond to the method according to the invention.

All four prepared erionite catalysts were subjected to comparative catalytic measurements under conditions that are very close to the technical ones. A reformate benzine fraction with a boiling range of 328 to 453 K and the following parameters was used:

ROZ + 88.5

Paraffins VoI % 51.9 Naphthenes VoI % 11.4

Aromatics VoI % 36.7

Light petrol <373 K VoI % 20.0

The test was carried out at 3.0 M Pa, a load of 30 v / v.h

3 3 and a gas-product ratio of 1000: 1 Nm / m. The consequences-

- 8 DE Table contains the achieved data ·

Table: Catalytic properties of the catalysts prepared according to Example 1 (Comparison) to 4 in the selective splitting of a reformate benzine

example 1 (comparative) 2 3 4 Temperature K 753 748 743 733 R0Z +0.04 92.5 93.5 93.0 94.5 Plüssigproduktausbeute mass% 95.5 95.0 95.5 94.5 Light petrol <373 K VoI % 20 22 24 25

The results of the catalytic test, which are summarized in the table and the mechanical characteristics given in the examples, show that the catalysts 2,3 and 4 produced by the process according to the invention are suitable for industrial use by virtue of their good properties very good catalytic properties of the erionite and the binder arise catalysts with improved catalytic properties. The advantage of the catalysts produced by the process according to the invention manifests itself both in lower reaction temperature and in higher octane number of the product with simultaneously higher yield of liquid product. The lower bulk density also reduces the catalyst mass of a reactor with better catalytic results.

Claims (9)

invention claim
1. A process for the preparation of alumina-containing erionite catalysts for the shape-selective cleavage of n-paraffins from hydrocarbon mixtures, preferably reformate, from alumina hydrosol and ion-exchanged erionite-containing mixtures, characterized in that one carries out the Peptisation of the alumina hydrogel in two stages, wherein in the first stage, converting a hydrogel containing predominantly boehmite with an acid / hydrogel molar ratio of 0.05 to 0.20 at room temperature to a low dispersity and viscosity hydrosol I and, in the second stage, hydrosol I by kneading or Stirring, optionally by heating to temperatures of 323 to 423 K, converted into a hydrosol II and treated until the desired degree of dispersity is reached, the hydrosol II optionally in combination with other components with the addition of finely ground ion-exchanged erionite optionally forms, under reaction with a coagulant, into molds which are thermally aftertreated and further processed in a known manner.
2. The method according to item 1, characterized in that the alumina hydrogel above the pH of 7.5 is precipitated and used in the form of a moist filter cake or in the form of finely ground, dried.Aluminiumtrihydroxid or mixtures ѵлэп filter cake and dried product becomes"
Method according to items 1 to 2, characterized in that the water content of the hydrosol I formed in the first stage is set within the limits of 50 to 90% by mass.
4 Process according to items 1 to 3, characterized in that nitric acid is used as acid which forms basic salts.
5 · Method according to item 1 to 4, characterized in that the optionally necessary heating of the hydrosol I in the second stage at temperatures of 323 to 423 K for 0.1 to 24 h.
6. The method according to item 1 to 5 », characterized in that the solids concentration of the hydrosole to be formed and their combinations with other components is 150 to 400 g / l.
7th method according to item 1 to 6, characterized in that the hydrosol II hydrosol I and / or alumina hydrogel and / or alumina and ion-exchanged erionite, which is optionally ground and thermally pretreated, in amounts of 1 to 80 % is added.
8. The method according to item 1 and 7 t characterized in that the ion exchange of the erionite is carried out in one or more stages with or without intermediate heat treatment with solutions or melts of salts.
Process according to items 1 to 8, characterized in that the moldings are thermally treated, optionally subjected to one or more further ion exchange processes, and are mixed with platinum and / or palladium in the form of their amine complexes in an amount of 0.1 to 1.0 mass%. of the precious metal are impregnated.
DD21553879A 1979-09-14 1979-09-14 Preparation of aluminum oxide-containing erionite catalysts with selective cold characteristics DD151557A3 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DD21553879A DD151557A3 (en) 1979-09-14 1979-09-14 Preparation of aluminum oxide-containing erionite catalysts with selective cold characteristics

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DD21553879A DD151557A3 (en) 1979-09-14 1979-09-14 Preparation of aluminum oxide-containing erionite catalysts with selective cold characteristics
CU35274A CU21293A (en) 1979-09-14 1980-06-17 Production of erionite catalyzer with aluminiun oxide content of selectives dissociations properties
BG4886480A BG37606A1 (en) 1979-09-14 1980-08-18

Publications (1)

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DD151557A3 true DD151557A3 (en) 1981-10-28

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CU21293A (en) 1982-08-24
BG37606A1 (en) 1985-07-16

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