DE1542348A1 - Process for the production of catalysts or catalyst carriers - Google Patents

Description

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Dr. LOITLk ¹ KS, tr.-lna- U., .... «·

6DC0 FrnnkiiK 'α. M. A «n <r.Wje 1V 1542348

SÜ fLIüfiSLiTI Ιι * Τ £ ΖΕΤ 25 July 1966

Budapest XI, Sst. Gelled the 5th

Process for the production of catalysts or Catalyst carriers

The invention relates to a method of manufacture of versatile catalyst carriers acidic baw. basic character, with excellent Adsorption properties, furthermore of catalysts high activity,

The majority of the oil processing, petrolchcmisehen, as well as organic-chemical reactions can be carried out, as is known, in the presence of catalysts, the active LIgtal! components in finer distribution by a carrier with appropriate

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chemical (composition), physical (specific surface, pore size) and technical (grain size, grain distribution, grain size) properties and corresponding heat stability are included. or mixed-phase reactors that often carry out reactions are: hydrogenation, dehydrogenation, isomerization, alkylation, cyclization, aromatization, cracking, hydrocracking, oxidation, Bntalky * - lation, reforming and hydrolysis The catalyst support, mostly consisting of aluminum oxide or aluminum silicate , is mostly made from sodium aluminate or from another aluminum prebond, for example from aluminum nitrate, furthermore from sodium silicate by bringing the starting compounds into solution, mixing them and then precipitating the aluminum oxide or aluminum silicate. In order to be able to ensure the fine distribution of the metal components, the basic compounds of these metal components are added to the solution before the precipitation. Activated charcoal can also be used as a carrier. When the catalytic conversion is carried out, in addition to the finished catalyst, the carrier itself plays a role in the shade; its acidic or basic active sites, as well as dielectric properties can promote the reactions taking place through the carbonium ion, baw _# ver

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Ale Aktirkomponente the carrier can be applied numerous MetalIo "The most effective hydrogenation eindi the nickel, platinum, palladium» Bi-

Sen, zinc, cobalt, molybdenum, and copper. The components most frequently used in oxidation catalysts are: silver, copper, and vanadium as the chemical components. ι Palladium, nickel, cobalt, molybdenum «s? wia proven. Components that are active in isomerization include platinum, tungsten and Ifolybda'n; that platinum is to use as a component deβ Roformierungskatalysators "The Motallkomponaflten represents hydrocracking Ki toron are of generally identical to those *

Bs. Already exists ee: i · '-] -: \ ^. Ia 6.w "-ίΐι-ι: ^^ ;; ^ to find such methods, ^ ΐ;' .. reactions described above / ds · ^ ,; l men synthetic catalysts _f au-s üen i :: -: ■ '- ■■■ - rm-occurring minerals nnü. Rocks « Κ & Ιη ^ with corresponding catalytic and i & ühnii - v'.j: r \'<^.

properties as well as suitable heat steel Ii tut l; ^ ¹ - ^; ^

can,
.be / Until now, catalysts could rait £ kv · :: - :.

on natural mineral-based only door cini.g · - i ;; jii :? Ie reactions (cracking, alkylation and oxine ^ -tlc: :) are observed, and even these only de ras: Y ₅₁ ί ^ ε :; j /.-j 'uv borrowed filling aue various V.

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stones was run out. Namely, can be a natural Obviously only one carrier due to its composition, but only a few at most Influence implementations beneficial for further. Implementations, however, require support with others chemical compositions. The change in chemical Composition of the carriers for the purpose of spreading., the field of application of the catalysts could, however, without modification of their other favorable properties until currently not yet be carried out.

The invention is based on the knowledge

daes containing at least 45 % clinoptilolite

• *

Rocks on the one hand without changing their composition Catalysts suitable for certain purposes are prepared, on the other hand, in turn, their chemical properties with the help of certain procedures - without changing their other favorable properties - modified can be. So can carriers with excellent Adsorption and variable chemical properties obtained and from the latter catalysts for all of the above goals.

The invention is a process for the production of supports and adsorbents which can be used on the side sour or. basic character and with excellent adsorption properties, furthermore of highly active, versatile catalysts, by using a crystalline aluminum silicate with

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high silicon content. According to the invention the procedure is such that a ground mineral product containing at least 45% clinoptilolite and having a bulk density of 0.70 to 1.00 kg / l is used as the crystalline aluminum silicate with a high silicon dioxide content

a / in a known way with solutions of metal compounds treated, the solution evaporates or separated from the solid phase, optionally the solid phase heated and / or reduced and in catalysts is converted, or

b / with a solution or melt of alkali metal, Brdalkali metal or ammonium compounds or is treated with acids, and optionally from the carriers (adsorbents) or catalysts obtained in this way by treatment according to point a / further active metal components-containing catalysts are also produced.

For the production of oxidation catalysts, it is useful to use the ground mineral product or the Carriers with solutions of silver, copper and / or vanadium salts to treat.

For the production of catalysts for hydrogenation, dehydrogenation or hydrodesulphurisation it is advantageous to mix the ground product or the carrier with solutions of platinum, palladium, iron, zinc, Treat cobalt, molybdenum and / or copper salts,

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Coating catalysts can expediently be produced by treating the mineral ground products bsw, the carrier with solutions of nickel, cobalt, molybdenum, chromium, copper, zinc and / or palladium ala.

For the production of ionization catalysts it is advantageous, the ground product or the carrier with a solution of tungsten, platinum and / or Treat molybdenum salts au.

In the production of reforming catalysts, it is essential to use the ground mineral product or treat the carrier with a platinum salt solution.

Boi the manufacture of hydrocracking catalysts the ground mineral product or the carrier is expediently coated with a nickel, cobalt, chromium, molybdenum, Tungsten, platinum, copper and / or bisene salt solution treated.

For the production of carriers of an acidic character, it is advisable to treat the hollow product with an approximately 0.01-5 normal mineral acid or formic acid or acetic acid, or with a 0.01-2 molar ammonium salt solution; in the latter case, a ^{heat treatment carried out between 20O 0} C and 55O ⁰ C is still required so that a carrier with sufficient

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has a strong acidic character.

For the production of carriers with a basic character, the ground mineral product is expedient with solutions or melting of alkali metal or alkaline earth metal compounds to treat.

It was found that the volcanic tuff found in the area of Tokaj (Hungary), which mostly consists of clinoptilolite and has the following chemical composition:

SiO ₂ . 60-75 wt. Al ₂ O ₃ 10-16 » Pe ₂ O ₃ 0.0-4 " K ₂ O 0.5-10 " Na ₂ O
CaO 0.5-6 "
0.0-5 " MgO 0.0-3 " Glow pre-excitement 3.0-15 "

as a basic material of the method according to the invention ausaerordentuch can be used favorably and can be converted into different carriers or catalysts by various treatments carried out according to the invention. But any rock can be found, baw. Any Kinerals variety with a KHnoptilolit content of more than 4-5 % can be used.

With the method of treatment according to the invention can

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the natural aluminum and bison content, as well as the magnesium, calcium, sodium and potassium content of the rocks and minerals can be changed. Their magnesium, calcium, sodium and potassium content can in turn be changed by treatment with salt or alkali solutions or molten salt, as these compotes bond with the crystalline (Klinoptilollt) part of the rocks. Instead of these last-mentioned ions, however, other components not originally present in the minerals, such as copper, barium, etc., can also be introduced into the product this V / else received numerous carriers have aus3crdom very important Adsorptionseigenschaftan and therefore also as adsorbents Vcrwondung find ·. "- by appropriate selection of the Bchandlungsv / ci3on according to the invention, the desired beneficial properties are imparted to the carrier, the active components can so with Can be applied to the carrier in a fine distribution using a simple process, whereby the finished ca-

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tnlyaator dio desired technical or heat atα-bility properties owns "

The method according to the invention is explained in more detail with the aid of the following examples.

example 1

To produce hydrogenation or dehydrogenation catalysts, a volcanic tuff from the Ratka quarry and containing about 80% clinoptilolite is ground, and the fraction with a particle size of 1.00 to 1.25 mm is sieved out, 100 g of this Pm ic tion are also stirred a solution containing 24 g of nickel nitrate in 150 ml of water in a porcelain dish and evaporated. The product is heated until the nitrous vapors are finally removed, then filled into a pressure-tight reactor and ^{treated with Hp stream at 400 °} C. for about 2 hours. The reactor is then cooled to 300 ⁰ C, and the ^ .Aufrechterhalten -Stromes benzene. 30strömt h with einor Räumteschwindigkeit of ".l 1.1" over the catalyst. The benzene is having at a temperature of 250-300 ⁰ C temperature a conversion of over 95 % to cyclohexane. Palis, however, kept the reactor at a temperature above 400-5OO ° C and instead of benzene, cyclo-

hexnn is poured in, lasturoo is dehydrated to benzene over 90% with just one itLon.

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Example 2

To prepare Ginoa Sntalkylierun £ skatalysa ~ tors, 100 g of the milled product according to Example 1 with a grain fraction between 1.00 and 1> 25 ram in 500 ml of 1 molar copper sulphate solution are boiled for 4 hours. The liquid is decanted and the Mah 1 product is washed free of copper with distilled water. The product then only contains ionically bound copper. The catalyst is dried in a drying cabinet, then filled into a pressure-tight, continuously operating reactor, and ^{heated to 650 °} C. in a stream of Hp. Toluene is now flowing through the reactor at a space velocity of 1.1.

Example 3

200 g milled product of the grain fraction from 1.00 to 1.25 mm (according to Example 1) are boiled with 1500 ml of 4 η hydrochloric acid for 4 hours; after that the liquid becomes decanted, the ground product washed neutral with distilled water and dried in a drying cabinet. The resulting product is an acidic carrier with a high silicon oxide content and, at the same time, a Drying of Gtaaon or * for chromatographic use also suitable large-pored? .Adsorbent.

For the production of oxidation catalysts

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evaporated the 100 g of this product with 8 g of silver nitrate dissolved in 150 g of water, and calcined at 45O ⁰ O, over this, 5 % silver-containing catalyst, methanol is in a laboratory oxidation proporate at 250 ⁰ C with 35 # conversion, or oxidized. at a temperature of 500 ⁰ C temperature with 100% Konvorsion to formaldehyde.

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Claims (1)

■ PATENT CLAIMS 2. Process for the production of versatile carriers and adeorbents of acidic or basic character and with excellent Adsorptionseigonschaften, furthermore of highly active, versatile catalysts, by using a crystalline aluminum silicate with high silicon dioxide content, characterized »daas as crystalline aluminum silicate with high silicon dioxide content at least Mineral ground product containing 45 % clinoptilolite with a bulk density of 0.70 to 1.00 kg / l is used a / treated in a known manner with solutions of metal compounds, the solution evaporates or separated from the solid phase, optionally the solid phase heated and / or reduced and in catalysts is converted, or b / with a solution or melt of the alkali metal, alkaline earth metal or ammonium pre-bonds or is treated with acids, and optionally from the carriers (adsorbents) or catalysts obtained in this way by treatment according to point a / also catalysts containing further active metal components getting produced" 009825/1860 BATH ORIGINAL 2 »Process according to claim 1 for the production of oxidation catalysts, characterized in that that the mineral ground product or the carrier with solutions of silver, copper and / or Vanadium Salts Treated " 3 »Process according to claim 1 for the production of hydrogenating, hydrodesulphurising or dehydrogenating catalysts, characterized » that you can bring the ground mineral product or the carrier with you Solutions of nickel *, platinum, palladium, iron, Zinc, cobalt, molybdenum and / or copper salts treated » 4 »The method of claim 1 for the preparation of Sntalkylierungskatalysatoren, characterized gekonneeichnet, treating the Mineralmahlprodukt or the carrier with the solution of nickel, cobalt, molybdenum _f chromium, copper, zinc and / or palladium salts. Process according to Claim 1 for the production of isomerization catalysts, characterized in that the ground mineral product or the carrier is treated with solutions of tungsten, platinum and / or molybdenum salts * ^: 6. The method according to claim 1 for the production of reforming catalysts, characterized in that that the mineral ground product can be mixed with platinum 009825/1860 BATH ORIGINAL treated alzlösun'gen -m. 7. The method according to claim 1 smr production of hydrocracking catalysts, characterized in that the ground mineral product or the carrier with solutions of nickel, cobalt, chromium, molybdenum, tungsten, platinum, copper and / odor Treated iron salts. 8. The method according to claim 1 for the production of carriers of acidic character, characterized in that that the mineral ground product with a 0.01-5 η mineral acid or treated with formic or acetic acid. 9. The method according to claim 1 for Herateilung · carriers 3auren character, characterized in that the Mineralmahlrprodukt treated with a 0.01-2 mole ren ammonium salt solution and thereafter the temperature turbereich subjecting of 200 to 55O ⁰ C to a heat treatment * 10. The method according to claim 1 for the production of carriers of basic character, characterized in that that .nan the Minoralmahlprodukt with a solution or melt of alkali metal or pulp alkali metal -Connections handled 00982S / 1860 BATH ORIGINAL