CA1196322A - Silica-containing shaped articles, a process for their preparation, and their use - Google Patents

Silica-containing shaped articles, a process for their preparation, and their use

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Publication number
CA1196322A
CA1196322A CA000419070A CA419070A CA1196322A CA 1196322 A CA1196322 A CA 1196322A CA 000419070 A CA000419070 A CA 000419070A CA 419070 A CA419070 A CA 419070A CA 1196322 A CA1196322 A CA 1196322A
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Prior art keywords
silica
base material
water
mixture
catalysts
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French (fr)
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Adolf Wissner
Josef Haydn
Udo Birkenstock
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Bayer AG
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Bayer AG
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00Preparation of quinones
    • C07C46/02Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/04Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • B01J37/0242Coating followed by impregnation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/006Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/04Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • C07C67/05Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
    • C07C67/055Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds

Abstract

Silica-containing shaped articles, a process for their preparation, and their use A b s t r a c t In the new shaped articles a hollow space or a lumpy inorganic base material is surrounded by a porous silica-containing layer. They can be prepared by apply-ing silica sol or a mixture containing water, silica sol and/or waterglass and, if appropriate, finely pulverulent water-insoluble silica and/or porosity producing agents to a lumpy base material, and, if use is made of or-ganic base materials, then removing these organic base materials by heating. The new shaped articles can be used as support material for catalysts or, if the layer containing the porous silica contains catalytically active substances, as catalysts.

Description

3~2 The present invention relates to new silica-con-taining shaped articles~ a process for their preparation, and their use as catalysts and support materials for catalysts.
Silica-containin~ shaped articles are widely used as catalysts and as support mater;al~ for cata-lys~s. A large group of shaped articles of this type 10 ;s formed by homogeneous sil;ca materials~ for example spheres having diameters with;n the range of 2 to 5 mm or extruded profiles, and ;s prepared by, for example, pouring s;l;ca hydrosol into organ;c l;quids not miscible ~;th water or by mechanical shaping (see, for example, 15 German Auslegeschr;ft 1,197,851 and the follo~;ng company leaflets: Kal;-Chemie Katalysatoren CCatalysts3, 19~0; Sud-Chem;e K-Katalysatoren CK Catalysts~, 1973;
and BASF Katalysatoren Verkaufsprogramm CList of catalysts for sale], 1967).
When directly used as catalysts or after having been coated with catalytically active materials, for example by spray;ng or ;mpregnating, shaped articles of th;s type have the d;sadvantage that the catalyticalLy act;ve centres are distr;buted more or less uniformly in 25 the entire shaped article (see, for example, U.S. Patent Specification 3,743,607). The result of this feature is that reactants and reaction products can be retained in the shaped article and initiate the formation of un-desirable byproducts and secondary reactions 5see, for 30 example, Suter, Phthalsaureanhydrid und seine Verwendung CPhthalic anhydride and its use~, published by Steinkopf, Darmstadt, page 20 (1972)). Moreover, by-products and catalyst poisons in the interior of the shaped article can increase in concentra~;on and hence be removable 35 by means of customary regenerat;ng methods only w;th extreme d;fficulty or not at all. These adverse effects Le A 21 277 ar;se to a particularly pronounced extent ~hen the shaped art;cles are porous throughout their entirety.
Attempts have therefore been already made to prepare catalysts which, in their interior, are almost free of pores and/or catalytically active centres. An example of such a catalyst is the catalyst described in U.S. Patent Spec;fication 1,~87,500 and in which 4 to o mm large grains of a slightly porous or poreless support, such as corundum or silicon carb;de, are coated with vanadiu~ pentoxide. To improve on this type of catalyst a mixture of vanadium pentoxide and titanium dioxide is appl;ed to inert, smooth spheres made of porce-lain, steatite or quartz (see Chemie-Ingenieur-Technik 4, 96~ to 970 ~1969))~ In these catalysts the catalyti-cally active constituent, owing to a low melting pointand the tendency to form a glass, is particularly suitable for being applied as a surface coating. Catalysts are also known which are based on the same preparation prin-ciple and in which catalytically active constituents other than vanad;um pentoxide are applied to a support either in pure form or mixed with titanium dioxide.
All such catalysts containing titar,ium dioxide have the disadvantage that they, together with other acidic cata-lyst constituents, acidic reactants or reactants contain-ing acidic compounds, have inadequate mechanical stability.
For example, German offenlegungsschrift 2,909,o70describes a process in ~hich catalytically active sub-stances, for example molybdenum, vanadium, tungsten and/or copper are sprayed as oxide mixtures in the form of an aqueous suspension onto ;nert supports, for example sili-con dioxide or silicates. In this process, the tempera-ture of the support must be below 100C~ the support must be moistened before the spraying step, a heated inert gas must be supplied and care must be taken that the water content of the support is always larger than that of the resulting coating. In all cases Le A 21 277 632l~

~ 3 -a catalyst is ~ormed, the external pdrts of which are not porous.
German Offenlegungsschrift 2,716,154 describes the preparation of a catalyst in which a porous silicon dioxide support ;s coated in a special appl;cation process ;n such a way with pallad;um and gold that th~se catalyti-cally act;ve const;tuents are depos;ted ;n a surf~ce layer which extends from the surface by less than 0.5 mm. However, this application method is very involved 10 and not generally utilisable and produces catalysts which, after a treatment w;th alkali metal acetate, consist of active sil;ca material and catalytically active substances also in their interior.
Silica-contain;ng shaped art;cles have now been 15 found which are characterised in that a hollow space or a lumpy ;norgan;c base mater;al ;s surrounded by a porous s;l;ca-conta;n;ng layer.
Insofar as, ;n the shaped articles according ~o the invention, a lumpy inorgan;c base mater;al is surrounded by 20 a porous s;lica-cont3in;ng layer, the inorganic base mater ;al can consist of a very wide variety of materials which can be non-porous, slightly porous or very porous and are sufficiently strong and inert. Examples ~hich may be men-tioned are sil;con diox;de and silicates, such as sodium 25 aluminosilicates, magnesium silicates tfor example stea-tites), zirconium silicates, silicate glasses, quartz, cal-cium zirconiosilicates and aluminium s;l;cates; aLum;na and products conta;ning alum;na, such as corundum, ~C-alu-mina, ~-alumina, calcium aluminate and spinels, such as - 30 lithium spinels; other oxidic materialsv such as titanium dioxide, zircon;um dioxide, thorium d;oxide~ magnesium oxide and zinc ox;de; metallic materials, such as steels, iron and copper; stone, such as granite, basalt, natural iron ox;des and pumice; materials customarily used as 35 packing media for columns, such as Raschig rings, Berl saddles and ceramic bodies made of, for example, glass, - Le A 21 277 3~2 porcelain or clay; and other inorganic materials such as carbides~ for example silicon carbide~ carbonates, for example calcium carbonate as well as slags, ashes, carbons and expanded clay.
The inorganic base mater;al preferably consis~s of mater;als of low absorbency and having a low ~ET sur-face area. The absorbency is preferably Less than 1û, part;cularly preferably less than 5, 9 of water per 100 9, and the 3ET surface area is preferably below 5 m2/g.
If inorganic base materials having a higher absorbency and/or a higher BET surface area are given, it is advan-tageous to arrange for there to be another layer between the inorganic base material and the layer containing por-ous silica which other layer reduces the porosity of the inorganic base material at its surface to such an extent that the preferable ranges are g;ven at the surface for the absorbency and the BET surface area. This point will be described in more detail further on. Moreover, the inorganic base mater;al preferably consists of sili-cates~ in particular magnesium silicates in the formof steatites, silicon dioxide, aluminas~ steelsr iron~
smelted ashes, smelted slags or packing media~
The crystal structure of the inorganic base mate-rial is of no particular importance. The inorgan;c base materials can be crystalline or amorphous.
The shape and particle size of the lumpy inorganic base material is likew;se of no particular importance~
The inorganic base materials can be, for example, table-ted, grainy or otherwise lumpy and be extrudates, spheres, collared spheres~ granules, tubelets~ rodlets, cylinders, grinding base and other optionally shaped articles, for example rings. In particular metallic materials can also be in the form of wires, wire nets~ bolts, nuts and other shaped hardware. The particles of the inorganic base materials preferably have dimensions within the range of 0.5 to 15 mm. Spheres, granules and mill base Le A 21 277 ~ a~3Z;~

having a mean diameter within the range of 0.5 to 15 mm are particularly preferable, and spheres, granules and mill base having a mean diameter of 2 to 10 mm are very particularly preferable. The inorganic base mat~rial can also sonsist of particles of various types, for ex ample steatite and slags~ and o~ d;ffer;ng shape, for example spheres and m;ll base.
In shaped articles accord;ng to the invention e;ther one of the ;norgan;c base materials described above or a hollow space is surrounded by a layer contain-ing porous silica. The thickness of ~his layer can vary within wide limits~ for example from 10 to 3,000 ~m. The mean thickness of this layer is preferably 20 to 2,000 ~m~
The layer thickness can vary ~rom particle to particle and also within a particle; the latter feature appLies in particuLar ~hen irreguLarly shaped inorganic base mater-ials are present such as, for example, in the case of ash or mill base.
In a particular embodiment of the invsntîon, the layer containing porous silica also contains catalyti-cally active substances or precursors thereof~ These catalytically active substances or precursors thereof can be of the most diverse type. They can be, for ex-ample, metals~ metal compounds, non-metals, non-metal compounds, complex compounds~ ion exchange materials, carbons and/or zeol;tes. Examples of what ;s suitable for th;s purpose are elements and/or compounds of elements o~ the 1st to 6th ma;n group and/or of the 1st to 8th secondary group of the per;odic system as well as com-pounds of rare earths and/or actinides. The followingelements may be mentioned as particular examples: lithium~
sodium, potassium, rubidium, caes;um~ beryllium, magne-sium, calc;um, strontium~ barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybde-num, tungsten, manganese~ rhenium, iron, ruthen;um, os-mium, cobalt, iridium~ rhodium, nickel, palladium~ plati-Le A 21 277
2~
~ 6 -num, copper, silver, ~old, zinc~ cadmi~m, mercury, boron, aluminium, carbon, silicon~ tin, lead, phosphorus, arse-nic~ antimony, bismuth, cerium, scandium~ yttr;um, gal-lium, thallium, germanium, samarium, thor;um and/or ura-nium. These elements can be present as such or in theform of compounds, but, of course, all those elements and compounds are excluded which are not sufficiently stable~ The porous layer containing silica can also conta;n metals of the Raney type, for example Raney nic-kel, Raney ;ron and/or Raney cobalt, or the precursorsthereof, for example f;nely d;v;ded Raney alloys.
Examples of possible compounds and complex com~
pounds are salts and/or complex compounds of the above-mentioned elements, preferably oxygen-conta;n;ng compounds such as oxides, hydrox;des, suLphates, carbonates, car~
boxylates ~for example acetates), n;trates, phosphates, s;licates~ borates and alum;nates, but also cyanides, fluorides, chlorides, bromides, phthalocyanides, ac-e-tyl-acetonates and other complex compounds. Examples of ZO suitable compounds are l;sted ;n A.F Wells, Structural Inorganic Chem;stry, 3rd ed;t;on, Oxford at the Clarendon Press ~1967) and in D. arown, J.H. Canterford and R.
Coltan, Halides of the Trans;tion Elements, volume 1 to 3, John Wiley and Sons, London (1968).
Preferable poss;ble compounds are l;thium sul-phate, sodium sulphate, sod;um acetate, po~ass;um sul-phate, potass;um acetateJ rub;d;um sulphate, caes;um sulphate, l;th;um carbonate~ sodium carbonate, potacsium carbonate, rub;d;um carbonate, caesium carbonate, and the correspond;ng b;carbonates, lithium oxide, sod;um oxide, potass;um ox;de, caes;um oxide, rub;d;um ox;de, beryll;um ox;de, magnesium ox;de, calcium ox;de, stront;um oxide, magnes;um carbonate, calcium carbonate, stront;um carbonate and the correspond;ng b;carbonates, vanadium pentox;de, vanadyl sulphate, vanadyl oxalate, chromium tr;ox;de, molybdenum trioxide, tungsten trioxide, Le A 21 77 i3Z2 ~anganese oxide~ manganese dioxide~ rhenium oxide, ;ron(II) oxide, iron~III) oxide, iron(IItIII) oxide, ruthenium dioxide, cobalttII) oxide, cobalt~II/III) oxide, nickel oxide~ copper oxide, zinc oxide, boron ~xide, aluminium oxide, tin diox;de, lead monox;de~ lead dioxide, leadtII/IV) oxide, phosphorus pentoxide, cerium dioxide, antimony triox;de, antimony pentoxide, arsenic acid, arsenic triox;de, beryllium nitrate, lead n;trate, lead acetate, cadmium nitrate, cadm;um sulphate, cer;um(III) nitrate, cerium~IV) sul-phate, chromium~III) nitrate, iron(III) n;trate, ;ron(II) sulphate, iron(III) sulphate, potassium dichromate, potas-sium chromate, potassium hexacyanoferrate(II), potassium hexacyanoferrate~III)~ potass;um tetrahydroxyantimonate, dipotassium hydrogenphospha~e, cobalt nitrate, copper nitrate, copper suLphate, lanthanum n;trate, manganese(II) nitrate, sod;um arsenate, sodium molybdate, sod;um vana-date, sodium tungstenate, nickel nitrate, nickel sulphate, mercury(II) nitrate~ s;lver nitrate, thall;um n;trate, thorium(IV) n;trate~ uranyl n;trate, bismuth nitrate~
z;nc nitrate, z;rconyl rhloride, hexachloroplatinic acid, potassium hexachloroplatinate, sodium tetrachloropalla-date, palladium chloride, palladium bromide, palladium iod;de~ potass;um hexachloropallad;nate, palladium ace-tate, pallad;um nitrate, pallad;um sulphate, pallad;um-d;amine d;chloride, rhodium trichloride, rhodium tr;ni-trate, hexachloroirid;c acid, iridium trichlor;de, ruthe-n;um tr;chloride, b;smuth trichlor;de~ chromium tr;chlo-r;de, samar;um trichloride and/or niobium oxychlor;de, ard phosphoric acid~ hydrophosphates, ~lihydrogenphos-phates, pyrophosphates, for example vanadyl phosphates, vanadyl pyrophosphates, ;ron phosphates, ;ron pyrophos-phates and copper phosphates.
Carbons~zeol;tes,;on exchanger materials, alum;nas and sil;cas are all of particular interest.
The carbons are preferably pulverulent, carbon-Le A 21 277
3~2 containing systems, for example act;vated carbons as described in "Lurgi Schnellinformat;on ~T 1091/~.75), Pulverform;ge Akt;vkohlen ~Pulverulent act;vated carbons]"
Su;table activated carbons have, for example, ~he composi-t;on: carbon 83 to 93X by weight, hydrogen 1 to 3~ byweight, oxygen 0.2 to 10% by weight, nitrogen traces, sulphur traces, and they contain ash to make up to 100%
by weight and have surface areas of up to 1,500 m2/9 and larger They have, for example, a particle s;ze of less than 1 mm, preferably a fineness of grind of about 20% by weight above 75 ~m.
The zeolites can be of the naturally occuring or synthetically prepared type, for example systems con-sisting of silica and alum;na ;n conjunction w;th alkali metal or alkaline earth metal ox;des. Suitable zeol;tes are extensively described in R.M. ~arrer~ Molecular Sieves Society of Chemical Industry, London, page 39 (1968) and in the guide of ~ayer AG "Bayer-Ieolith", edition of 1st January 1978. Suitable zeolites have, for example, the following characteristics: pore width 3 to 9 k, screen size 1 to 6 mm and bulk density 600 to 750 9/1 and they are preferably fine powders having a particle size of consi-derably less than 1 mm.
The ion exchange materials can be synthetic resins which, owing to their chemical make-up and to a porous, ~ater-permeable structure, are extremely reactive in the sense of bonding foreign ions via cation or anion exchange. Examples of suitable ion exchange materials are described in the guide of Bayer A~ with the title "Lewatit(R)tLewasorb(R)", product information~ edition January 1981. Not only cation but also anion exchange materials, for example the types strongly acidic gel like Na or H form, strongly acidic macroporous Na form, weakly acidic macroporous H form, strongly basic gel-like Cl or OH form, strongly bas;c macroporous Cl form, weakly basic macroporous Cl form and weakly basic macroporous Le A 21 277 ~63~
_ 9 _ r 0~/Cl form~ are suitable. The part;cle s;ze of the ion exchange materials should ;deally be less than 1 mm, preferably less than 0.5 mm.
The aluminas can be all intermediate stages, from alum;nium oxide hydrates to pure aluminium oxide, as described, for example, in the company leafle~s issue~
by Rhone-Poulenc with the titles "Activated Alumina" and "Alumina catalyst carriers SpheraliteSR)". For example aluminas containing more than 95% by weight of Al203 are possible. However, the aluminas can also have lower Al203 contents. PreferabLy, possible alumina is a pulverulent material having a particle size of less than 1 mm, preferably below O.S mm.
Possible silicas are the fine-porousO water-in-soluble silicas described below.
The present invention also relates to a processfor preparing silica-containing shaped articles of the type described above~ which is characterised in that silica sol or a mi~ture containing water, silica sol and/or ~aterglass and, if appropriate, finely pulverulent water-insoluble silica and/or porosity-producing agents are applied to a lumpy base material, the temperature of which is, at the start of the application of the silica sol or of the mixture, below the softening point of the base material and, as the application of the silica sol or of the mixture proceeds, above the boiling temperature of water, the silica sol or the mixture being added in such a way that the water evaporates rapidly, and the water content of the base material is al~ays less than 5% by weight, and, if use is made of organic base materials, these organic base materials are then removed by heating to temperatures within a range of 200 to 1,300C.
Inorganic and organic materials are suitable for use as base material for preparing shaped articles according to the invention~ Suitable inorganic base mater;als are those described above, but care should be Le A 21 277 .

taken to ensure their average residual moisture content at the start of and during the applicat1on of the silica sol or of the mixture is kept very low, that is always below 5% by we;ght, preferably s;gnif;cantly lower.
Suitable organic base mater;als are those which are non-porous~ hardly porous or highly porous, sufficiently f;rm, and sparingly soluble in water. Pre-ferred are solid polymeric materials, for example polysty renes~ polycarbonates, polyolefines, cellulose, cellulose derivatives, polyurethanes, polyacrylonitriles, acrylo-nitrile-styrene-butadiene copolymers, polyesters, poly-vinyl chlorides, polyfluoroethylenes, polyfluoroethylene derivatives, polyamides, epoxy resins or polycondensates, for example of phenol and formaldehyde. Preferably the organic base material consists of non~porous materials which have a softening point above oOC. The shape and size of orgaric base materials can correspond to those of the inorganic base materials described above. Suitable organic base materials are in general hydrophobic, so that in general their water content before or during the appli cation of the mixture need not be particularly watched.
The organic base materials are removed by heating after the silica sol or the mixture has been applied.
This heating step generates hollow spaces which are surrounded by a layer containing porous silica.
The base material used can also be a mixture of var;ous organic base materials, for example polystyrene and polycarbonate, or even a mixture of inorganic and organic base materiaLs, for example steatite and poly-carbonate. It is also possible to use organic basematerials which contain inorganic constituents, for ex-ample glass fibre reinforced polymers.
Examples of what can be applied to the base material are:
- only s;lica sol or - m;xtures wh;ch, in addition to water, contain the fol-Le A 21 ~7?

low;ng constituents:
a~ silica sol, b) waterglass, c) silica sol and waterglass in any mix;ng ratios, S d) 10 to 90X by weight of silica sol and an amownt to add up to 100X by we;ght of finely pulverulent, water-insolubls s;lica, in each case calculated and relative to anhydrous S;02, e~ 10 to 60% by weight of waterglass and an amount to add up to 100% by weight of finely pulverulent, water-insoluble s;lica~ in each case calculated and relative to anhydrous S;02, f) 10 to 90X by weight of s;lica sol and waterglass, the waterglass content being at most 60% by weight of the mixture, and an amount to add up to 100X by weight of finely pulverulent, water-;nsoluble s;lica, ;n each case calculated and relat;ve to anhydrous S;02.
Mixtures wh;ch conta;n only waterglass as the s;l;ca-type component are generally only used ~hen~ for example when using strongly porous base materials or those ha~ing very smooth surfaces, it is intended to produce a first layer to reduce the porosity and/or improve the bonding and one or more layers containing further or other silica~type components are applied there-after. When s;lica sol is solely used and in the caseof all other water-containing mixtures, it is of no par-t;cular importance to which type of base material they are applied, whether they are used to produce single or mult;ple coatings and whether the layer produced is to be followed by one or morP further layers. Silica sol and mixtures as described under d), e) and f) are preferably used, if appropriate together with porosity-producing agents.
If water is used for preparing the components or component mixtures to be applied, a very wide variety of organic solvents can~ if appropriate, be added to Le A 21 277 the water as an auxil;ary medium, but it is not always necessary to establish a homogeneous liquid phase. Ex-amples of poss;ble organ;c solvents are aliphat;c, cyclo-al;phat;c or aromat;c as well as heterocycl;c compounds wh;ch can also be subst;tuted. Su;table al;phatic hydro-carbons are stra;ght-chain or branched hydrocarbons having 1-lZ, preferably 5-8, hydrocarbon atoms. Possible cyclic hydrocarbons are those which have 5-7, preferably 6, carbon atoms ;n the r;ng system. Poss;ble heterocycl;c compounds are those wh;ch have 5-7 and preferably o, atoms in the r;ng system. Preferable suitable hetero~
cycl;c compounds are S- and 6-membered systems wh;ch can conta;n oxygen and/or n;trogen as the heteroatom.
The solvents added can have subst;tuents, such as halogen atoms, for example fluorine, chlor;ne or bro-mine, hydroxyl, amino, sulphon;c ac;d or carboxyl groups and esters thereof, C~-C4-alkoxy groups and C1-C12-alkyl rad;cals. Part;cularly preferable organic solvents are hydrocarbons such as hexane, cyclohexane, benzene, toluene and xylene, alcohols such as methanol, ethanol, propanol, ;sopropanol, butanol~ amyl alcohol, ethylene glycol, glyceroL and cyclohexanol, ethers~ such as ethy-lene glycol monoethyl ether, ethylene glycol d;ethyl ether, ethylene glycol monotolyl ether and tr;ethylglycol methyl ether, ketones, such as acetone, am;nes, such as ethylamine, cyclohexylam;ne and ethylened;am;ne~ phe-nols, such as phenol, 3-acetoxyphenol, resorc;nol and pyrocatechol, as well as blends and mixtures of these compounds in the most diverse compositions.
If organic base materials and organic solvents are used, care should be taken to ensure that onLy those organic solvents are used in which the particular organic base material is insoluble or only spar;ngly soluble.
In part;cular cases it is also possible to use m;xtures in which the liquid medium contains only very small proportions of water.
Le A Z1 277 ~3~2 Any silica-conta;n;ng materials or mixtures to be applied to the base material can optionally conta;n in addition one or more porosity-producing agents, for example O to 100~ preferably O to 50, X by weight, rela-tive to all silica constituents present and calculatedas anhydrous sio2.
The silica sol used can be aqueous, colloidal, silica solutions having the most diverse properties and described, for example, in the guide ~ayer-1û Anorganika~ Silica Sol, Order No. AC 10006 e of the 1stFebruary 1973. The silica sol preferably contains 15 to 45% by weight of SiO2 and below 0.5% by weight of Na20 and has a pH value w;thin a range of 3.4 to 10, a density within a range of 1.09 to 1.33 g/cm3 and a particle size within a range of 7 to 30 jum. Suitable silica sols are commercially available.
Aqueous solutions of alkali metal silicates, in particular commercially available alkali metal s;licate solutions obtainable under the labels ~aliwasserglas ~potash waterglass~ and Natronwasserglas (sodium water-glass) and containing up to 30~ by weight of SiO2 are poss;ble for use as waterglass. Other suitable waterglass types are those described ;n Hollemann-Wiberg, Lehrbuch der anorganischen Chemie CTextbook of inorganic chem;stry]
71st to 80th edition, published by Walter de Gruyter, 8erlin, page 497 t1971). However, solid alkali metal metasilicates, for example potass;um metasilicate, which contain up to 75% by weight of SiO2 can also be used as waterglass. Sil;ca sol can be used on its own, but it is also possible to use a mixture of water and sil;ca sol, mixtures of water and waterglass or mixtures of water, silica sol and waterglass.
Examples of what can be used as finely pulverulent - water-insoluble sil;ca are the most diverse amorphous or crystalline silicas, with the primary particle size being, for example, 1 to 200 nm and the agglomerate size Le A Z1 277 -be;ng, for example, 0.5 to 10n ~m.
Such silicas are commercially available and des-cr;bed, for example, in H. Ferch, Chemie-Ingenieur-Technik 48, pages 922 et seq. ~197~?. They are in general synthe-S tic silicas~ which can be prepared in various ways~ forexampl-e from silicon tetrachloride, hydrogen and oxygen by the flame hydrolysis method or from quartz and coke by the arc method. Of particular importance are the silicas prepared by the so-called "wet process" and where silica is obta;ned from waterglass and ac;d by precipita-tion and subsequen~ dry;ng or from sand and chalk by the hydrothermal process. All silica products obtainable by th;s process are commerc;ally available.
The finely pulverulent, water-;nsoLuble silica preferably has the following characteristics: specific surface area 30 to 2~000 m2/g, primary particle size 3 to 100 nm, agglomerate size 1 to 40 um, density about 2.0 g/cm3, compacted volume ~according to DIN 53,194) 100 to 2,000 ml/100 9, loss on drying ~according to DIN
53,198) 3 to 7X, loss on ;gnit;on (accord;ng to DIN
55~921) 3 to 15%. pH value (accord;ng to DIN 53,200) 2 to 9, predom;nant pore d;ameter above 200 ~ and S;02 content (relat;ve to dry substance) above 93%.
The finely pulverulent~ water-insoluble s;l;cas to be used can contain small amounts of contam;nants~
for example up to 1X by weight of aluminium (calculated as Al203), up to 0.5~ by we;ght of ;ron (calculated as Fe203) and up to 2X by we;ght of sulphur (calcula-ted as S03), ;n each case relat;ve to the dry weight of the sil;ca.
The silica preferably contains less than O.S~
by weight of alumin;um, less than 0.1% by weight of ;ron and less than 1% by we;ght of sulphur, in each case cal-culated and relative to the dry weight of the silica.
Kieselguhr can also be used as finely pulverulent, water-insoluble silica.
Le A 21 277 Kieselguhr can be the natural product commercially ava;lable under th;s label and described, for example, in Rompp's Chem;elexikon ~Rompp's Chemistry Dictionary~, volume H ~o L, 7th edition, Franckh'sche Verlagshandlung W. Keller ~ Co., Stuttgart~ page ~770 (1973). The natural product is preferably a -Fine-grained, light powder which conta;ns 70 to 90% by weight of amorphous silica, 3 to 12% by weight of water and small impurities of oxides of other elements, for example of aluminium and of iron.
The silica sol and the mixtures containing water~
silica sol and/or waterglass, either of which may contain added amounts of solvents and/or finely pulverulent, ~ater-insoluble silica, do not necessarily require the add;tion of porosity-producing agents. Particularly ~hen larger amounts of Kieselguhr are present, porosity-producing agents can be dispensed with, since kieselguhr exerts a loosening action on the silica-containing layer.
However, one or more porosity-producing agents are pre-ferably added regardless of the presence of kieselguhr.
Suitable porosity- producing agents are the activa-ted carbons, carbon blacks and graphite previously des-cribed and materials which can be decomposed thermally in an easy and largely residue-free manner. Such porosity-producing agents are in themselves known. Possible ex-amples are organ;c and/or inorganic materials, such as ammonium salts, aliphatic alcohols of the empirical for-mula CnH2n+20~ aliphatic dihydroxy, trihydroxy and polyhydroxy compounds~ aliphatic carboxylic acids of the empirical formula CnH2n02 (also in the form of their salts, esters and other derivatives), aliphatic dicarboxyl;c ac;ds of the emp;rical formula CnHzn_204 higher aliphatic carboxylic acids and sugars (also in the form of deri~atives and polysaccharides), and readily and completely decomposable polymers, such as polystyrene.
Examples of single compounds or materials suitable for use as porosity-producing agents are ammonium carbo-Le A 21 277 3~2 - 16 ~
na~e, ammonium hydrogencarbonate, ammonium nitrate, ammo-nium ace-tate, ammonium formate, ammonium oxalate, ethylene glycol, glycerol, sugar alcohols, acet;c ac;d, propionic acid, oxal;c ac;dr sod;um acetate, malon;c acid, ascorb;c ac;d, tartaric acid, citr;c ac;d~ glucose~ sucrose, starch~
cellulose and graph;~e.
The porosity-produc;ng agents preferably used are ammonium salts, oxalic acid and graphite.
The graph;te can be natural or synthetic graphite~
The graphite can contain, for example, 70 to 90% by weight of carbon and 10 to 30~ by we;ght of ash and have a parti-cle s;ze wh;ch is essent;ally below 0~1 mm. The ash fractions in general essentially contain s;l;ca and also alkal; metal and alkal;ne earth metal oxides as well as, if appropr;ate, oxides of ;ron and/or of other transition metals.
In the mass to be appl;ed to the base material the fractions of silica sol, water and/or waterglass and, if appropriate, finely pulverulent water-insoluble sil;ca an~/or porosity-producing agents can vary w;th;n w;de lim;ts. If all s;l;ca constituents present are calculated as anhydrous S;02, the content of silica sol, relative to anhydrous sio2, can be, for example, 10 to 100X by weight, provided no waterglass is used. If s;lica sol and waterglass are used, their total content, calculating all silica constituents present as anhydrous S;0~, can be, for example, 20 to ~0~ by weight, with the waterglass fraction thereof preferably not exceeding 55% by weight. The mass to be applied to the base material should contain enough water, if appropriate together with added solvents, that the mass is highly mobile. The mass can contain, for example, relative to all silica constituents present and calculated as anhydrous sio2, 30 to 95% by we;ght, preferably 40 to ~5~ by weight~ of water.
By varying the composition of the mass to be Le A 21 277 applied to the base material within ~he scope of the limits ;nd;cated, the physical parameters of ~he silica-conta;ning layer formed can be affected, namely, for example, the pore volume, the tmean) pore d;ameter, the pore rad;us d;str;but;on, the poros;ty, the apparent dens;ty, the true dens;ty, the fraction of coarse pores, the fract;on of fine pores, the absorbency, the abrasion res;stance, the mechan;cal strength, the spec;fic (~ET) surface area, the spec;fic active surface area and the surface acidity.
This mass can be applied to the base material by methods which are in themselves known, for example by means of casting~ spray;ng or granulating methods, in wh;ch the particles of the base mater;al are preferably ;n permanent ;ntr;nsic mot;on and ;n wh;ch uniform and constant mix;ng is aimed at.
In applying the mass to the base material it is essentiaL, on the one hand, that the temperature of the base material at the start of the application OT the silica sol or of the mixture is below the softening point of the base material , and, on the other hand, that the water applied to the base material together with the silica sol or the mixture evaporates rapidly.
If use is made of inorganic base materials, which in general have high softening or melt;ng po;nts, their temperature ;s therefore preferably kept above the boiling temperature of water, that ;s above 100C when work;ng under atmospher;c pressure, throughout the ent;re appl;ca-t;on of silica sol or of the mi%tures described above.
Preferable temperatures are w;thin a range of 105 to 800C, in part;cular w;th;n a range of 110 to 400C, more par-~icularly within a range of 110 to 300C.
organic base mater;als can have soften;ng po;nts below the bo;l;ng temperature of water. If organ;c bas materials are used, their temperature at the start of the application of silica sol or of the mixtures described Le A 21 277 3Z~

above is therefore kept below their softening point, even if as a result the temperature is below the boiling tem perature of water. The application of silica sol or of the mixtures described above must then if necessary be carried out more slowly to ensure that the water still evaporates rapidly. Immediately after the organic base mater;al has been coated with a silica-containing layer, the temperature of the base material ;s raiced to values above ~he boiling temperature of water and the application of silica sol or of mixtures is completed at temperatures above the boiling temperature of water. The maximwm tem-perature which can be used in this case depends on the nature of the organic base materialO In general this heating is carried out at temperatures within a range of 15 105 to 300C, preferably 110 to 22QC. Organic hase mater;als wh;ch have a soften;ng po;nt above about ~10C
are treated with silica sol or the m;xture preferably throughout at temperatures above the boiling temperature of water.
If the mass to be applied ~silica sol or one of the mixtures described above~ contains in addition to water sig-nificant amounts o~ solvents having a higher boiling point than water, the temperature of the base material is prefer-ably chosen to be higher than the boiling point of the sol-vent having the highest bo;l;ng po;nt. Care must also be taken that the part;cles of the base material have a res-idual moisture content of less than 5X by weight, prefer-ably less than 1X by weight, before the appl;cation process.
If a spray;ng method is used to apply the mass to the base material, it is possible, for ex-ample, initially to introduce the base material into a heatable coating drum and to apply the mass to be applied by means of nozzles, for example cone nozzles, hollow-cone nozzles, dusting nozzles, one-material nozzles or multi-material nozzles. If a casting method is used, the mass to be applied can be, for example, added dropwise Le A 21 277 i32~

to the mov;ng base material. In granulating methods, -for example, the base material and a finely divided, solid catalytically active substance or a precursor thereo~ are granulated with the aid of silica sol or one of the mixtures described above. SpraYing methods are preferably used.
The t~mperature o~ the mass to be applied is in general not critical~ However, the temperature should not be so high as to evaporate significant amounts of water already before the application to the base material.
Suitable temperatures are therefore for example those within a range of 10 to S0C.
It ;s essential that the mass to be applied is applied to the base material in such a way that the water contained in the mass to be applied is r~pidly evaporated. The water content of the base material and of silica which may have already been applied to the inorgan;c base material must always be belo~ 5% by weight. The water content should preferably always be below 1% by weight. In this way firm adhesion of the layer applied is obtained, in particular when using inorganic base materials.
In applying the mass to an inorganic base material the procedure used may be~ for example, that the base material is heated to about 200 to 250C in a heatable coating drum and is then sprayed with the silica-contain-ing mass until the temperature of the charge has fallen to about 105 to 150C, and the charge is then heated up again to about 200 to 250C and newly sprayed. When strongly porous inorganic base materials are used the spray-- 30 ing is advanta~eously ca-ried out at temperatures within a range of 250 to 300C. This measure can minimise as far as possible the extent to which the silica-containing mass penetrates into the inorganic base material. When ~ using strongly porous inorganic base materials the use of elevated temperatures can also be necessitated by the fact that otherwise the limits indicated above for Le A 21 277 3~

the water content cannot be adhered ~o.
The silica-~ontaining layer can be applied to an organic base material by~ for example, heating the base material in a heatable coating drum to a temperature which is about 5 to 15C below the softening po;nt of the base material. If th;s step has to be carr;ed out at tempera-tures below 100C, the s;lica-containing mass is sprayed on only very br;efly, the water is allowed to evaporate, and the charge is heated back up to the starting tempera-ture and sprayed again with the silica-containing mass.
In this method, the temperature of the charge should preferably not drop belOh 60Co As soon as sufficient silica-conta;n;ng mass has depos;ted on the organic base mater;al for th;s base material to withstand heating to temperatures above 100C w;thout deformat;on~ the spray ;ng ;s carr;ed out at temperatures of 100C, for example at temperatures w;thin a range of 110 to 220C. If the soften;ng point of the organ;c base material is above 110C, appl;cation of the s;l;ca-conta;ning mass may be carried out from the start in the way described above for the use of inorganic base mater;als, without, howeverO
us;ng temperatures so h;gh that the base mater;al deforms.
The max;mum temperature at which organic base materials can be coated depends on the nature of the organic mater-;al. In general, ;t ;s advantageous to avoid temperaturesof above 220C.
The s;l;ca-conta;n;ng layer can be appl;ed ;n such a way that a layer of any mean th;ckness, for example w;thin a range of 10 to 3,000 ~um, ;s formed on the base material ;n one operat;ng step. However, ;t ;s also poss;ble to proceed ;n such a way that, in one operat;ng step, only a th;n layer, for example with;n a mean thickness range of 1 to 100 ~m, is formed and, ;f appropriate, several such layers are appl;ed ;n success;on. It ;s also possible to apply several relatively th;ck layers, for ex-ample those having a mean thickness range of 100 to 1,000 ~um, Le_A 21 277 3Zi~

;n succession. If it is intended to apply a relatively th;ck layer to the base material, for example a layer having a mean thickness above 100 ~m, it is in general advantageous to produce this layer in se~eral operating steps~ by superposing several relati~ely ~hin layers, ~or example by preparing a layer having a mean thickness of 3,000 ~m either in three operating steps ;n each of which layer having a mean thickness of about 1,000 ~m is applied or in 30 operating steps ;n each of wh;ch a layer hav;ng a mean th;ckness of about 100 ~m ;s appl;ed.
If the s;l;ca-conta;n;ng layer is applied to the base material in several operating steps, the intervals between the individual operating steps can be arbitrarily long. It is also possible to use differently composed masses for the individual operating steps, that is to apply in succession several layers ~hich differ in composition. For instance, it is advan-tageous ;n some cases, for example when us;ng strongly porous base materials, or those having a very smooth surface (for example steel spheres~, first to pro-duce a layer from a rnixture containing only water and sil-ica sol and/or waterglass, whereby the porosity of the base material is reduced and/or its ability to bond further layers is improved, and then to apply one or more layers from mixtures which also contain finely pulverulent, water-insoluble silica, porosity-producing agents and, if appropriate, catalytically active sub-stances or precursors thereof.
The thickness of the layer applied in one opera-ting step depends essentially on the water content ofthe mixture to be applied and on the time during wh;ch the base mater;al, wh;ch may already be coated with one or more silica-containing layers, ;s brought ;nto contact with the mass to be applied. To apply layers of the desired thickness by varying these two parameters will not present any problems to an expert.
Le A 21 277 The mean thickness of an individual layer is pre-ferably at least 10 ~m, particularly preferably at least 20 ym.
The thickness of a layer, essentially due to the- me~hods of application, can vary not only from particle to particle but also with;n a particle. However, this is generally without adverse effect on the ut;Lisa-bility of shaped art;cles prepared according to the inven-tion as catalysts or catalyst supports. When using 10 irregularly shaped base materials, for example mill base, ashes or slags, an approximation to the sphere shape generally takes place during application of one - or more layers, since the layer applied is relatively thin at the vertices and strongly convex-shaped areas of 15 the particles, but is relatively thick in concave-shaped regions o-f the particles. Th;s feature likewise generally has no adverse influence on the utilisability of shaped articles prepared according to the invention 35 catalysts or catalyst supports.
After silica has been applied to an inorganic base material, the product thus obtained can, if appro-priate, be thermally aftertreated~ In this step, a very wide variety of temperatures can be used, for example those within a range of 200 to 1100Co In this step 25 preferable temperatures are ~ithin a range of 200 to 700C, particularly preferable temperatures are within a range of 200 to 500C, and very particularly pre-ferable temperatures are within a range of 20û to 300C.
A thermal aftertreatment is particularly advantageous 30 if poros;ty-producing agents have been used.
After silica has been applied to an organic base material a thermal aftertreatment at temperatures within a range of Z00 to 1,300C is necessary in every case to re-move the organic base material. Preferable temperatures 35 for this step are within the range of 300 to 700C. The general procedure followed is to remove the organic base Le A 21 277 ~632~

material slowly via melting~ decomposition~ carbonisation and slow combustion, for example by raising the tempera-ture from 200 to 700C at a rate of 30 to 70C per hour and then ma~ntaining 700C until the entire residual carbon, recognisable by the black discoloration of the silica-containing layer~ has been combusted. As a result hollow spaces are obta;ned wh;ch are surrounded by a layer conta;n;ng porous s;l;ca. The organic base material can also be removed only when catalyt;cally act;ve mater-;als, or precursors thereof, haYe been ;ntroduced intothe silica-containing layer~
If sil;ca-containing shaped articles which contain catalytically active substances or precursors thereof are ;ntended to be prepared accord;ng to the invention, cata-lytically active substances or precursors thereof, forexample of the type descr;bed above, can be applied to the base material together with the s;lica-contain;ng mass. In th;s step, the temperatures dur;ng and after appl;cat;on of the layer(s) conta;n;ng sil;ca are to be controlled in such a way, if apprupriate, that the catalytically active substances, or the precursors thereof, do not change in an undesirable way. However, ;t is also possible to proceed by first applying to the base material a mass which produces a sil;ca-containing layer free of catalytically active substances or precursors thereof and then ;ntro-dùc;ng solut;ons or suspens;ons of catalyt;cally act;ve substances, or precursors thereof, ;nto the s;l;ca-con~
ta;ning layer, for example by customary impregnating or spray;ng methods.
Regardless of how the catalyt;cally act;ve sub-stances or the;r precursors have been ;ntroduced, the most diverse aftertreatments can be performed, if appropriate, to obtain active or more act;ve catalysts. This after-treatment can consist, for example, of a heat treatment~
a reduction or an ox;dation.
The products according to the invention are Le A 21 277 ~63.~2 dist;nguished by the fact that a layer of any th;ckness and wh;ch con~a;ns porous silica surrounds a hollow space or an opt;onal inorganic base material~ If these products are prepared as described above, solid silica~containin~
layers are obtained. The products according to the inven-tion can be used 3S catalyst support material provided they do not contain any catalytically activ~ centres.
They can be used to prepare a very wide variety of cata-lysts which then all have the advantage that the catalyti-cally active constituents are present only in the silica-containing layer, a state of affairs which yields very ac-tive and selective catalysts and wherein catalytically ac-tive material can be saved, since the interior o~ these catalysts is free thereof. If catalytically active substan-ces are introduced or produced together with or after thesilica-containing layer(s) has or have been applied, these advantages are likewise obtained. Compared to known cata-lysts, which have a TiO2-containing layer, the products according to the invention have the advantages that they are porous not only at the surface but also within the applied layer(s) and that in respect of catalytically active constituents they are not restricted to those which have low melting points. The stability of the silica-containing layer to ;ncorporated catalytically active components of acid;c character and to acidic reactants has proved particularly advantageous, ~hereas TiO2-containing layers are uns.able~ to the point of decomposition~ under these conditions due to a chemical change of the Tio~.
Silica-containing shaped articles according to the invention which contain catalytically active substan-ces can be used as catalysts.
For example, an excellent hydrogenation catalyst can be obtained from a product according to the invention and which does not contain catalytically active constitu-ents by applying a palladium salt solution by impregnationfor example an aqueous palladium chloride solution, then Le A 2 277 3~i~

dry;ng and reduc;ng the pallad;um salt. A catalyst thus prepared is particularLy su;table, for example, for the hydrogenat;on of nitro compounds.
I~ products according to the ;nvention and free of catalytically active constituent3 are to be impregnated with metal salt and/or noble metal salt solutions, for example one or more metals can be appLied by ;mpregnat;on, fo~ example dissolved ;n the form of the;r salts. Phys;- -cal parameters, such as, for example, absorbency of the support and solubil;ty of the metal and/or noble me~al salts, can necessitate several impregnat;ons to obta;n the concentration of active ;ngredient required in the prepared catalyst. The concentrat;on of the metal salt and/or noble metal salt solut;ons is adjusted in such a ~ay, for example, that the prepared catalyst conta;ns 0.5 to 200 9, preferably 1 to 100 9, of one or more cata-lytically act;ve components per litre of support. If the catalyt;cally act;ve component ;s a noble metal or a noble metal compound or ;f se~eral catalyt;cally act;ve components are present ;n the support catalyst of wh;ch at least one ;s a noble metal or a noble metal compound, the content of these components can be, for example, in each case 0.5 to 100 9, preferably 1 to 50 9~ particu-larly preferably 2 to 20 9, calculated as noble metal in elemental form, per litre of support.
For example, such a catalyst can contain 1 to 20 9, preferably 2 to 10 9, of pallad;um or 1 to 100 9, preferably 2 to 50 9, of a non-noble metal, or, in the case of a multi-component support catalyst, 1 to 20 9 of palladium, 1 to 50 g of a first transition element and 1 to 50 9 of a second transition element, in each case calculated as the metal in elemental form, per litre of support.
How this impregnating is performed in industry may be illustrated by means of the preparation of a palla-dium-contain;ng Sio2/steat;te catalyst:
Le A 21 277 a support containing a silica layer is prepared according to the invention from steatite as the inorganic base material and impregnated commensurate w;th its absor-bency with a metal salt solution, for example sodium palladium chloride, and dried. If necessary, the metal salt applied is first reduced to metal by known methods, for exalnple by treatment with hydrazine hydrate solution, before a subsequent washing process and drying.
In the catalyst thus prepared the palladium is exclusively in the silica-containing layer. The support catalysts thus prepared can be used for the most diverse catalytic processes, for example hydrogenation, dehydro-genation, hydrogenolysis, oxidation, acetoxidation, poly-mer;sat;on, isomer;sation or cyclisation. In these cata-lytic reactions support catalysts thus prepared can be used not only when working in the bottom phase but also when working ;n the trickle phase or the gas phase. The trickle phase and the gas phase are preferable. The reactions can be carried out under atmospheric pressure, overpressure, or reduced pressure.
~ atalytic hydrogenations are a preferable area of application for catalysts thus prepared. According to the composition of active ingredient the catalysts are particularly suitable for hydrogenating aliphatic multiple bonds, for example for selective hydrogenations, for the nuclear hydrogenation of aroimatic systems or for hydrogenating certain constituents, for example nitro or carbonyl groups contained in aromatic systems. Cer~ain compositions of active ingredient of the support catalysts thus prepared have a preferable application in catalytic hydrogenations, for example of substituted aromatics, wherein, depending on the combination of catalytically active substances as well as on other process parameters, such as temperature or pressure, either the aromatic system and/or the substituent can be hydrogenated.
A further important area of use is the acetoxida-Le A 21 277 3%~

tion of olefines~ for example the formation of vinyL
acetate from ethylene, acetic acid and oxygen wsing cata-lysts prepared according ~o the invention and containing palladium, gold and 3lkali metal acetate as catalytically active sub3tances.
Catalysts prepared by the process accord;n~ to the invent;on and conta;ning the act;ve substance palla-dium on S;02/steat;te are preferably used for the cata-lytic hydrogenat;on of n;troaromat;cs, for example of n;trobenzene, n;trotoluene, d;n;trobenzenPs~ din;trotolu-enes, trin;trotoluenes, nitrophenols and nitrochloro aromatics, to the corresponding aromatic amines. In the catalytic hydrogenation of nitro compounds~ the gas phase reaction is preferable for mononitro compounds, while the liquid phase and, especially, the tr;ckle phase is pre-ferable for d;nitro or tr;n;tro compounds. Not only ;n the gas phase but also ;n the trickle phase the compound to be reduced ;s generally passed over a fixed catalyst.
An excess of hydrogen ;s advantageously usedO When work-;ng ;n the tr;ckle phase the nitro compound to be reduced;s usually d;luted w;th the am;no compound result;ng in the reduction or w;th another diluent to such an extent that carry;ng out ~he reduction is free of hazardsJ The preferable reaction temperature in the trickle phase is ZS w;th;n a range of 50 to 150C, and the preferable pressure range is between 1 and 100 bar.
The hydrogenat;on ;n the gas phase ;s preferably carried out within a temperature range of 150 to 350C
and under 1 to 10 bar.
A very general po;nt to be made ;s that the appli-cation of products according to the ;nvent;on as catalysts and catalyst supports ;s virtually not restricted. Vir-tually any catalyt;cally active substance suitable for heterogeneous and/or homogeneous catalys;s can be intro-duced, or produced, ;n the s;l;ca-conta;ning layer of the prsducts according to the invention~ and the catalysts Le A 21 277 3Z~

thus obta;ned can then be used in processes in which the act;v;ty of the particular catalytically active sub-stances is known. The process conditions of such cata-lytic processes (quantities used, pressure, temperature, residence time and the like) vary in general when using catalysts according to the invention only to the extent possible on the basis o~ the improved activity and/or selectivity of the catalysts according to the invention.
In many cases it is also possible simply to use catalysts accord;ng to the ;nvent;on ;n lower act;ve ingredient amounts than h;therto and obtain the same results as h;therto w;th unchanged process;ng conditions.
Examples wh;ch may be listed of the use of cata-lysts accessible according to the invention are:
a) catalys~s for hydrogenations and which contain noble metals and/or other metals~ and which are~ in particular, for example the following:
For the hydrogenation of triple to double bonds catalysts which contain palladium or pallad;um with added amounts of lead, zinc, copper, chrom;um or amines and sulphur compounds. For the hydrogenation of diolef;nes to mono-olefines catalysts which conta;n pallad;um. For the hydrogenation of monoolef;nes, for example ;n the har-den;ng of fat~ catalysts wh;ch conta;n Raney nickel.
For the hydrogenat;on of unsaturated aldehydes to satura-ted aldehydes catalysts which contain platinum metals.
For the hydrogenation of unsaturated nitriles to saturated nitriles catalysts which contain palladium. For the nuclear hydrogenation of aromatics catalysts which contain Raney n;ckel or rhodium. For the nuclear hydrogenation of phenols to cyclohexanols catalysts which contain palla-dium. For the hydrogenation of phenol to cyclohexanone catalysts which contain plat;num. For the hydrogenation of aldehydes to alcohols catalysts wh;ch contain nickel.
For the hy~rogenation of unsaturated aldehydes to unsatu-rated alcohols catalysts which contain platinum, if appro-Le A 21 27?

priate ~ith added amounts of z;nc and/or ;ron. For the hydrogenation of carboxyL;c ac;ds to alcohols catalycts wh;ch conta;n Raney cobalt~ For the hydrogenat;on of carboxyl;c anhydr;des to lactones or diols catalysts wh;ch conta;n n;ckel. For the hydrogenation of acid chlor;des to aldehydes catalysts which conta;n palladium and sulphur-containing compounds. For the hydrogenation of nitriles to amines catalysts which conta;n either Raney cobalt or iron together with manganese and phos-phorus-containing add;tives. For the hydrogenation of unsaturated nitriles to unsaturated am;nes catalysts which contain copper chrom;te and added amounts of bar;um compoundsc For the hydrogenat;on of aldox;mes to hydrox-ylam;nes catalysts wh;ch con~a;n pallad;um or plat;num.
For the hydrogenation of aldoximes to amines catalysts wh;ch conta;n rhod;um or plat;num. For the convers;on of ketones by means of hydrogen and ammonia to am;nes catalysts which contain cobalt and nickel. For the con-version of alcohols with ammon;a and/or am;nes and hydro-gen to am;nes catalysts wh;ch conta;n n;ckel. For thehydrogenat;on of n;tro compounds to am;nes catalysts wh;ch conta;n copper chrom;te and bar;um compounds or pallad;um. For the ammon;a synthes;s catalysts wh;ch conta;n ;ron w;th added amounts of alum;n;um, potass;um, magnesium and s;l;con compounds.
b~ Catalysts for dehydrogenat;ons and oxidative dehydro-genat;on and wh;ch contain metal compounds, and wh;ch are, in particular, for example, the following:
For the oxidative dehydrogenation of olefines to d;ole-f;nes, ;n part;cular the convers;on of butenes to buta-d;enes, catalysts wh;ch contain magnesium ferrite w;th add;tives contain;ng phosphorus and n;ckel or add;t;ves conta;n;ng calc;um n;ckel phosphate and, ;f appropr;ate, stront;um and/or chrom;um or m;xed molybdates (for example n;ckel cobalt ;ron b;smuth molybdate and, if appropriate, addit;ves containing phosphorus and potassium) or nickel Le A 21 277 -i322 calcium phosphate or mixed antimony tin oxides. For the dehydrogenation of hydrocarbons, in particular from ethylbenzene to styrene, catalysts which contain iron oxide and added amounts of chromium oxide and potassium S compounds. For the dehydrogenat;on of l;near hydrocarbons to aromatics~ ;n part;cular from n-hexane to benzene, cataLysts wh;ch conta;n chrom;um ox;de and alum;nium ox;de w;~h added amounts of alkal; metal compounds.
For the convers;on of cyclohexanol to cyclohexanone, catalysts wh;ch conta;n z;nc ox;de and added amounts of alkali metal and alkal;ne earth metal compounds.
c) Catalysts for hydrat;on or dehydration and ~h;ch conta;n phosphorus compounds and/or zeolites, and ~hich are, in part;cular, for example as follows:
For the hydrat;on of olef;nes to alcohols, for ex-ample from ethylene to ethyl alcohol, catalysts wh;ch conta;n phosphor;c ac;d and sil;con dioxide. For the dehydration of secondary alcohols to olef;nes, ;n part;cular from ~-hydroxyethylbenzene to styrene, cata-lysts wh;ch conta;n sod;um metaphosphate and sil;condiox;de or zeolites or alum;n;um ox;de~ For the conver-s;on of carboxylic a~;ds using ammon;a with elim;nat;on of water to gi~e n;tr;les, ;n part;cular from ad;p;c ac;d to ad;pod;n;trile, catalysts which contain phosphoric ac;d and s;l;con d;oxide. For the dehydrat;trat;on of 1,4-butaned;ol to tetrahydrofuran, catalysts wh;ch conta;n ac;d;c zeol;tes.
d) Catalysts for reactions in the presence of carbon monox;de and wh;ch contain transition metals or transition metal compounds, and which are, ;n part;cular, for example the follow;ng:
For the synthes;s of alcohols, in particular of methanol, from carbon monoxide and hydrogen, catalysts which contain either z;nc ox;de or chrom;um ox;de or copper and added amounts of z;nc ox;de, alumin;um ox;de, chrom;um ox;de and/or alkal; metal compounds. For the F;scher-Tropsch Le A 21 277 3~

synthes;s catalysts which contain iron and added amounts of alkal; metal compounds~ thorium oxide and magnesium oxide or catalysts wh;ch contain iron and aluminium oxide.
For methanation catalysts which contain nickel and/or aluminium oxide or spinels or catalysts which contain ruthenium. For the conversion of carbon monoxide by means of steam catalysts which contain iron oxide and chromium oxide, or copper, zinc oxide and aluminium oxide or cobalt molybdenum sulphide and alum;nium oxide. For ~0 steam reforming catalysts which contain nickel and alkaLi metal compounds.
e) Catalysts for ammoxidation and which contain transition metals, and which are, ;n particular, for example the following:
For the conversion of propylene to acrylonitrile, cata-lysts ~hich contain vanadium antimony oxides or molybdenum bismuth iron cobalt ~nickel) oxides and added amounts of potassium compounds and phosphorus compounds or of antimony iron oxides. For the conversion of o-xylene to phthalodinitrile catalysts which contain vanadium antimony oxides.
f) Catalysts for oxidation reactions and which contain transition metals or transition metal oxidesf and which are, for example, the following:
For the conversion of olefines to unsaturated aldehydes, in particular from propylene to acrolein, and from i-bu-tene to methacrolein, catalysts which contain copper oxide or molybdenum bismuth iron cobalt (nickel) phos-phorus oxides or molybdenum niobium (tantalum) bismuth oxides, in each case with promoters if appropriate.
For the conversion of unsaturated aldehydes to unsaturated acids, in particular ~rom acrolein to acrylic acid and from methacrolein to methacrylic acid, catalysts which contain molybdenum vanadium tungsten oxides or molybdenum phosphorus niobium (tantalum) oxides~ in each case with promoters if appropriate~ For the conversion of C4-~ea 21 277 hydrocarbons to male;c anhydr;de, catalysts which conta;n vanad;um ox;de and phosphorus ox;de or molybdenum anti-mony vanad;um oxides, in each case with promoters if appropriate. For oxyacetylations of olefines wi~h the formation of esters of ur~saturated alrohols, for example vinyl acetate and allyl acetate~ catalysts which contain palladium and alkali metal acetates and, if appropriate, further metals or metal compounds (for example, gold, bismuth~ cadmium or manganese). For the ox;dation of ethylene to ethylene ox;de, catalysts which contain silver and, ;f appropriate, added amounts of alkal; metal com-pounds. For the oxidation of alcohols to aldehydes, in particular of methanol to formaldehyde, catalysts which contain silver or molybdenum iron ox;des. For the ox;da-t;on of hydrocarbons to carboxylic ac;ds or aldehydes,;n part;cular from n-butene to acet;c ac;d, catalysts wh;ch contain titanium vanadate. For the ox;dat;on of aromat;cs to ac;d anhydrides or quinones, for example from benzene, naphthalene or o-xylene to phthalic anhy-dride and, ;f appropriate, naphthoqu;none, catalystswh;ch conta;n vanad;um pentox;de together with added amounts of molybdenum ox;de/phosphorus ox;de or silicon d;ox;de/potassium pyrosulphate and for the oxidation of anthracene to anthraquinone catalysts ~hich contain vanadium pentox;de.
g) Catalysts for clean;ng gas and which contain metals or metal ox;des, and wh;ch are~ in particular~ for example the following:
For the detox;ficat;on of gases from ;nternal combust;on eng;nes, catalysts wh;ch conta;n plat;num and ruthen;um or plat;num and pallad;um or plat;num and rhod;um~ ;n each case w;th promoters ;f appropr;ate. For the removal of hydrogen sulph;de by the Claus process, catalysts wh;ch conta;n act;vated alum;na. For the removal of small amounts of chlor;ne or sulphur, catalysts which contain copper or z;nc ox;deA For the removal of small Le A 21 277 ~ 33 -amounts of carbon monoxide or carbon d;oxide, catalysts which Gonta;n n;ckel and magnes;um aluminium sp;nell or ruthen;um.
The examples wh;ch follow ;llustrate the present invent;on w;thout restr;cting ;t in any way.
Examples Survey:
Part A
~escription of starting materials 10 Part B
Description of methods for preparing products according to the invention Example 1 Spraying method - single coat;ng 2 Spraying method - multiple coating 3 Thermal aft~rtreatment Part C
Comparison of catalysts according to the invention with the state of the art Example 1 Acetoxidation preparation of vinyl acetate 2 Oxidation of naphthalene 3 Hydrogenation of o-nitrotoluene Part D
Preparation exampLes of products according to the inven-tion Examples 1-29 The percentage data, unless otherwise indicated, are percentages by weight.

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Material No~
9. Silica sol _. .
Type ~ayer Kieselsol ~sil;ca sol) 300 30% ~commercial name) S;2 content LX~ about 3û
NazO content C%] about 0.35 pH value about 9.8 Dens;ty Cg/cm3~ 1.2 Yiscosity CmPa.sec~ 4-6 Specific surface area about 280-320 Cm2 / 9~
Particle size Cnm3 7-8 Ionic character an;on;c Colour clear Material No.
10. Silica Type Ultrasil VN2 (commPrcial name) Loss on ignitior at 1000C CX] 11 of which moisture at 105C ~X]
SiO2 content C%] 87 Al203 content CX] 0.2 Na20 content C%] 0~8 S03 content C%] 0.5 Fez03 content ~%3 Co.05 Specific density Cg/cm3] 2.0 30 Compacted density ~g/litre]200 pH value 7 8ET surface area 130 ~m2/9~
Mean primary particle 28 size Cnm]
Le A 21 277 3~

Material No.
11. Waterglass Type Potass;um sil;cate ;n the form of an aqueous solution Dens;ty Cg/cm3~ 1.25 S;2 ~] 21 K2 C%~ 8.1 Material No.
12. K;eselguhr Ty~e Purified and ignited in accordance with DAB (German Pharmacopoeia ) Supplement B6 SiO2 C%] >96 pH value 5_9 Fract;ons soluble ;n hydrochlor;c ac;d CX~ ~1 Ac;d-soluble sulphate C%~ ~0.02 Acid-soluble ;ron CX] <0.04 Loss on ;gnition (600C) C~3 ~0.5 Sieve residue ~ .1 mm CX] ~2 Material No.
13. Vanadyl oxalate solution Aqueous solution containing 17~8% by weight of vanadyl oxalate~ which corresponds to 10.4% by weight of V205, and having a dens;ty of 1.165 g/cm3.
Material No.
14. Activated carbon Bayer Carboraffin P tcommercial name~
Water at time of packing ~10 [% by weight]
F;neness of grind C% by 20 75 ym weight~
Vibrated density tkg~ about 0.3 litrel Le A 21 277 ;3~

p~ value 5-7 Ash C% by weight~ 2.0-3~0 MoLasses factor about 1.0 Material No.
5 15. Zeolite Bayer Zeolite T-Pulver Czeolite T powder] (commercial name) (alkal; metal alumosilicate of A type in the K form) Pore width Cnm] 40 Crystall;te d;ameter C~m~ 2-10 Bulk dens;ty Cg/litre] 350 pH ~alue 11 Material No.
16. Ion exchange material ~ . .
Bayer Lewasorb S~ 12 (commercial name) Supply form Na Grain form Microgranules Basic structure Polystyrene Anchor group Sulphon;c acid Grain size range Cnm~ ~0.1 (95% ~0.075 Bulk density Cg/litre] 700-800 Density Cg/cm3] 1.28 Material No.
17. ALumina Identical to Material No. 8, but particle si~ ~ 0.1 mm Material No.
18. Polystyrene Granules, ellipsoid up to 3 mm; bulk density 682 g/l;
softening temperature: 75 to 80C; commercial pro-duct from BASF under the name Polystyrol 143 c.
Material No.
19. Polymer alloy of polycarbonate and ABS
Granules, extruded pieces up to 3 mm long; bulk density 640 g/l, softening temperature; 120C;
commercial product from Bayer AG (see Bayer publica-tion KL 46150 of june '81).
Le A 21 277 Material No~
20. Polyethylene Granules, ellipso;d up to 3.5 mm; bulk dens;ty 638 g/l; softening temperature: 90C; commercial product from Bayer AG (see Bayer publication KL 43570 o~ June '82).
Ma~erial No.
21. Cellulose ester - Granwles, extruded p;eces up to 3.1 mm; bulk den-sity 754 g/l; soften;ng temperature: 60 to 11ûC;
commercial product from Bayer AG (see Bayer publ;cao t;on KL 40001 of August '75).
Mater;al No.
22. Glass f;bre re;nforced_polyam;de Granules, extruded pieces up to 3.5 mm long; bulk den-sity 730 g/l; softening temperatureO 255C; 50%
glass fibre content; commerc;al product from Bayer AG
(see Bayer publicat;on KL ~0360 of Apr;l '78).
Mater;al No.
23. Polycarbonate Cylindrical granules up to 3 mm; bulk density 773 g/l; softening temperature up to 150C; commercial product from Bayer AG (see Bayer publication KL 46~00 of August '79).
Mater;al No.
24. Acrylon;trile-butad;ene-styrene polymer (ABS polymer) Granules cut ;n the form of cubes, up to 305 mm;
bulk density 673 g/l; softening temperature 102C;
commercial product from Bayer AG (see Bayer publica-tion KL 41654 of October '78).
Material No.
25. Glass fibre reinforced polyester Granules, extruded p;eces up to 3.8 mm; bulk den-s;ty 864 g/l; soften;ng temperature up to 185C;
30% glass f;bre content~ commerc;al product from Bayer AG (see Bayer publicat;on KL 41100 of June '81~.
Le A 21 277 i3~

Part B Descr;pt;ons of methods for preparing products according to the invention using inorganic base materials Example 1: Spray method - single coating 1615 9 of Material No 1 ~see Part A) are initially introduced into a 50 litre capacity, heatable coating drum and heated to 200C at a speed of 3 rpm.
Meanwh;le, 443 g of silica sol, 133 9 of Ultrasil VN2 and 133 9 of kieselguhr ~Materials Nos. 9, 1û and 10 12, see Part A) are st;rred ;n a 3 litre container together with 1300 9 of water to give a 20X streng~h by w~ight suspens;on. Thi 5 suspension is discontinuously sprayed pneumatically w;th continuous stirring from a pressure vessel onto the continuously moving, hot, in;tiaLly intro-15 duced ;norganic base material at 200C.
In this spray;ng step, the speed of the drum ;s ;n-creased ~lith;n 15 m;nutes from 3 to 15 rpm and 300 9 of suspens;on are sprayed on. As soon as the temperature of the mov;ng mater~al has d;pped below 150C, the spray-20 ;ng process ;s discc:ntinued until 200C is again reached.
The 1709 9 of suspension still present are discontinuously appl;ed w;th;n 45 minutes at a speed of 15 rpm. During this period, the moving material is maintained within the temperature range of 15û~200C. After the applica-25 tion of the product is complete, the material is allowed to cool down to 40C while the drum is stationary and the drum is then emptied.
1765 9 of a product containing 150 9 of silica in the form of a layer having a mean density of 175 lum are ob~
30 tained. The absorbency of this product is 4.2% while its bulk density is 1428 g/litre and it has a residual moisture content of ~1%.
Example 2: Spraying method - multiple coating Corresponding to Part ~ Example 1, 4038 9 of Mate-35 rial No. 1 are sprayed with 4500 9 of a mixture consisting of 100û 9 of silica sol, 300 9 of Ultrasil VN2, 300 9 Le A 21 277 3~;~

of kieselyuhr ~Materials Nos. 9~ 10 and 12, see Part A) and 2900 9 of water in the course of 2 hours. 400 9 of the total mixture are applied w;thin the first 15 minutes, and the rest is applied in the rema;n;ng 105 minutes.
~494 g of a product conta;n;ng 456 g of siLica ;n the form of a layer hav;ng a mean thickness of 150 ~m are obtained~
In a further operating step, 2085 9 of the product are sprayed again under the same cond;t;ons with 4500 g of the abovementioned mixture.
2498 9 of product containing 413 9 of silica in the form of a second layer are obtained. This product now has a total silica layer having a mear; total thickness of 700 ~m, a bulk dens;ty of 1180 g/l;tre and an absorbency of 11.9 ml/10û 9.
Example 3: Thermal aftertreatment The silica-contain;ng product obtained in accordance ~ith Part B Example 2 after a two-fold coating was subjected to a thermal aftertreatmentO in which the product was thermally treated within a range of 200 to 1100C
at various temperatures for 3 hours each, namely up to 500C in the coating drum by means of an acetylene oxygen burner and up to 1100C in an ignition furnace. The thermal aftertreatment produce~ the following BET surface areas as a function of the temperature.

Temperature 200 300 400 500 600 700 800 900 1000 110U
~ ~: ]

~ET surface area rela-30 tive to original coa-ted spheres ~m2/g] 25.8Z6.32S.b~25.924.421.46.9 1.2 0.5 002 Le A 21 277 ~q~32~

Identical results are obtained when the thermal after~reatment is carried out in an ignition furnace from the start.
Part C Comparison of catalysts according to the invention __ with the state of the art Example 1: Acetoxidation, preparation of vinyl acetate a) Comparative catalyst German Patent Specification 1,668,08~ describes a catalyst for synthesising v;nyl acetate. Replication of the examples o~ this patent specification shows that the catalyst support conta;ns an interior zone which con-tains a palladium/gold alloy, whereas the alkali metal acetate is distributed throughout the entire support.
The catalyst produces 245 9 of vinyl acetate per hour and per litre of catalyst at 140C. The catalyst is prepared according to Example 1 of German Patent Spec;fica-tion 1~668,088 by treat;ng the support simultaneously with a solution of palladium salts and gold salts and a solution wh;ch conta;ns compounds capable of reaction on the catalyst support w;th the palladium salts and the gold salts to form water-insoluble palladium and gold com-pounds, then converting the water-insoluble palladium and gold compounds by treatment w;th reducing agents into the noble metals and then washing out the water-soluble compounds. Then alkali metal acetate (potassium acetate) is applied by impregnation, so that the prepared catalyst contains about 30 9 of potassium acetate/litre.
b~ Catalyst according to the invention 1180 9 = 1000 ml of the product prepared in Part B Example 2 by two-fold coating are impregnated with 140 ml of a solution containing 3.3 9 of Pd in the form of Na2PdCl4 and 1.5 9 of Au in the form of HAUCl4.
The volume of the impregnating solution corresponds to the absorbency of the product. To reduce the noble metals the product thus impregnated is coated with 5% strength hydrazine hydrate solution and left to stand for 4 hours Le A 21 277 ~9~i3~2 - ~3 -to complete the reduct;on. The produ~t is then washed with water, and adhering water is then removed by drying.
1168.7 9 of a catalyst which, commensurate with its absor-bencyr is further impregnated with 135 ml of an aqueous solution containing 15 9 of potassium acetate, are thus obtained. After a drying process at 115C, 1180 9 =
~70 ml of a catalyst ~hich can be used for preparing vinyl acetate are obtained.
c) Preparation of vinyl acetate 900 ml of the catalyst prepared in accordance with b) are pa~ked into a 2 m long react;on tube of 25 mm inter-nal diameter under the cond;t;ons descr;bed ;n German Patent Specif;cation 1,668,088, Example 5. 77 mols of ethylene, 19 mols of gaseous acetic acid and 5.8 mols of oxygen are passed per hour over the catalyst at 140C
and under a pressure of 8 bar. 357 9 of vinyl acetate were formed per hour and per litre of catalyst.
Example 2: O~idation of naphthalene a) Comparative catalyst Catalyst A of Example 1 of German Offenlegungs-schrift 2,453,232 ~as prepared.
In this preparat;on, a vanadyl sulphate solut;on obta;ned from V205, H2S04 and S02 ;s mixed w;th finely pulverulent silica prepared from potassium silicate solution and suLphur;c acid. The paste thus obtained is introduced into perforated plates having a thickness of 5 mm and a diameter of 5 mm and dried for 2 hours at 50C. The shaped articles thus obtained are then dried at 125C and then heat-treated for 12 hours at 425C.
This produced Catalyst 1.
b) Catalyst according to the invention Corresponding to Part P of Example 1, 500 9 of silicon carbide (see Part A~ Material No. 7), 253 9 of silica sol, 76 9 of Ultrasil VN2, 76 9 of kieselguhr (Mate-rials Nos. 9, 10 and 23, see Part A), 106 9 of 97% strengthsulphuric acid, 301 9 of an aqueous vanadyl oxalate solu-Le A 21 277 ~9~ 2 tion ~corresponding to 31.8 g of vanadium pentoxide) and 183 9 of ~o-tassium sulphate are mixed with 215 9 of water to give a 46X strength suspens;on. This suspension is appl;ed to the s;licon carb;de ;n a manner corresponding to Part B Example 1.
965 9 of a coated product are obta;ned w;th a Layer thickness of 1000 ~m. Th;s produced Catalyst 2.
c) NaphthalenP ox;dat;on Naphthalene was reacted with oxygen in the presence of Catalyst 1 and, separately thereof, in the presence of Catalyst 2, both reactions being carr;ed out under the conditions described in German Offenlegungsschrift 2,453~232. The reactions were carried out in a 3 m long steel reaction tube hav;ng an ;nternal d;ameter of 30 mm and being heated by means of a salt bath. A gas mixture of 94% of nitrogen and 6X of oxygen was passed at a rate of 4 Nm3/h into the reactor, first at room temperature under a pressure of 6 bar~ This gas mixture was heated to 200C and then additionally enriched with water at a rate of 300 ml/hour. The mixture was then heated to 350C, and the catalyst was treated for 24 hours at this temperature and under 6 bar with the n;trogen/oxygen/
steam m;xture. The temperature was then reduced to 320C
and naphthalene was passed ;n the form of a gas at a rate of 690 g/hour over the catalyst ;n addition to the mixture contain;ng nitrogen, oxygen and steam~ The temperature was then increased to 360C at a rate of 6C/hour.
After the catalyst had run for 500 hours the foLlow;ng results were obta;ned:
Cata- Space-t;me yield (g Space-time yield Ratio by weight lyst of naphthoquinone (g of phthalic of naphthoquin-per l.itre of cata- anhydr;de per one to phthal;c lyst and per hour) l;tre of cata- anhydride lyst and per hour) __ __ _ 1 39.1 50.7 0.77:1 2 45.8 46.4 0.98:1 _., __ _ _ . _ __ _ .. _ ___ ._ . _ _ Le A 21 277 ~63~Z
- ~5 -Catalyst 2 thus produced cons;derably ;mproved y;elds ;n respect of the naphthoqu;none space-time yield and ;n respect of the ratio of naphthoquinone to phthalic anhydr;de.
Example 3: Hydrogenation of oYnitrotoluene a) Compara~ive catalyst German Patent Specification 1,545~297 describes the preparation of a hydrogenation catalyst. Example
4 was repeated in such a way that a catalyst containing
5 g of Pd per l;tre o-f L; spinel was obtained. This produced Catalyst 1.
b) CatalYst according to the invention Corresponding to Example 24 (see Part D), 50 ml = oS g of a support tprepared in a manner corresponding to Part D of Example l5~ are impregnated with 5.3 ml of a solution which contains 1.67 9 of Na2PdCl4 (corres-ponding to 0.25 9 of palladium)~ 20 ml of a 10~ by weight strength hydra~ine solution are added to convert the palla-dium into the elemerltal state, and the support is washed with demineralised water until neutral and chloride-free and then dried to constant weight at 110C in a stream of warm air.
50 ml of a catalyst which contains 5 g of Pd per litre of catalyst are obtained~ This produced ~atalyst 2.
c) Hydrogenation of o-nitrotoluene The hydrogenation of o-nitrotoluene is carr;ed out under atmospheric pressure in a shaking flask with a small built-in basket to receive the catalyst. In each case 10 ml of catalyst, 5 9 of o-nitrotoluene and 35 ml of methanol are introduced into the flask at 50C and under 0.1 bar hydrogen pressure. The quantity measured was the time of hydro~en absorpt;on.

Le A 21 277 ~ 46 -Ca~alyst ~Iydrogenation time Conversion of o-nitrotoluene _ Cmin~ c%]

1 270 ~8.9 2 220 99.0 S Catalyst 2 produced improved value in respect of hydrogenat;on time and ~he degree of conversion of o-n;trotoluene.

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Examples 20 and 20a Procedure in accordance with Part B Example 1; prepara-tion of catalysts with the addition of porosity~producing -agents.
.
5 Experimental conditions _ Example No.
20a ._ Starting materials - No. from Part A -Inorgan;c base material No.
10 Amount used Cg~ 1615 1ol50 Silica sol No. 9 9 Amount used Cg] 288 3335 Kieselguhr No~ 12 Amount used Cg] 80 15 Potassium waterglass No.
Amount used Cg~ _ _ Ultrasil No. 10 Amount used Cg] 86 Vanadyl oxalate solution No. 13 13 20 Amount used Cg] 344 4498 Potassium sulphate Cg] 209 2668 Sulphuric acid 97~ Cg] 121 1511 Water Cg~ 816 3200 OxaLic acid dihydrate Cg]125 25 Graphite Cg~ - 2400 Yield Cg] product 2095 23305 An increase in weight relative to the weight of inorganic base 30 material used Cg] 480 7155 ~%] 30 44 The products thus obtained are catalysts suitable for the oxidation of naphthalene. They were activated by passing 35 over 1 m3 of air per litre of catalyst for 8 hours at 40~C, Le A 21 277 The graph;te used ;n Example 20a ;s a so-called fine powder graph;te obta;ned from Messrs. ~rockhues, N;ederwalluf ~Federal Republ;c of Germany~. According to its specif;cat;on, th;s graphite has a particle size ~of 95~ belo~ û.1 mm, a carbon content of 85X by ~eight and an ash content of 15~ by weiyht.

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3~

Examples 24-29 Var;ous products according to the invention and coated with a silica-conta;ning layer are coated with various act;ve ;ngredients.
Preparat;on and properties of the starti~ng products:
Preparation Absorbency Bulk den-Cg of ~ater/ slty Cg/
100 9 of litre of starting starting material~ material~

. ~
for Example 24 In accordance 8.2 1296 with Part D
Example 15 15 for Examples 25 In accordance 4.2 1428 to 29 with Part B
Example 1 _ _ Example 24 50 mL = 65 9 of the starting product indicated above are impregnated with 5.3 ml of a solution contain;ng
6.9 y of Na2PdCl4 solut;on (correspond;ng to 1 9 of palladium), 20 ml of a 10g by weight strength hydrazine solution are added to convert the palladium in~o the ele-mental state, and the support ;s washed ~ith demineralised water until neutral and chloride-free and then dried to constant ~eight at 110C in a stream of warm air.
50 ml of a catalyst which contains 20 9 of Pd per litre of catalyst are obtainedO This catalyst ;s suitable for the hydrogenation of o-nitrotoluene.
Example 25 100 ml = 143 9 of the start;ng product ;ndicated above are impregnated with 600 ml of a solution containing 1.b45 9 of ruthenium nitrate hydrate (corresponding to 0.5 9 of Ru), dried and heat-treated at 400C. The ruthenium oxide thus deposited is reduced to the metal Le A 21 277 i32~

by treatment with hydrogen at an elevated temperature.
100 ml of the catalyst wh;ch con~a;ns 5 g of Ru per litre of catalyst are obta;ned. This catalyst is su;table for the hydrogenation of o-nitrotoluene.
Example 26 100 ml = 143 9 of the starting product indicated above are impregnated with 6.0 ml of a solution containing
7.5 9 of NiCl2.6H20 (corresponding to 1.85 9 of Ni) and dried to constant weight in vacuo at 80C.
100 ml of a catalyst which contains 18.5 g of Ni in the form of nickel chloride per litre of catalyst are obtained.
Example 27 100 ml = 143 9 of the starting product ind;cated 15 above ar ;mpregnated with 6.0 ml of a solution containing 10.0 9 of (Cu(N03)2.3H20 (corresponding to 2.6 g of Cu~ and dr;ed to constant weight in vacuo at 80C.
100 ml of a catalyst which contains 26 9 of Cu, in the form of copper n;trate, per litre of catalyst are Z0 obtained.
Example 28 100 ml = 143 9 of the starting product indicated above are impregnated with 6.0 ml of a solution containing 10.0 g of Co(N03)2~6H20 (corresponding to 2 g of 25 Co) and dried to constant weight in vacuo at 80C.
100 ml of a catalyst which contains 20 9 of Co in the form of cobalt nitrate, per litre of catalyst are obtained.
Example 29 100 ml = 1~3 g of the starting product indicated above are impregnated with 6.0 ml of a solution containing 6.0 g of FeCl3.6H20 (corresponding to 1.24 g of Fe) and dried to constant weight in vacuo at 80C.
100 ml of a catalyst which contains 1.24 g of Fe in 35 the form of iron chloride per litre of catalyst are ob-tained.
Le A 21 277 _ 59 _ The products of Examples 2~-29 are catalysts yet to be activated by hydrogen treatment. The catalysts thus activated can be used for the hydrogenation of o-n;trotoluene S Part E Description of preparation methods for products ac~ording ~o the inYention using organic base materials _. , .
Example 30 341 g of polystyrene ~material No. 18~ see Part A) are initially introduced into a 50 litre capacity, heat-able coating drum, and heated to 70C at a speed of 4 rpm In the meant;me, 2~5D0 g of silica sol and 250 9 of potass;um waterglass (mater;als 9 and 11~ see Part A) are added to each other in a 3 l;tre vessel with stirring.
Th;s m;xture ;s then pneumatically sprayed ~;th cont;nuous st;rring from a pressure vessel onto the cont;nuously ag;tated, ;niti-ally introduced polystyrene which at the start of the appl;cat;on was at 70C. As soon as the temperature of the agitated material drops belo~ 60C~
the spray process is interrupted until the temperature has returned to 70CC. Th;s process is carr;ed out four times.
This is followed by four appl;cat;ons w;thin a temperature range of 80 to 70C, six in a temperature range of 100 to 85S, s;x ;n a temperature range of 1Z0 to 100C, and the rema;n;ng ones within a temperature range of 150 to 100C.
After the applicat;on ;s complete, the product is a~lowed to cool down to 40C at a drum speed of 1 rpm~
and the drum ;s emptied.
763 g are obtained of a product wh;ch contains 422 9 of s;lica in the coat;ng. The absorbency of the product is 12.48% at a bulk dens;ty of 785 gtl and at a residual moisture content of ~1%.
The product thus obta;ned ;s heat-treated in a muffle furnace to remove the polystyrene, the ~emperature being raised to 700C at a rate of 50C/h. The starting Le A 21 277 .

~632Z

-- oO --product is kept at th;s temperature unt;l the en-t;re organic content has been dr;ven off. Th;s ;s recogn;sed by the atta;nment of constant we;ght.
417 9 of product are obta;ned~ wh;ch correspond to 98.8X of theory.

Le A 21 277 ~ ~ . .

Unable to recognize this page.

63~

Example 38 393 9 of material ohta;ned as ;n Example 30 but w;thout removal of the polystyrene are sprayed ;n the course of 4 hours as ;n Example l of Part B w;th 1,489 g of a m;xture consist;ng of 337 9 of vanadyl oxalate solu-tion (material No. 13, see Part A), 113 g of 98X strength sulphur;c acid, 201 9 of potassium sulphate and 83~ g of silica sol (mater;al No. 9~ see Part A).
725 9 of product are obtained, which corresponds to a weight increase relative to the amount of starting materiaL used of 85% or 332 9. The product thus obtained was heat-treated at 400C for 17 hours, th;s tempera-ture being reached over a per;od of 8 hours.
Th;s produced 507 9, corresponding to a 30%
~e;ght decrease, as f;nal product, wh;ch can be used as catalyst for the ox;dat;on o~ naphthalene~

Le A 21 277

Claims (9)

Patent Claims
1) Silica-containing shaped articles, characterised in that a hollow space or a lumpy inorganic base material is surrounded by a layer containing porous silica.
2) Silica-containing shaped articles according to Claim 1, characterised in that the silica-containing layer contains catalytically active substances or pre-cursors thereof.
3) Process for preparing silica-containing shaped articles, characterised in that silica sol or a mixture containing water, silica sol and/or waterglass and, if appropriate, finely pulverulent, water-insoluble silica and/or porosity-forming agents is applied to a lumpy base material while the temperature of the base material is, at the start of the application of the silica sol or of the mixture, below the softening point of the base material and, as the application of the silica sol or of the mixture proceeds, above the boiling temperature of water, and the silica sol or the mixture is added in such a way that the water evaporates rapidly and the water content of the base material is always less than 5% by weight, and, if use is made of organic base materials, these organic base materials are then removed by heating to temperatures within the range of 200 to 1,300°C.
4) Process according to Claim 3, characterised in that an inorganic base material which, at least at the surface, has an absorbency of less than 10 g of water per 100 g and a BET surface area of less than 5 m2/g and a finely pulverulent water-insoluble silica which has a primary particle size in a range of 1 to 200 nm and an agglomerate size within a range of 0.5 to 100 µm and/or kieselguhr are used, and the silica sol or the mixture is applied at temperatures above the boiling point of water.
5) Process according to Claim 4, characterised in that the temperature of the inorganic base material is within a range of 105 to 800°C during the application of the silica sol or of the mixture.
6. Process according to claim 3, characterized in that an organic base material is used, the temperature of the organic base material at the start of the application of the silica sol or of the mixture is kept below its softening point, as the application of silica sol or mixture proceeds the pro-cess is carried out at temperatures within a range of 105 to 200°C, and the organic base material is then removed by heating to temperatures within the range of 200 to 1,300°C.
7. Process according to claims 3, 4 or 5, characterized in that silica sol or a mixture is applied until a silica-containing layer having a thickness within a range of 10 to 3000µ has formed.
8. Process according to claims 3, 4 or 5, characterized in that catalytically active substances or precursors thereof are applied together with silica sol or with the mixture con-taining silica or a mixture is first applied which produces a silica-containing layer free of catalytically active substances or precursors thereof and solutions or suspensions of catalyti-cally active substances or precursors thereof are then introduced into the layer.
9. A method of promoting a reaction using a silica-containing shaped article having a hollow space or a lumpy inorganic base material surrounded by a layer containing porous silica, which supports a catalyst material said method comprising including said shaped article in a reaction environ-ment so as to be present as a catalyst for the reaction.
CA000419070A 1982-01-09 1983-01-07 Silica-containing shaped articles, a process for their preparation, and their use Expired CA1196322A (en)

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DE19823200483 DE3200483A1 (en) 1982-01-09 1982-01-09 MOLDED BODIES CONTAINING SILICA, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DEP3200483.4 1982-01-09

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US4764498A (en) 1988-08-16

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