DE1946171C - Process for the production of a disperse system - Google Patents

Description

The present invention relates to a method for producing a disperse system from aluminum oxide and one or more metals that have a higher single-electrode potential than aluminum to have. In particular, the present invention relates to a method of making a solid dispersant System (hereinafter referred to as the "disperse system"), consisting of aluminum oxide and eTnem or more metals or metal oxides. these constituents being dispersed in one another uniformly and in a fan-distributed form, where em new metal complex used as raw material is dried and calcined. If necessary, will this complex initially as a gel or as a sprinkling manufactured.

For the various phemic industries such as Manufacturers of catalytic converters and ceramic materials as well as other branches of industry that produce powder Making or using materials it was a major problem, such as metals or metal oxides in finely divided form m the aluminum carrier dispcr-egg-rt could become. Much research and improvements have been made in this regard has been proposed. For example .st the idea v "" Morikawa in “The Kogyo Kagaku Zasshic S 5 (1967) and another idea in »Th ·· Sh'oku'bai Kagaku Ko / a ", VoI. 5, p-4, etc. ;-light been. The task is based on these ideas. based on metals or metal oxides so uniformly v., possible and with such a small particle size a! ·. if possible / u disperse or in a stretcher to distribute fabric. In detail is from the state d.r Technique known in this regard as follows:

a) A method for dispersing and for Au: applying to a carrier, wöbe: with MetalisaWöMingen active alumina that was obtained by calcining aluminum oxide-hydral. z. B. Powder or moldings au-, Gamma aluminum oxide (/ -aluminium oxide), impregnated is, or that such aluminum oxide is immersed in metal salt solutions, then concentrated, dried and calcined, these processes, case? desired, repeated can be.

b) A procedure according to which a precipitation \ <'. Aluminum oxide hydrate is produced by adding a precipitant such as NH ₄ OH to an aluminum salt solution on the one hand and according to ■ lern a precipitate is produced from a metal salt using a precipitant on the other hand and these are then mixed and stirred evenly then, after careful washing, dry this mixture and calcine it.

c) A process in which a mixture of an aluminum salt solution and a metal salt solution or solutions is produced and a precipitate is produced by adding a precipitant such as NH ₄ OH, which is filtered, washed, dried and calcined.

d) A precipitation method according to which a precipitate of aluminum hydrate is generated by adding a precipitating agent such as NH ₄ OH to an aluminum salt solution and then concentrating, drying and calcining it after sufficiently washing and adding a metal salt solution.

e) A method according to which alumina and the metal component are in a powdery state is well mixed with each other, the mixture in wet or in dry state and molded then is calcined.

However, these procedures are not entirely satisfactory, in technical and economic terms, especially with regard to the intended extremely fine dispersion and distribution of the metal and metal oxides on the Carrier t of f.

In all of method (a) described above, a dilute solution becomes a supersaturated solution when it is concentrated and dried. This clogs the capillary tubes and the surface of the carrier material, and the solids begin to separate out around the openings of the capillary tubes during the drying process. By the ! When drying, the solution is sucked into the capillary tubes ( irund the capillary activity, and during calcination the dispersed particles are coarsely and not uniformly due to the remarkable W-.; ", mmes" of crystals at the places where Uk In addition, there is a risk of sintering if heated to a high temperature.

I- all of method b), according to the separate note; are mixed, it is evident that it is difficult to achieve a high degree of eccentricity. a ₅

In the case of assumption c), the neutralization of a liquid mixture, it is very difficult to achieve that there! ¹ > let both components of the mixed solution from ve! Various ions are precipitated at the same time and thus obtained in a rapid joint precipitation. because of the difference in metal ions due to ·. he difference in the pH range for the production of a precipitate no uniform precipitation is achieved.

Therefore, a co-precipitation method is also proposed according to which it is mixed and precipitated at the same time. Has in microscopic relation but even this method does not solve the above problems. In the technical implementation In addition, considerable difficulties arose in the implementation of the proceedings.

It is also evident that metals or metal oxides are not present in the carrier in high fineness Can be dispersed, if prepared according to the method d), according to the in a separately Solution is immersed, and according to method e), according to which two differently manufactured substances mechanically / mixed, is worked.

Apart from this, in the known dipping method, the co-precipitation method and the Mixed precipitation process is initially a very voluminous one Gel or precipitate obtained when the aluminum salt or the mixture of the aluminum salt and another metal salt is treated with alkali. Such a gel or such a precipitate consists of more than 90% water. The solids content, for example in the case of aluminum oxide hydrate gel cannot exceed a maximum of 10 to 20%. It is common knowledge that it is very it is uneconomical to age and repeatedly wash this precipitate, and that it is impossible completely remove the impurities.

In order to ensure that a carrier material produced in this way carries other activated metals or metal oxides, the immersion process is usually used. It is customary to start with a solution of the first component to dip or to impregnate with it and then the component by drying and To fix calcine and then to dip or impregnate with a solution of the second component.

It is therefore necessary that many procedures be carried out until one carrier has two or more Components. This not only takes a long time. It is also a significant one Labor required, and the production «« - coster. are extraordinarily high. Therefore, this method is very disadvantageous from an economic point of view. As stated above, various studies and improvements have been carried out has been proposed to obtain a uniformly dispersed system. All of these attempts however, have not proceeded satisfactorily in economic and technical terms.

After extensive research by the inventors, it is now a completely new and technical one found advantageous method by which the above-mentioned problems are solved in a simple manner and wherein a disperse system is obtained which consists of aluminum oxide and metals and / or metal oxides which are dispersed in one another with great uniformity and fineness.

The present invention relates to a method for producing a disperse system from Aluminum oxide and one or more metals that have a higher one / el electrode potential than aluminum have, or oxides of such metals, which is characterized. that one or more Metal complexes containing aluminum and one or more metals that have a higher single-electrode potential than aluminum, with the empirical formula

AI "M". (OHUX _s »-p,"

where η is the number of aluminum atoms. M one or more metals, n ' the total number of atoms of these metals, m the number of OH groups. X one or more rponovalent anions, ρ the total sum of the valencies' Jer M and 3 / i4 p- m the total number of X atoms and where / wipe / i, />. n ' and »ι the exchange drawings

η η

3/1 ■ ρ > / 11

commit,

dried and calcined.

The method according to the invention thus consists in using a new metal complex, aluminum and other metals with a higher single-electrode potential than aluminum as a crude product or starting product for the process to use a disperse system of aluminum and Manufacture metals or metal oxides in which the components are uniform and extremely fine with one another are dispersed. Drying and calcination can be carried out after gelation with a gelation agent or after treatment with a base which yields a salt which decomposes at elevated temperatures, or take place after formation of the gel or precipitate in the presence of a normal base.

As metals, which are designated with "M" in the above formula and which have a higher single-electrode potential as aluminum can be used, for example:

5 ι 6

Mn, Ti, Zr, Th. Zn, Ac (Ac group), Cr, Mo, W, produced complex to avoid. That's why im

U, Ga, Fe, Cd. La (La group), In, Tl, Co, Ni, generally a temperature between 60 and l (b C

Sn, V, Pb, Te. Sb, As, Bi, Cu, Hg, Ag, Ru. Rh, appropriate.

Pd, Os, Ir, Pt, Au etc. ■ The ratio between metal salt and aluminum

5 complex may depend on the number of

The anions that can stand for X are metals and their ratio to one another fluctuates

called Cl, Br, 1 \ NO ₃ -, NO _{,, CIO 4} , HCOO-, In general one can say that more than I MuI

RCOO etc. (R means an alkyl group such as aluminum to be added to I MoI metal

Methyl, ethyl, propyl, etc.) The time required for the above reaction

The new complexes can be carried out by reactions, usually about 1 to 50 hours. The time

between the metal salts of the mentioned metals varies depending on the kind of the metal salts

and metallic aluminum or unaged and the aluminum used as the starting product

Aluminum hydroxide or between the mixed complex, the grain size of the metallic aluminum

Solutions of metal salts and aluminum salts ums, the concentrations of the solutions and d, -:

and metallic aluminum or unaged 15 reaction temperature.

Aluminum hydroxide or between metal salts and As the reaction progresses, the tensile, .-

Aluminum complexes, etc. can be produced. (The given metallic aluminum or aluminum

The product obtained in the process gradually increases in the sense of the hydroxide gel, and the viscosity d:

Invention referred to as a metal complex.) Reaction solution increases. That way you will.

If they are produced by the reaction of a »» the produced metal complexes generally!

Salt of the metals mentioned with metallic aluminum form a homogeneous .. solution obtained. Your Ulli

Minium or non-dissolved aluminum hydroxide violet absorption spectra are remarkable.

or a mixture of a solution of the metal salt different from those of the metal salts and the

and aluminum salt with metallic aluminum starting product, aluminum components used

or unaged aluminum hydroxide, where the 25 This indicates. that the reaction solution does not

Reaction usually in an aqueous solution from a simple mixed solution of the metallic salt.

is the concentration of the complex, and the aluminum complex is.

d. H. the concentration of all contained in the solution. The reaction solution '., g usually results in a ι

ten metal salts, in the range of 0.1 mol / l up to one or a precipitate if they are with a low

gesätii _e tcn solution. The same applies to the concentration of 3 ° amount of base added, as the equivalent ....

tration of aluminum. However, concentrations of anions are equivalent to those in the Meiall salt or in the Mci

generally more appropriate in the upper range. The salt and the aluminum complex, which are used as output,:

Reaction can take place at room temperature or until the products have been used.

The boiling point of the reaction solution. One can therefore assume the existence of a cation. -.

Temperatures between 60 and 1O5 ^C C are, however, reaction products of the reaction mentioned :,

particularly preferred. The grain size of the metallic whose amount is equivalent to the amount of the mentioned a

Aluminum that is added can be between anions or below.

Powder form and leaflet form lie. Grains under a solid which, by drying the reactu.iis-

1.68 mm is generally preferred. solution is obtained by dissolving in water: r

When the reaction with aluminum hydroxide at 4 ° easily converted back into a homogeneous solution

Place of metallic aluminum.

It is advisable to use non-aged aluminum when considering the structure of the by drying the

hydroxide gel obtained immediately after its preparation by means of the reaction solution

to use. Crystalline or aged aluminum X-ray diffraction method examined, one sets

so hydroxide is not particularly suitable. 45 one perfect; amorphous structure, and one finds

Regarding the ratio of the addition of no X-ray diffraction spectrum, which is typical

metallic aluminum or aluminum hydroxide for the metal salt, which is used as the starting product

Regarding the other metal salts, it can be stated that they had been used.

preferably 1 to 5 moles of aluminum to 1 mole of the A study of the thermal properties

all other metal salts are given. 50 according to the differential thermal analysis showed that the

When the new complexes are made, the curve of the new substance produced is remarkable

Reaction of metal salts with an aluminum deviating from those of the metal salt and the aluminum

complex of the following general formula aluminum complex, which can be used as starting products

Al (OH) X were applied.

ni im 311-m ₅₅ It is therefore assumed that the

where X is a monohydric anion and metal complexes are oligomeric of relatively high

between the other symbols the relations are molecular weight and have a structure,

1 </; g 6 and 3 "> in exist, as a rule, in the bridging bonds of hydroxyl groups such as

worked an aqueous solution, and the Konzentra- in aluminum-Aquo complexes are present. diesel

tion of the complex l'cgt in the range between 0.1 mol / l 6 ° metal complex is usually in the form of a homo-

up to a saturated solution. The same applies to the gen ^ n aqueous solution obtained.

Concentration of the aluminum. Again, however, the following are examples of metal complexes

the higher /, concentrations preferred. given, which corresponds to the above general formula

This reaction can speak at room temperature or
at elevated temperature up to the boiling point of 65

Rcaktionslüsang be carried out. The through- AI ₅ Cr (OH) ₁₅ Cl ₃ , Alj, Cr (OH) _e Cl ₃ ,

The reaction at the boiling point itself is, however, Al ₃ Cr (OH) ₉ I (OOC ■ CH ₃ ) ₃ , AI ₃ Mn (OH) ₉ CI ₂ ,

not particularly preferred to prevent decomposition of the Al ₃ Zr (OH) ₉ CI ₄ , AO

7 8

Al ₇ Cr ₂ (OH) ₂₂ (NO ₃ ) S, AI ₁₀ CoMo (OH) ₃₀ CI ₇ . The calcining temperature varies with the Al ₁₂ NiCoMo (OH) ₃₆ (NOa) ₁ Cl ₅ , AI ₄ Cr (OH) ₁₂ Cl ₃ , type of metal present and the use Al ₄ Ni ₂ (OH) ₁₃ (NOa) ₃ , Al ₄ Fe ₂ (OH) ₁₅ (NO ₃ ) j, purpose of the end products. Generally this will Al ₅ Mo (OH) ₁₅ Cl ₆ , Al ₄ Pt (OH) _{12 Cl 1} , calcining at temperatures in the range from 120 to Al ₂ Sb (OH) ₆ Cl ₃ , AlMn (OH) ₃ Cl ₂ , Al ₆ Cr (OH) ₁₅ CI ₆ , 5 1400 ° C. If the product is a disperse Al ₁₁ Cr (OH) ₃₀ CI ₆ , Al ₅ Cr (OH) ₁₂ (NO ₃ ) _e , system made of metal or metal oxide with active Al ₉ Co (OH) ₂₄ (NOa) ₅ , Al ₁₁ Mo (OH) ₃₀ Cl ₈ , aluminum oxide is a temperature desired AI ₂₀ CoMo (OH) ₅₄ Cl ₁₃ , between 300 and 90O ⁰ C particularly advantageous. Al ₃ Cr (OH) ₄ (OOC · CH ₃ ) ₃ CI ₃ , Al ₇ Bi (OH) ₁₈ CI ₄ , A disperse system can also be produced in this way Al ₃ Mn (OH) ₄ CI ₆ , Al ₄ Zr (OH) ₉ Cl ₇ , io are that a gelling agent to the solution of the Al ₃₀ Mn (OH) ₇₆ Cl ₁₇ , Al ₁₂ Co (OH) ₃₀ Cl ₂ Br ₈ , metal complex is added to this in a gel AI ₁₈ CoMoNi (OH) ₄₄ (NOa) ₂ Cl _n , to be transferred. Then it is aged and, if desired, AIs ₀ Pt (OH) ₁₂₀ Cl ₃₄ , Al ₁₀₀ Pd (OH) ₂₄₀ Cl ₈₄ , washed and then dried and calcined Al ₂₃ Cr ₂ (OH) ₈₀ Cl ₁₆ , Al ₆ Cr (OH) ₁₂ Cl ₈ , nated. A commonly used gelling agent Al ₈ Co ₁ (OH) ₈ (NOa) ₆ , Al ₆ Co (OH) ₁₂ (NOa) ₆ , 15 is also suitable for this purpose. However is a Al ₉ Sn (OH) ₂₄ Cl ₇ , Al ₃₇ ThZrSb (OH) ₉₀ CI ₃₂ , 'means that a precipitate immediately after Al ₄ Cr (OH) ₁₀ Cl ₆ , Al ₂ Cr (OH) ₆ (NOa) ₄ , forms contact with the solution of the metal complex, Al ₄ Ni (OH) ₁₀ Cl ₄ , Al ₄ Fe (OH) ₁₀ (NOa) ₆ , not desirable. Are particularly useful Al ₁₀ Mo (OH) ₂₆ Cl ₁₀ , Al ₈ Co (OH) ₁₆ (NOa) ₆ , weak bases, their basic dissociation constant AI ₂₀ CoMo (OH) ₆₀ Cl ₁₇ , * o is below 10 *, such as hexamethylenetetramine, urinary Al ₁₄ NiCoMo (OH) ₂₈ (NOa) ₁₈ Cl ₆ , substance, ethylenediamine, diethanolamine, triethanolamine, Al ₁₈ Mn (OH) ₄₉ CI ₁₀ , Al ₂₀₀ Pt (OH) ₆₀₀ (NOa) ₁₀₀ Cl ₄ , propylene oxide (process variant 2). AI ₂ Sn (OH) ₄ (OOC · CHa) ₂ CI ₂ , The gel formation depends on several conditions Al ₃₀₀ Pt (OH) ₇₆₀ (NOa) ₁₆₀ CI ₄ , ab, --vie the concentration of the metal complex, the Al ₄₀₀ Pd (OH) ₁₀₀₀ Cl ₂₀₁ , Al ₂ Mn (OH) ₆ Cl ₃ ,> s concentration of the gelling agent, the temperature AI ₄ Th (OH) ₁₀ (NOa) ₈ , Al ₈ V (OH) ₁₈ (NOa) ₈ Q ₃ . etc. A concentration generally used Al ₆ Cr (OH) ₁₆ Cl ₃ , Al ₂₀ Ni ₁₇ (OH) ₆₀ (NOa) ₄₄ , the metal complex for gel formation is included Ai ₁₄ NIa (GH ₄₀ (NOa) ₁₄ , AI ₄₀ Ni ^ (OH) Jg ₉ (NOs) _29. Less than 30%, whereby a loading AI ₁₂ CoMo (OH) ₃₀ Cl ₁₃ , Al ₁₀₀ Pt (OH) ₂₆₀ Cl ₆₄ , rich "from 10 to 20% (based on the total Al ₈ Co ₂ (OH) ₂₃ (NOa) ₆ , Al ₃₀ Fe (OH) ₇₆ Cl ₁₈ . 30 amount of oxides and metallic aluminum and

all other metals present). The concentration

In order to produce a disperse system which, according to the gel forming agent, can vary within wide limits of the invention, one or more metals or metals. A very soft gel or an oxide in the desired ratio to the aluminum-very hard gel can be obtained. It is sufficient to contain oxide, a metal complex must be added according to the method described above, when about such an amount of gelling agent as the amount of anions (the amount of which the desired metal takes in the correct ratio of hydroxyl groups) corresponds that contains to the aluminum. The treatment of the metal-metal complex is described below. By Gel formation is usually at room This treatment is then obtained a disperse 40 temperature or carried out below 100 ° C, said system, which more preferably the desired metal or metal oxide at a temperature of 60 to 90 ⁰ C uniformly dispersed in the desired ratio. The higher the temperature, the shorter the time. ^{Time required for} gel formation. If, for example, a disperse system, consisting for example of about 24 hours at room temperature, consisting of 20 mol percent Cr ₂ O ₃ and 80 mol percent Al ₂ O ₃ , 45 but only 30 minutes at 80 "C., Is to be produced, according to the The anion constituents which, in the process, produce an aqueous solution of a complex corresponding to the metal complex and the gel-forming agent, which are the sums, are generally removed by converting them into Al ₄ Cr (OH ) ₁ JCIa, A ^ CriOH ^ rfNO,) ,, during the drying and calcination process Al ₄ Cr (OH) ₉ Cl _8. Al ₄ Cr (OHy NO ₃ ) ,, Al ₄ Cr (OH) ₉ Cl ₃ 50 If the mentioned (NOj) _{3 can} correspond, and this complex will not be able to remove constituents, however, it is used as the starting product for the production of the dispersing system because the calendering temperature is kept too low. ° deT the calcining time too short is under consideration -If a disperse system consisting of 33.3 molar consideration of the intended use of the desired percent NiO and 66.7 molar percent Al ₂ O _{3 is} produced, and if the present is to continue, the starting product is an aqueous one with regard to the The above-mentioned uses of the analogous solution of the complexes prepared in accordance with the above process can be used, which are prepared in that the gel obtained is sums AkNi (OH) ₆ (NOa) ₈ , Al ₁ Ni (OH) ₈ Cl * first washed and then dried and have Kal-Al ₁ Ni (OH) ₁ (NO,) * Al ₂ Ni (OH) ₁ Cl ₈ . 60 zmiert throw.

During drying, these solutions of the metal- The drying and calcination conditions form complex resinous solids. Therefore, those for the gel obtained are similar to those already given above for the disperse systems desired in accordance with the invention, prepared by calcining the complexes for the preparation process according to the invention. The method of drying disperse systems through the formation of a is not particularly critical. In general, gels or precipitates are used which are dried and kaizi temperatures of 60 to 12O ⁸ C are expedient «Earth, rens variant 1). A base can be added to the solution of the metal complex

(ο

₉ 10

ceeeben will provide a decomposable salt. These disperse systems according to the invention can

It must be ensured that the salt formed is also produced by mixing two or more of the dried and calcined gel complexes or their solutions containing various metals, which decompose and volatilize, with one another For example, NH ₄ OH, NH ₄ HCO ₃ , 5 and then according to one of the above-described Sh), C0 propylene oxide, hexamethylenetetramine, processes are treated (process variant 7) ^ rnTtofathylenediamine, diethanolamine.Triethanol- If according to the above-described Ve -

Furthermore, can amtaeefonet weak bases be t take measures disperse systems prepared wend value whose basic dissociation constant to, these are usually in the form of _a:; itant is below 1 <H. The salts formed in this way can be present in the metal oxide-aluminum oxide system, i.e. h., · lefcht excellently disperse systems, since alumina is dispersed with the metal oxide.. S complete during drying and calcination - if the calcination is decomposed under an oxidizing atmosphere, without being carried out in the dispersed atmosphere. If, on the other hand, impurities remain in the system (process calcination in a reducing atmosphere rens variant 3) ^{15 is} carried out, the disperse system becomes the form r

It is sufficient if there is about such an amount of metal alumina, i.e. i.e., aluminum or a small excess of the base applied oxide dispersed with reduced metal, is like the amount of anions (except it is also possible to have a disperse system in the

Hydroxyl groups), which are complexly linked with the metal form metal-aluminum oxide to be obtained thereby. ^ao that initially a disperse system in the form

The conditions for drying and calcining metal oxide-aluminum oxide by cabrination in Ren of the gel or precipitate obtained are produced in an oxidizing atmosphere and this is essential the same as they have already been given above for an aftertreatment in reducing were written. Atmosphere.

In addition, it is possible to produce the disperse systems according to the invention in that a production method of the desired precipitate is formed analogously to the dispersed systems by various methods of a precipitate Wuci ^; Metal complexes are used as a common base product from a solution of metal salts. The solution of the metal complex is added to the Μερίζω ¹ solution and the anionic constituents contained in the complex can then precipitate is dried and calcined. Wonfcn undahgirnfcn, during the procedure wet-

As the usual base, which in this sense can be used as precipitation taking ds Trorio.-.ps and calcining = the medium, alkali Mct; i !! i.omp!; ··, -! &, ·· _: κ, although here also a cissed metal hydroxide, alkaline earth metal hydroxide, carbon fiber 35 lower rope:. · ..; Partial difficulty of the entnate in question, which has a strong alkalinity in a watery distance, f mc; * .r; r , \ n of the anions. If have solution. If the presence of alkali, however, soih-i gy.-.ng. Quantities of anions that are added as precipitants in the finished parts. Should be ^ .Ii-- ijr Ae :: bsichtigten use * wake th disperse system undesirable way of ^as; PJpR - ";:!.! ': T ialtenen disperse sytems view of its use, for example by 40? undesirable ..- 1-.J ₁ ν i'isi and strength to be removed, the alkali metal lowers the catalytic activity if we-.r or "-.fe Mopiichkcit is given that c nige the disperse system as a catalyst used Aniopeu -! <·; tarnffle in the disperse system as to be, it may conveniently be characterized finished product at the r: _{r, ir} .j insufficient Zcrsethergestellt be that the generated precipitate wetting and Verfh-.i first washed and the above-mentioned alkali can be unlocked remain UifeUng da! 45 perhaps under _a Pc7ück ichligung of use is removed * he bevoi dried and calcined. The purpose of the final products is to reduce the amount of alkali added as a precipitating agent, temperature or limited calcination corresponds approximately to the amount of anions (the anionic hydroxyl groups can be used) that are completely contained in the metal complex components according to one of the following. The conditions for drying 5 ° methods are removed.

and calcining the resulting precipitate. In accordance with the method described above, essentially those that have already been carried out above, variant 2, were stated from the solution. ^{of the} metal complex formed a gel and the crhal-

Furthermore, disperse systems can then be dried and calcined according to the previous gel, lying invention can also be produced by 55 According to the method variant described above that two or more gels or precipitates prepared according to 3, wherein by adding the base to the solution of the metal either the above-mentioned methods obtain a gel or precipitate from a complex complex, are mixed together and the settable salt is formed and then the Mixture then as in the case of the first described gel formed or the precipitate dried and Method is dried and calcined (Method 60 is calcined.

Variant 5). According to the above process variant 4, with

The desired according to the invention disperse of an ordinary base produced a precipitate Systems can also be made by being, which is then dried and calcined, two or more complexes or their solutions, which in the case of yellow soil according to process variant 2,

Contain the same metals, but from different s ₅ is produced by the reaction of the weak base, which are from which composition, with each other venniscnt gel-forming agent is used, with the anion and then treated as described above, when the gel thus prepared is washed delt (process variant 6). finished salt completely ^excluded: is being born there!

11 "12

wash, so that in this way the removal of the if one after the process variant 4 first

Anions is achieved. . a precipitate by adding a customary base

Even if the produced gel is formed without washing and then dries and calcines it, than

is dried and calcined, the salt formed is that, according to process variant 1, the aqueous

completely decomposed and volatilized, so that the solution of the complex mentioned dries immediately

removal of the anion more perfect than in the case of the calcined and calcined ones,

driving variant 1 can be achieved. It is therefore possible to produce disperse systems,

In the process variant 3, according to which a gel in which a metal or its oxide with a or a precipitate after being obtained by adding the higher single-electrode potential than that of Aluein The decomposable salt-yielding base has been produced uniformly in a desired ratio is, is dried and calcined, the anions are distributed in the aluminum oxide or carried by it nen components are converted into a decomposable salt. It is also possible that the aluminum oxide, which during drying and calcining additionally salts or oxides of metals with a just as easily as according to the above-described lower single-electrode potential than alumines Process variant 2 is decomposed and volatilized. 15 possesses nium, such as alkali metals and alkaline earth metals In this way, the removal of the anion is perpetuated by the disperse systems obtained after achieved more effectively than according to process variant 1. conventional methods, for example according to the

According to variant 4, whereby by the action dipping method or using any

an ordinary base formed a precipitate such as the method methods described above

and is treated, as a result of the reaction ao gelation or addition of a usual base to

the base formed a salt with the anion. When the result is treated to produce a precipitate

generated precipitate is washed, the salt will be.

completely washed out, and the objective of the disperse state and the size of the disperse

Removal of the anion can thus be easily achieved. Particles of the disperse systems thus obtained were

If an anion, which is easily decomposed by heat 95 by means of electron microphotography, X-ray diffraction

such as organic acid radical, process analysis, X-ray microanalysis, etc. can be examined

is the salt produced by the drying and and compared with those of disperse systems,

Calcination of the precipitate formed even without the prior art.

Washing completely and easily decomposed and cursed. It was found that according to the

be done. In this case, the objective of the method of the invention can be obtained in the disperse system

Removal of the anion is therefore also more perfect than is superior in accordance with the systems of the prior art.

Option 1 can be achieved. Specifically, it was found that the particles of

According to the method of the invention, disperse systems according to the invention can therefore be extremely

u the desired disperse systems using uniform and fine, while those made according to

it «r metal complexes were produced as starting material according to the state of the art, are coarser,

any of the aforementioned process variants are found in electron photomicrographs

■ Titles 1 to 4 and 5 to 7 are produced, with those with 100,000 to 250,000 times magnification. When

Process variants are combined with one another disperse systems according to the invention and according to

be able. Those obtained by these process variants are state-of-the-art, both at 500 to 600.degree

Ten disperse systems differ in terms of 40 how long they had been calcined using X-ray diffraction

the specific gravity, the specific surface area, were examined, the former showed almost

^! there is pore diameter, pore distribution and no diffraction lines, while the latter

"Orenvolumens as well as other properties and showed three diffraction lines, albeit one of them

chemical activities if they showed great breadth as catalysts. If at temperatures above

*. be used. It is therefore possible that 45 800 ⁰ C had been calcined, the disperse showed

suitable and expedient variant of the method to make systems according to the invention a remarkable one

choose to produce a disperse system with the lower diffraction power than those of the prior art

desired properties and chemical technology.

Activities, in accordance with the use- The fact that no inflection lines are received

purpose of the desired disperse system. 50, or that, although preserved, the power of diffraction

For example, if a disperse system of the formula is extremely small, it shows that crystals with a regu-

CoO - MoO ₃ - Al ₁ O ₃ containing 3.0 percent by weight of the general form are either not present or,

cent CoO and 11.5 percent by weight MoO ₃ , although they are present, these are extremely fine,

a metal complex with the empirical formula, which in turn indicates the presence of a good dis-

AleMojCoiOH ^ a ^ Noa), may indicate 55 persity.

a disperse system with a larger surface is obtained when examined by means of X-ray analysis with a by showing a gel or a low resolution of 1 μ forming the disperse system and drying this according to the method variants me according to the invention a highly uniform dis-2 to 4 and calcined, so that ttuji directly persion of the metal constituent particles in the aluminum, the aqueous solution of said complex according to 60 nium oxide particles, while in the systems of process variant 1, drying and calcining. Prior art a rather inconsistent use when a disperse system of the formula division was found. In both disperse systems Ni - Al ₄ O ₃ , containing 50 percent by weight Ni, the size of the dispersing particles was smaller than a metal complex with the empirical formula than 1 μ, which establishes the limit of the resolution AW ^ iM (OH) So (NOs) ₄₄ , one receives a dis- 65 of the analytical apparatus.

Oerses system with a higher activity when comparing the areas per unit of measure

Use as a catalyst for a method of measuring the amount of nitrogen absorbed

Hydrogenation of benzene in liquid or in gas phase, it has been found that the disperse systems according to the

13 14

Invention mostly a noticeably larger upper- are included. It is therefore much lower than the

area than those of the prior art. nige that to produce a disperse system with

The pore distribution curve obtained from the nitrogen - the same composition from a usual

Adsorption and desorption curves were obtained. Salt is required.

den, showed a remarkably sharp distribution, which 5 According to process variant 4, where by indicates that the size of the base particles is uniform. Addition of bases a precipitate is produced, Different disperse systems, which after the failure can make the generated precipitation easier and easier drive according to the invention and are filtered and washed as de. "Precipitation, uniformly and finely, the above-mentioned metals from the conventional ones according to the prior art and / or contain their oxides in dispersed form, are obtained as a salt. In addition, the low-activity catalysts for various reactions is obtained in such an advantageous manner that the impact is used so long as an appropriate selection is made in terms of basic particles extremely uniform therein. Therefore made of the dispersed metals or their oxides is a uniform and characteristic of it will. disperse system available that differs from those

If these disperse systems as material for the 15 differs, those of common known salts are ceramic Industry can be used.

Different products with different properties - The amount required for this process variant

th can be obtained. Base can be roughly the same as that of the anions (except for

The first advantage of the process according to the invention will be hydroxyl groups), which are contained in the metal complex in the excellent accessibility of ao. This is, as has already been mentioned, uniformly and finely dispersed systems from the considerably less than the amount obtained in the case of the new metal complexes mentioned. Another known common salts is required
The advantage lies in the remarkable simplification. As has already been stated, the process of the production process, the reduction of the measure of the invention with regard to various inherent requirements for the main and secondary output from technical and economic face products and a remarkable improvement are points Prior art method over economy based on the above. Reasons given by the method according to the invention. solves several problems that were previously encountered with the

When the above-mentioned new metal complexes manufacture of disperse systems of metals for the process according to the invention as starting materials or their oxides.

products are used, the amount consumed is The following examples illustrate the

Amount of anion much lower than further explained in accordance with the prior art.

Technique in which an aluminum carrier made of aluminum. .

Halides is made to make the metal constituents Example 1
to wear. 35 590 g of a solid obtained by drying

The amount of bases required to produce 1500 g of an aqueous solution (pH 3.0) of a metal

of gels or precipitates from this new complex, containing 8.63% Al and 3j33% Cr and

Metal complexes is required, much less than the general formula Al ₅ Cr (OH) ₁₅ Cl ₃ , accordingly

that obtained for precipitation or gelation of one was required in a common metal salt for 5 hours. 40 oven kept at 120 ^° C. Dai η was 2 hours long

Process variant 1 described above is calcined at 500 "C., with 320 g of a disperse

Production of a disperse system by drying system containing chromium oxide and aluminum oxide,

and calcining a metal complex without washing. This disperse system consisted of

is very advantageous from a technical point of view, since it has 22.8% Cr ₂ O ₃ and 77.2% Al ₄ O ₃ and not only has a loss of metals or their oxides 45 specific surface of 190 m ^a / g.

and aluminum oxide is avoided, but because in order to improve the dispersion state of the higher dispersed

To examine the procedure itself in a remarkable sen system became a disperse:

Extent is simplified. System of the same composition according to the

In process variant 2, according to which a state-of-the-art gel is used as a comparison sample a gelling agent is produced, the 50 represents that gamma-alumina after the more common

Reagent amount, as already said, was impregnated with chromium trioxide in a significantly lower immersion process

than that for treating a common salt. The two disperse systems were emphasized unc

Process variant 3, on the other hand, according to the method below compared using electron micrographs

Formation of a decomposable salt with a base graphic, X-ray diffraction and X-rays can only be done using the new 55 microanalysis. The electron photomicrographi

Metal complexes are carried out. It is basically shown that the disperse system according to the invention

also not applicable to common salts. After consisted of uniform particles of about 25 Å

this variant will be a precipitate or a gel that the chromium oxide and aluminum oxide will not of

generated by the fact that a decomposed one could be distinguished from one another by the added base. The system painted hard salt was formed. This method includes 60 the prior art, on the other hand, was pretty much the case

therefore a simple and advantageous method for dissimilar particles of about 50 A. The result de

Preparation of a disperse system where the gel X-ray diffraction showed that the disperse

or the precipitate is dried without washing and the system according to the invention has an amorphous structure

can be calcined, causing a loss of material. From this one can see the smallness of the tiny is avoided. 65 particles and the crystal growth rate

Withdraw the amount of required for this method. In contrast, the system of the state de

Base is roughly equal to that of the anions (using three diffraction lines

taken hydroxyl groups), which in the metal complex in the X-ray microanalysis apparatus with 1.01

Dissolution became an extremely uniform dispersion of in the disperse system according to the invention Chromium and aluminum were found while the prior art system was fairly uneven Had dispersion. It has also been found that the size of the dispersed particles in the both disperse systems was heavier than 1.0 μ, which is the limit of the resolution of the analysis apparatus was.

The one used as the starting product in this example Metal complex was prepared by the following procedure.

799.2 g (3 mol) of CrCl ₃ · 6 H ₂ O were dissolved in 3.61 of water. Thereto, 405 g (15 mol) of metallic aluminum in the form of grains of 10 to 100 mesh was then added and dissolved while heating to about 80 ° C. with stirring. It took about 5 hours to completely dissolve the metallic aluminum, with vigorous evolution of hydrogen. The solution turned blue in color during the reaction. After completion of the reaction, 4650 g of an aqueous solution of the complex having a pH of 3.0 were obtained.

The ultraviolet absorption spectrum of this solution showed a maximum transmission at 364 μm. The corresponding spectrum of the chromium chloride solution, the starting material, had a maximum transmission at 324 Γημ. On the basis of the elemental analysis it was found that the complex has the empirical formula Ai ₁ Cr (OH) ₁₅ Cl ₃ . The result of the Röntgen -'-, · .is- iiig showed that this complex has an amorphous ·.;: Iccture, while the starting salt has many peaks> vi, ite. The result of the differential thermal analysis showed contrary to the original material! a broad endothermic peak extending from 150 to 400 ° C.

T. ■ -ίο

350 ml of an aqueous solution containing 105 g of hexamethylenetetramine as a gelling agent were added to 1500 g of an aqueous solution of the same metal complex as was used in Example 1. Gel formation was carried out at 80 ° C and the gel was then aged for 2 hours. After the gel obtained ^{had been dried for 10 hours in an oven kept at 120 °} C., 560 g of a black-green solid were obtained. After this was calcined at 500 ° C. for 2 hours, 319 g of a disperse system was obtained. This consisted of 22.4% Cr ₂ O ₃ and 77.7% Al ₂ O ₃ and had a specific surface area of 220 m ² / g

To check the state of dispersion of the disperse system obtained, according to the prior art the technology produced a disperse system with the same composition as described in example 1, by impregnating gamma aluminum oxide with chromium trioxide using the usual dipping process would. Both disperse systems were examined and used by electron photomicrographs, X-ray diffraction and X-ray microanalysis compared. The results are the same as in Example 1 were obtained.

η ■ · _e 1 3

To 1500 g of an aqueous solution of the same metal complex as used in Example 1 was added 350 ml of an aqueous solution containing 105 g of hexamethylenetetramine as a gelling agent. Gel formation was carried out at 80 ° C. and aged for 2 hours. The Gd was crushed as desired and in 1500 ml of a solution containing 300 g / l hexamethylenetetramine, optionally, which was heated to 80 ⁰ C. It was then aged for 3 hours.

It was then washed 5 times with 5 l of distilled water each time, 3 times with 11 l of water each time, containing 50 g of ammonium nitrate and 2.5 ml of concentrated ammonia water, and then twice with 2 l of distilled water each time. After washing, this gel was dried for 10 hours in an oven which was maintained at I2O ^C C. 450 g of solid material were obtained in this way. When this was also ^{calcined for 2 hours at 500 0} C, were. 250 g of a disperse system consisting of chromium oxide and aluminum oxide were obtained. This system consisted of 23.0% Cr ₂ O ₃ and 77.0% Al ₂ O ₃ and had a specific surface area of 230 m ² / g.

In order to check the dispersion state of the disperse system obtained in this way, was, as in Example 1, a disperse system with the same composition according to the state of the art produced by that Gamma-Alumir.ijmoxid according to the usual Immersion process was impregnated with chromium trioxide. The two disperse systems were investigated and compared by electron photomicrograph, X-ray diffraction, and X-ray microanalysis. The results are the same as in Example 1.

If the according to Example 1, 2 and 3 prepared

disperse systems were used as catalysts for the dehydrogenation reaction to convert propane into propylene, they all showed a rate constant which was 2 to 4 times that of the systems obtained by the conventional immersion process. This shows that they have ■ · isgezeichnete catalytic activities.

B e 1 s ρ 1 e 1 4

10OC g of an aqueous solution of a metal compound containing 5.4% Al and 9.98% Ni, and the empirical _{formula Al 20} Ni ^ (OH) _{5 OiNO 3} ) ,,., accordingly, with vigorous stirring, were 2200 nl of a solution of 2 mol / l caustic soda to produce a precipitate. This was then adjusted after completion of the P.eaktion to pH 7.5, heated to 8O ⁰ C and aged for 1 hour at this temperature. The aged precipitate was filtered and washed 6 times with 2 liters of distilled water each time. When the precipitate thus obtained was dried at 105 ° C. for 16 hours, 520 g of solid was obtained.

When half of this solid was dried in an electric oven kept at 500 ° C. for 3 hours, 115 g of the disperse system was obtained. This consisted of 55.2% NiO and 44.8% Al ₂ O ₃ .

The results of observation through an electron microscope revealed that the dispersed system obtained

consisted of uniform particles of about 25 Å. The result obtained by X-ray diffraction showed that Existence of an amorphous structure. The results of the X-ray microanalysis showed that both the nickel and the aluminum were distributed in an extremely even state and that the The size of the dispersed particles was less than 1.0 μ, which was the limit of the resolution of the analyzer was.

This disperse system was then converted into another disperse system of the form Ni - Al ₄ O ₃ by reduction in a hydrogen atmosphere at 450 ^° C. for a period of 1.5 hours. When this was then used as a catalyst for the hydrogenation of benzene in the liquid phase and in the gas phase, it showed a considerably better reaction activity than various other disperse systems with the same nickel content which had been produced according to the prior art.

The other half of the dry mass obtained above was placed in a quartz tube and reduced in an atmosphere of hydrogen gas flowing through at a rate of 60 ml / min at 450 ^° C. for 1.5 hours. Then, after the hydrogen in this system was replaced by a stream of nitrogen, gas containing a small amount of oxygen was inactivated by passing nitrogen over it, and 101 g of a disperse system was obtained. This consisted of 49.4% Ni and 50.6% Al ₂ O ₃ .

When examining the state of dispersion of the disperse system obtained, as in the others cases previously described by the electron microscope, X-ray diffraction and X-ray microanalysis the same results as above were obtained.

If this system is used as a catalyst in the liquid phase and gas phase hydrogenation reaction was used, it showed excellent reaction activity.

The meta-complex used in this example was made by the following procedure.

450 g of an aqueous solution of an aluminum _{complex with the empirical formula A1., (OH) 5} NO ₃ and containing 12.00% "(2 mol) of aluminum at pH 4.7 were mixed with 600 g of an aqueous solution containing 495 g (1.7 mol) Ni (NO ₃ ) ₂ · 6 H ₂ O, by heating for 2 hours ^{with stirring at 90 °} C. 1020 g of an aqueous solution of the complex with pH 4.3 were obtained.

It was found by elemental analysis that this complex corresponds to the _{empirical formula Al 20} Ni ₁₇ (OH) ₆₀ (NOg) _{41 J.} The result of X-ray diffraction showed that it has an amorphous structure in contrast to the starting material.

Example 5

To 1000 g of an aqueous solution of a metal complex containing 6.48% Al and 2.64% Ni and with the _{empirical formula Al 18} Ni ₃ (OH) ₄₀ (NOa) ₁₄ , 245 ml of an aqueous solution containing 73, 5 g of hexamethylenetetramine, optionally uad, gelation was carried out at 80 ⁰ C. It was then aged at the same temperature for about 2 hours. The resulting gel was dried in an oven kept at 50 ° C. for 12 hours. It was then dried at 20 ° C. for 10 hours. About 400 g of solid were obtained.

When this was calcined for 3 hours in an ^{electric furnace kept at 800 °} C., 157 g of a disperse system was obtained. This consisted of 21.5% NiO and 78.5% Al ₂ O ₃ .

The results of observation through the electron microscope revealed that the dispersed system obtained was composed of uniform particles of about 100 Λ. When examining by X-ray diffraction a broad diffraction line of the gamma-alumina was shown. X-ray microanalysis disclosed that both nickel and aluminum were distributed in a very even state and that the size of the disperse particles was less than 1.0 μ, which is the resolution limit of the analyzer.

Example 6

1000 g of an aqueous solution of a metal complex, containing 5.40% Al and 0.88% Ni with the

ίο empirical formula Al ^ NijiOHWNO ^ a ,, were 12

For hours in an oven kept ^{at 8O 0 C and}

then dried at 120 ° C. for 10 hours. There were so obtained 230 g of solid.

When this 3 hours long, calcined in an electric furnace which was maintained at 900 ⁰ C, to obtain 114 g of a disperse Systcns. This consisted of 9.8% NiO and 90.2% Al ₂ O ₃ .

The results of observation by electron photomicrograph showed that the obtained dispersed

System consisted of uniform particles of about 100 A. When examining by X-ray diffraction a rather broad diffraction line of the gamma aluminum oxide was found. X-ray microanalysis disclosed that both nickel and

Aluminum were dispersed in a very uniform state and that the size of the dispersed particles was below 1.0 μ, which is the size of the resolution of the Analysis apparatus is

Example 7

135O g of an aqueous solution of a metal complex containing 1.09% Co, 1.76% Mo and 10.1% Al with the sum formula Al _2n CoMo (OH) ₅₄ Cl ₁₃ were dried in an oven kept at 120 ° C. for 5 hours. 620 g of a pinkish-purple solid were obtained. When this was calcined at 550 ° C. for 3 hours, 320 g of a disperse system consisting of 5, S5% CoO, 11.1% MoO ₃ and 80% Al ^ O _{3 were} obtained.

This disperse system was examined by X-ray diffraction and showed an amorphous structure. The results of the X-ray microanalysis revealed that each metal was uniformly dispersed and di i3 the size of the dispersed particles below 1.0 µ lag. which is the resolution limit of the analyzer is.

The metal complex used as the starting product in this example was produced as follows.
I] Sg (O ₁ SMoI) CoCl ₂ - 6 H ₂ 0.137 g (0.5 mol) MoCl _{5 and} 241 g (! Mol) AlCl ₃ · 6 H. ₄ O were dissolved in 2 l of water and heated to 80 ' C heated. To this, 270 g (10 mol) of metallic aluminum were added, which dissolved in about 3 hours. As a result of this reaction, 2,700 g of an aqueous solution of the complex having pH 3.4 was obtained.

The result of the elemental analysis shows i, u that this complex has the _{empirical formula AI 20} CoMo (OH) ₅₄ Cl ₁₃ . The result of X-ray diffraction shows that it has an amorphous structure in contrast to peaks obtained with the starting material.

Example 8

in 1350 g of an aqueous egg. To a solution of the same metal complex used in Example 7, 610 ml of an aqueous solution containing 61 g of ammonia (NHj) was added as a gelling agent. The GdbiUiuMp was carried out at ^{<70 0 C "!}

f (\ 946 171

¹⁹ 20

'P 5J "5 ² f ^{unden 8aged} - ^{If for the test} f" »g *» the state of dispersion of the

\ ^ "NRS ί Hm i ^ang '" ^{a to 8O' requested JC} disperse system as a comparative sample was held oven and then for 10 hours at 120 "C a disperse system containing 0.35% Pt, was dried thereby," was thought to 690 g of solid. When gamma-aluminum oxtd was calcined with chlorine for three hours at 550 ° C., 5 platinic acid was impregnated to produce 330 g of a disperse system _/? CoO 10.8 / _o MoO ₃ and 78.5% Al ₂ O _3. Radiation microanalysis carried out.

Uk Lrgeonisse of the X-ray diffraction and the electron-photomicrograph could the platinum metal Roiüi -.- n-ray microanalysis concerning the disperse in both disperse systems does not differ «Ons .stand and the particle size of the dispersed io will be. However, that according to the invention showed Teik; ·. η etc. in this disperse system a similarly produced disperse system was a more amorphous one hch OL-njemgen obtained in Example 7. Structure than the system that, after the impregnation

Example 9 was obtained approximately method.

innn · η · ^ ^{as the} result of the X-ray diffraction was that the

V, η IUUO g of an aqueous solution of a metal disperse cone obtained by the impregnation method, containing 1.09% Co, 1.76% Mo and system 4 gave strong diffraction lines, while the 10, 'Al and with the empirical formula AI ₂₀ CoMo obtained according to the invention provided only three diffraction (Oi ', Cl ₁₃ , and 1000 g of another aqueous solution lines which were only half as strong as the one · Meiallkomplexes containing 0.89% Co, 1.45 % first mentioned. This proves the lower crystalline and., 32 _{/ o} Al with the empirical formula ao growth rate of the system according to the Er-A, IMo (OH) ₃₀ CIi ₃ , mixed and then 5 hours of discovery. lai -n a held to 120 C oven dried that the disperse Wi obtained according to the invention -n, one of a pink-purple system received 940 g of a highly uniform dispersion of platinum L-. ■■-Stoffes. When this 3 hours at 55O ^J C is kai- and aluminum, while that by the impregnation. i, 420 g of a disperse system were obtained, a fairly un-S> -ms, consisting of 4.75% Co, 7.6% Mo and uniform D ^; spersion is. The size of the disper-8 'AI ₂ O ₃ . yawed particles was less than 1 μ, which is the

. The result of X-ray diffraction and the X-ray limit of the X-ray microanalysis apparatus is. g _t radiation microanalysis with regard to the dispersion

Si. Condition and the size of the dispersed 30 Example 12

Ti i.hen etc. showed that this disperse system was based on 1500 g of an aqueous solution of the same

la; that obtained in Example 7. Metal complex as used in Example 11

When D i e I ') was, 330 ml of an aqueous solution,

holding 92 g hexamethylenetetramine as a gel-forming

To 2000 g of a mixture of an aqueous solution 35 medium, added. Gel formation was at 80 ^; C passes through the same metal complexes as those given in the supplement. Then the same game 9 was used for 2 hours, 740 ml of a water temperature were aged. If the gel obtained 24 Stunrigen solution containing as a gel in a long genaltenen at 8O ⁰ C oven and then forming agent added to 170 g urea. The gelation was carried out for 90 ° C at 7 hours in a held at 12O ⁰ C oven. It was then dried for 2 hours at the 40th time, 615 g of a yellow aged at the same temperature were obtained. If the gel obtained is a solid. When this 3 hours calcined at 580C for 10 hours in a maintained at 120 ⁰ C oven, to obtain 277 g of a disperse was dried to obtain 1,100 g of a solid. Systems, consisting of 98.0% Al ₂ O ₃ and 0.36% Pt.
When this was calcined for 3 hours at 550 ⁰ C, to check the D-dispersion state of the received

425 g of a disperse system were obtained, consisting of 45 th disperse systems, 5.98% CoO, 11.40% MoO ₃ and 82% Al ₂ O _{3 were used} as comparison samples. The He- a disperse system containing 0.35% Pt, as in the results of the X-ray diffraction and the X-ray example 11, produced by impregnating gamma-aluminum ray microanalysis with regard to the dispersion nium oxide with chloroplatinic acid. Then, the state and size of the dispersed particles were determined by the electron-based disperse system investigations were similar to the results obtained by 5c · photomicrograph, X-ray diffraction and X-ray obtained in Example 7. Radiation microanalysis performed. It became the

If the results obtained in Examples 7, 8, 9 and 10 are the same as in Example 11,
keep disperse systems as catalysts for the. . .,

Hydro-desulfurization reaction of a petroleum fraction - Example

tion, they all showed a noticeable 55 to 1500 g of an aqueous solution of the same desulfurization activity, which indicated that this metal complex, as used in Example 11, had excellent catalytic activity, when 330 ml of an aqueous solution were lacking possessed. containing 80 g of urea as a gelling agent. Example Il ^{The Gelbildun} S was performed at 8O ⁰ C. The

60 held gel was arbitrarily crushed and divided into 2 1

When 1500 g of an aqueous solution of a metal of an aqueous solution containing 2 mol / l Harnkomplexes containing 9.72% Al and 0.06% Pt with the material, given and 2 '/ ₂ hours aged at 80 ° C. Empirical formula Al ₁₀₀ Pt (OH) Cl _{280 54,} 24 hours The mixture was then washed with 2 1 of ammonia water of pH 8.0 and a maintained at 8O ⁰ C oven and then 7 hours by 2 1 of water per 5 times. When this gel were dried at 12O ⁰ C, to obtain 510 g of a 65 for 24 hours in an oven maintained at 8O ⁰ C yellow solid. If this was calcined for 3 hours at 58o ⁰ C and then for 7 hours at 120 ° C getrocknei, there was obtained 272 g of a was dispersed, was obtained 390 g of a yellowish white system, consisting of 99.0% Al ₂ O ₃ and 0 , 37% pt. Solid. If this 3 hours at 580 ⁰ C calci-

21 "22

was ned, 254 g of a disperse of the empirical formula AI ₃ Zr (OH) ₉ Cl _{4 were obtained} for 12 hours

Systems, consisting of 99.0% Al ₂ O ₃ and 0.35% Pt. were dried in an oven kept at 95 ° C.

To check the state of dispersion, 56 g of solid were obtained. If this is 3 hours at

The dispersed system held was calcined as a control sample at 550 ° C., 29 g of dispersed material were obtained

a disperse system containing 0.35% Pt, as in the 5 system, consisting of 42.5% ZrO ₂ and 52.0% Al ₂ O ₃ .

Example 11 by impregnating gamma-aluminum. X-ray diffraction showed that this was dispersed

nium oxide made with chloi platinic acid. The system has an amorphous structure. The result

electron photomicrography and X-ray microanalysis studies showed that each

graphy, X-ray diffraction and X-ray mi-metal was uniformly dispersed, and that

croanalysis carried out. The same er- io the size of the dispersed particles was below 1.0 μ,

results as in Example 11 were obtained. the resolution limit of the analytical apparatus.

. The starting point used in this example

Example 14 the metal complex was produced as follows.

To 1000 g of an aqueous solution of a metal 233 g (1 mol) of ZrCl ₄ were dissolved in 0.51 of water and

complex, containing 5.4% Al and 2.4% Fe with the 15 heated ^{to about 70 0 C with stirring.} These were

Molecular formula Al ₁ Fe (OH) ₁₀ (NO ₃ ) S, 425 ml were then given about 4000 g of a gel and roughly

an aqueous solution containing 42.5 g of dissolved ammonia of a state. This gel was made by

(NH ₃ ) as a gel forming agent. Gel formation and washing "": s aluminum hydroxide gels

was carried out at SO ^{0 C.} Then 2 hours were obtained, which by adding 1.5 l

aged for a long time at the same temperature. When the 20 6 N ammonia water to 3 1 of a vigorously stirred

Gel obtained 12 hours' -mg in a 90 ° C aqueous solution containing 723 g (3 mol) of AlCl ₃ -

held furnace and then at 120 ° C 6H ₂ O for 7 hours. Ais result of this

dried -.vurde. 354 g of a solid were obtained. Reaction were 4600 g of an aqueous solution of the

If this was calcined for 2 hours at 550 ^c C, complex with pH 2.1 obtained,

190 g of a disperse system were obtained. According to the result of the elemental analysis, this possessed

consisted of 4? .0 ^{o /} , Fe ₂ O ₃ and 53.6% Al ₂ O ₃ . This complex has the empirical formula Ai ₃ Zr (OH) ₉ Cl ₄ .

Examination by X-ray diffraction showed that the result of X-ray diffraction showed that it was a

this disperse system had an amorphous structure. has amorphous structure.
The result of the X-ray microanalyser ^ ab that

the distribution was uniform and that the 30 Example 17
The size of the dispersed particles was below 1.0 μ, the limit of dissolution of the analytical apparatus is for 500 g of an aqueous solution of a metal soft. complex, containing 9.85% Al and 4.80% Sn with _H ... the empirical formula Al ₉ Sn (OH) ₂₄ Cl ₇ , were 220 m! Example 13 _{a laundri} ß _r j _gen solution containing 110 g ammonium When 1200 g of an aqueous solution of a metal bicarbonate 35 as gelling agent was added. The Gelkomplexes containing 4.5% Al and 4.55% Mn with formation was conducted at 6O ⁰ C. Then, the lithium formula Al ₂ Mn (OH) ₅ Cl _{3 was} aged for 12 hours for 2 hours at the same temperature. When dried in an oven kept at 95 ° C, the obtained gel 24 stalls in an oven kept at 80 ° C gave 350 g of a solid. When this holding oven was dried, 200 g was obtained and calcined at 550 ° C. for 3 hours to give 40 solids. When this was calcined for 2 hours at 500 ^° C. 183 g of a disperse system consisting of 43.5%, 125 g of disperse system were obtained. This Mn, O ₃ and 55.4% Al ₂ O ₃ consisted of 24.0% SnO ,. and 73.5% Al ₂ O ₃ . The X-ray diffraction revealed that this disperse system. Examination by X-ray diffraction showed that it had an amorphous structure. The result that this disperse system had an amorphous structure. X-ray microanalysis revealed that each metal was dispersed 45. which the resolution limit of the analysis apparatus was below 1.0 μ, is the resolution limit of the apparatus. rates.

The 50 B '' el 18 used as the starting product in this example

The metal complex was prepared as follows: ^P

been. To 1050 g of an aqueous solution of a metal

To 570 g of an aqueous solution of an aluminum complex containing 5.14% Al and 11.0% Th with

complexes with the empirical formula AI ₂ (OH) ₅ CI, or the empirical _{formula Al 4} Th (OH) ₁₀ (NO ₃ ) _{e, were 500ml}

containing 9.54% (2 moles) of aluminum at pH 4.6 were 55 of an aqueous solution containing 100 g of urea

700 g of an aqueous solution containing 198 g (1 mole) as a gelling agent was added. The gelation was

MnCl ₂ · 4 H ₂ O was added. These solutions were carried out 2 at 85 ° C. Then was 2 hours at

Hours heated at 8O ⁰ C and stirred. Aged as the same temperature. If the received

The result of this reaction was about 1200 g of a gel in an oven kept at 80 ° C. for 24 hours

obtained aqueous solution of the complex of pH 3.0. 60 was dried, 500 g of solid were obtained. When

The elemental analysis showed that this complex was ^{calcined at 500 °} C. for 2 hours

the sum fornel has Al ₂ Mn (OH) ₅ Cl ₃ . The Erman 240 g disperse system. This consisted of

The result of the X-ray diffraction showed that it was an amorphous 55.0% ThO ₂ and 42.5% Al ₂ O ₃ .

Structure. The examination by X-ray diffraction showed

j,. . -., 65 That this disperse system has an amorphous structure

^c ' ^s P' ^e . The result of the X-ray micro-

When 470 g of an aqueous solution of a metal analysis showed that each metal in a uniform manner

complex, containing 1.75% Al and 1.98% Zr was dispersed with and that the size of the dispersed

23 ^ 24

Particles below 1.0 μ was the limit of dissolution 7 times with 2 liters of diluted ammonia water each time

Apparatus. of pH 8.0 and then 5 times with distilled water

Example 19 washed. When the obtained precipitate is placed in an oven kept at 80 ° C for 12 hours and then

102C g of an aqueous solution of a metal particle S was ^{dried for 7 hours at 120 3} C, were obtained

plexes containing 5.3% Al and 2.92% Co with the 480 g of solid. If this is 3 hours at 500 ³ C

Molecular formula Al _e Co ₂ (OH) ₂₃ (NO ₃ ) ₅ , and 1500 g of a calcined one obtained 280 g of disperse system,

aqueous solution of a metal complex containing this consisted of 13.4% NiO, 10.3% MoO ₃ and

9.90% Al and 3.19% Mo with the empirical formula 74.5% Al ₂ O ₃ . The examination with X-ray diffraction

Al ₁₁ Mo (OH) ₃₀ Cl ₈ , were mixed and about 30 Mi- to showed that this disperse system has an amorphous structure.

utes stirred. If this solution was kept in the door for 5 hours. The result of the X-ray micro-

an oven maintained at 12O ⁰ C was dried, analysis showed that each metal in a uniform manner

960 g of solid were obtained. When this was dispersed at 3 hours and that the size of the dispersing

550 ° C was calcined, SOO g of disperse particles were obtained below 1.0 μ, the limit of dissolution of the

System consisting of 7.6% CoO, 14.4% MoO ₃ and 15 apparatus. 76.6% Al ₂ O ₃ .

Examination by X-ray diffraction showed 'B e i s ρ i e 1 21 that this disperse system has an amorphous structure

owned. The result of the X-ray microanalysis If 1800 g of an aqueous solution of a metal

Analysis showed that each metal was uniformly ⁹ ° complex, containing 9.0% Al and 0.62% Fe with the

was dispersed and that the size of the dispersed empirical formula Al ₃₀ Fe (OH) ₇₆ Cl ₁₈ , for 12 hours in

Particles below 1.0 μ day, the resolution limit of an oven maintained at 8O ⁰ C, and then S hours Apparatus. were dried tang at 105 ° C., SSO g were obtained Example 20 hours of solid. If this gradually increases in 5 hours

as heated from room temperature to 1200 ⁰ C and

1300g of an aqueous solution of a metal complex, then calcined at 1200 ° C for 2 hours

Contains 4.44% At and 2.23% Ni with a total of 322 g disperse system, consisting of 4.97% Fe ₄ O ₃

formula Al ₄ Ni (OH) ₁₀ Cl ₄ , «nd 760 g of an aqueous and 95.0% Al ₂ O ₃ .

Solution containing 7.16% Al and 2.6% Mo with the X-ray diffraction study showed this Sum formula Al ₁₀ Mo (OH) ₂ SCl ₁₀ , were mixed 30 disperse system some Ct-Al ₁ O ₃ and weak a-Fe, O _a

and stirred for about 30 minutes. Then were under diffraction lines. The result of the X-rays'

vigorous stirring 1000 ml of an aqueous solution, microanalysis showed that each metal in uniform egg

containing 120 g of caustic soda as a precipitant, was dispersed in a manner that the size of the dispersed

added to produce a precipitate. These yawed particles were below 1.0μ, the limit of resolution

was aged at about 70 ^° C. for 2 hours. Then became 35 of the apparatus.

Claims (5)

Patent claims: 1. Process for the production of a disperse system from aluminum oxide and one or several metals, which have a higher single-electrode potential than aluminum, or oxides of such metals, characterized in that containing one or more metal complexes Aluminum and one or more metals that have a higher single-electrode potential than Have aluminum, with the empirical formula Al _n M _n , (OH) "| X _3n ip-m wherein ;; the number of aluminum atoms, M one or more metals, n ' the total number of atoms of these metals, m the number of OH groups, X one or several monovalent anions, ρ the total of the valencies r'.er M and 3 / i Ι ρ m mean the total number of X atoms, and where between n, /; ', ρ and m are the interrelationships n / n ' a I
and 3/1 f ρ > m consist, be dried and calcined. 2. The method according to claim 1, characterized in that the complex or complexes before Drying and calcining can be converted into a gel with a gelling agent. 3. Process according to Claims 1 and 2, characterized in that the metal complex or complexes before drying and calcining by adding a base that provides a decomposable salt, be converted into a gel or a precipitate. 4. Process according to Claims 1 to 3, characterized in that the metal complex or complexes before drying and calcining by adding a common base to a gel or a precipitate be transferred. , 5. Metal complexes containing aluminum and one or more metals that have a higher single-electrode potential than aluminum, with the empirical formula AI _n M _n , (OH) _m X ₃ "."", where // the number of aluminum atoms, M one or more metals, > i ' the total number of atoms of these metals, m the number of OH groups, X one or more monovalent anions, ρ the total sum of the valencies ^{of M and 1 Zn-} Yp — m mean the total number of X atoms, and where between n, n \ ρ and m are the interrelationships 55 n / n ' a I
and Zn-Yp> m
exist.