DE1542392B - Process for the production of platinum metal catalysts on basic carbonate carriers - Google Patents

Description

1 2

The invention relates to a method for producing ren for producing abrasion-resistant spherical mixed

of platinum metal catalysts based on basic carbon catalysts, in which the spherical shape by

natträgern by impregnating basic Metallcar- introducing one with hexamethylenetetramine or one

bonaten with a platinum metal salt solution, added another base, a basic aluminum salt

basic solution, filtering, washing, drying and 5 solution-containing mixture in one with water

Reduce with hydrogen. immiscible liquid is generated, as

Such a process is known per se from the mixture components pure oxides or hydroxides or German patent specification 1 070 160, according to mixtures of oxides and / or hydroxides which catalysts for the selective hydrogenation used alone or together with active alumina of unsaturated aldehydes are thereby produced. The patent documents mention that a solid, slightly alkaline writing, for example Al ₂ O ₃ , SiO ₂ , MgO, ZnO, TiO ₂ , carrier with a solution of compounds of the Pia-ZrO ₂ , Cr ₂ O ₃ , NiO, Oxides of the rare earth metals, tin metals in hydrous organic solvents with aluminum hydroxide and chromium hydroxide. Basic materials soaked, the product obtained, optionally carbonates of rare earth metals, are not mentioned in the patent specification with an aqueous solution of an alkali hydroxide, and in any case be -carbonate or -bicarbonate, and the catalyst support is due to the platinum metal oxide formed as a result of its production Metal reduced to a substantial part from aluminum oxide. As kata becomes. The slightly alkaline acting metal can be lytically active in the examples of. ger a solid and practically water-insoluble oxide, patent specification called platinum, chromium and nickel. The hydroxide, basic oxide, carbonate or basic 20 platinum catalysts described in the examples can be carbonate of a metallic element. Aluminum oxide, ren and isomerization are used as additives, not for hydrogenation, but for reforming such carriers. . Magnesium Oxide, Titanium Oxide, Chromium Oxide, Charcoal, Given these significant differences, it was called silica gel and pumice stone. not obvious, platinum metal catalysts according to,

The invention is based on the object of producing a method of the invention described above for the production of platinum metal carrier catalytic converters, which are exclusively used as catalytic converters to make available, in which catalysis contains carbonates of rare earth metals, gates arise that are not only selective and it was besoriders in view of revelation Hydrogenation of unsaturated aldehydes, but the German patent 1 070 160 surprisingly, also for all other reactions (like hydrogenation 3 ° to find that the cata reactions produced according to the invention in general, carbonylation and oxidizers in the hydrogenation of substituted cyction reactions) which, with the help of platinum-metallic compounds, yield almost quantitative yields metal catalysts can be carried out, and deliver on the desired product, which are particularly characterized by the fact that for the purposes of the invention it is essential that Hydrogenation reactions, especially when the catalyst has the smallest possible crystallite size, the hydrogenation of substituted cyclic compounds - preferably below 400 Å, in particular below 100 Å, fertilize, as the hydrogenation of ρ, ρ'-methylenediani- exhibits. The usual processes produce PIalin to p, p'-di (aminocyclohexyl) methane, far less tin metal catalysts with crystallite sizes within ger to the formation of undesired by-products in the ranges given above; however, it has to be on it Ren than the previously known platinum metal support cata 40 should be respected that the. Catalyst not that long analyzers. is heated until the crystallites are above the specified

This task will grow in the area mentioned at the beginning. With a 3-hour reduction

The method according to the invention is achieved in that one takes place at about 600 ° C. B. a crystallite growth

Ammonium carbonate to an aqueous platinum metal- the desired size addition. A similar crystal

Salt solution is added until the pH value rises to 3.8 to 4.2 gel growth occurs at higher temperatures, e.g. B.

has increased, then finely divided basic carbonates of 30 minutes long reduction at 800 ^° C. The above

rare earth metals, the CO ₃ content of which are boundary conditions, and

20 to 95 percent by weight of the compound with the crystallite size should, if you are so sharp

all rare earth metals theoretically required conditions works, controlled, are.

COg amount is, and the crystallite sizes of not 50. The crystallite size is the easiest to pass through

have more than 400 Å, then the pH value by means of small-angle X-ray produced in a known manner

Determine further addition of ammonium carbonate on 7.8 to diffraction diagrams. The special

8.1 increased, then the resulting slurry will have preferred products according to the invention

at a temperature above 5O ⁰ Q at least 20 micro crystallite um.etwa 80 to 100 Å or less,

Nuts digested, filtered slurry, the FH-55.

washes out the residue, and the washed filter- In the catalyst prepared according to the invention

Residue at about 125 to 500 ° C, preferably below ren, there is a platinum metal, one of the

300 ° C; calcined under such conditions that hydroxycarbonates of the rare earth metals or

a CO ₃ content: the carbonates, the rare earth-based on a mixture of hydroxycarbonates

metals from. about 5 to 80 percent by weight of the rare earth metal used as a carrier. There are numerous

Connection, with all rare; Erdmetallen Theo- technical mixtures of rare earth metals or

retisqhv required CO ₃ content, achieved. Compounds of rare earth metals available that

In _{: the} preferred way is to go with. the process as by-products of isolation _; the individual

the invention of basic carbonates of the rare rare earth metals. There are e.g. Bi mixtures,

Earth metals that have crystallite sizes less than. 65 such as the by-product known as didymium that is found in

about 100 A ₁ .. the removal of cerium from naturally occurring

Out. of the patent specification: 20: 704, of the office for inventions, mixtures of rare earth metals accrue,

education and ^; Patent system in East Berlin is a process similar to falling mixed rare earth metal products

I 542 392

3 4

also when separating lanthanum, praseodymium or the platinum metal usually in amounts of about

Europium from naturally occurring mixtures 0.01 to 10%, based on the total weight of the

on. Supported catalyst on; Quantities from about 2 to

The rare earth metals are lanthanum, cerium, praseo - 5 percent by weight platinum metal is common

dym, neodymium, promethium, samarium, europium, 5 preferred.

Gadolinium, Terbium, Dysprosium, Holmium, Er- The platinum metal compound on the hydroxy

bium, thulium, ytterbium; Yttrium and luterium. carbonate of the rare earth metal contained as a carrier

The hydroxycarbonates of the rare earths corresponding supported catalyst can be in the form of grains

chen in their structure to the cerium hydroxycarbonate, or other molded bodies directly into the

which has the following empirical formula: io hydrogenation vessel must be entered. One works at

_r , _rn χ _r , _nm such temperatures that the platinum metal compounds

^^ vj _3h u ^ unj, _{dung in the} ^ _{metal and the hydroxycarbonate te} ii.

The other rare earth metals form in a similar way merges into the oxide. The extent of the latter

basic carbonates or, as they are preferably referred to, conversion depends on the temperature.

net, hydroxycarbonates. 15 Usually, however, the calcining takes place

The carbon content in these compounds can be added to the supported catalyst before it is introduced

according to the invention vary within wide limits, reaction vessel .. Such a supported catalyst is

especially since so ,, because the carbonate and Hydroxyver- heated to about 125 to 500 ⁰ C. Preferably turns

Bonds in calcining both to a large extent at temperatures below 300 ° C, and in each

pass into the oxide. 20 trap, the heating should not take longer than it is for

In general, the hydroxycarbonate of the rare product is said to require the desired calcination of the product.

Earth metal 20 to 95 _{% of the amount of CO a} contained, is borrowed. Typical conditions are in the following

which is theoretically required to give the carbonate of the examples given,

rare earth metal. When heated in the presence of hydrogen goes

The rare earth hydroxycarbonates can convert the platinum metal compound into the metal, while

be produced by known methods. The hydroxycarbonate can transform itself into an oxide

a soluble salt, such as chloride, nitrate or acetate, which still contains some carbonate is delt. The Um-

or the like, a rare earth metal or a conversion to oxide should not proceed so far,

Mixtures of rare earth metals dissolve in water until the carbonate completely decomposes. The end-

and the carbonate with sodium or potassium carbonate 30 measured the conversion of the carrier and the amount

fail. of carbonate, which is still in the by decomposition of the

The proportion of hydroxyl groups or the extent of hydroxycarbonate formed oxide remains, the basicity of the catalyst support can easily be varied by adding an acid, such as hydrochloric acid, the temperature at which the carbonate is precipitated to the product and determining the gas evolution. At higher temperatures, measure 35 decomposed. The carbonate content (CO ₃ ) insures more carbonate than the hydroxide form. Hydroxyl bond of the rare earth metal can also be introduced from the groups but can also be introduced by calculating the evolution of carbon dioxide and should be used to precipitate together with the carbonate. as mentioned above, in the range of about 20 to 95% sodium hydroxide or ammonium hydroxide compared to the theoretical amount of CO ₃ which is required. 40 Hch is to stock up on all of the rare earth metal

After the precipitation, the precipitate is collected.

trated or centrifuged and heated with water or preheated in the manner described above

preferably with a carbonate-containing solution, hydroxycarbonate of the rare earth metal works

wash to remove soluble foreign ions. at temperatures below 200 ⁰ C with respect to his

The products precipitated in this way normally have a hydroxide content almost quantitatively in the oxide.

Crystallite sizes below about 100 A. If the product The conversion of the carbonate content into the oxide

However, drying at higher temperatures tend to depend on the temperature and duration of the drying

the crystallites tend to enlarge and prolonged heating.

Drying or calcining at high temperatures. According to the invention, this should be done after heating

should therefore be left behind in all stages of the procedure for 5.0 of the rare earth connection

Manufacture of these products should be avoided. There CO ₃ , determined by measuring the CO ₈ , about 5 to

must be paid attention to * that the crystallites are 80 percent by weight of the amount that

do not grow above 400 A; Preferably, nian holds the theoretically required to be with everyone in attendance

Crystallite size below about 100 A. Rare earth metals form the carbonates. The catalysts used in conjunction with the hydroxide support Amount: the platinum metal compound can usually be used for carbonylation reactions, e.g. B. with Wise; fluctuate within wide limits. Under carbon monoxide and hydrogen, for production Under certain circumstances, amounts of 0.0001% are sufficient; mixed long-chain alcohols are used,

but they are usually used no less than. Particularly suitable for the hydrogenation of

about 0.01% platinum metal, calculated as metal and 60 substituted cyclic compounds, such as the hy-

based on the total weight of the supported catalysis of nitrobenzene to aniline or. Amino

tors including the hydroxycarbonate. The upper cyclohexane, from methylenedianiline to p-aminocycIo-

Limit for the amount of platinum metal is based on hexylmethane, from dicyanobutene to dicyanobutane and.

purely practical; Considerations in amounts over about continue in the presence of ethylene.

10% the catalytic metal separates to a large extent 65 Except for those hydrogenation reactions for which

as a coating on other particles of the platinum metal- the catalysts are particularly preferred, can-

connection because not sufficient. They are also used for all those reactions

more space is available. Therefore, one turns, for which one has already used platinum metals

has applied, such as the oxidation of malodorous or disruptive exhaust gases to carbon dioxide, whereby Hydrogen and nitrogen form harmless products.

In the following examples, parts and percentages relate to the amount by weight.

example 1

1. A reaction vessel equipped with a stirrer is charged with 1000 parts by weight of water. To this end, ruthenium chloride is added in an amount corresponding to 5 parts by weight of ruthenium. The ruthenium chloride will be dissolved in the water and the solution heated to 70 ⁰ C.

2. Separately, a solution of 100 parts by weight is used Ammonium carbonate made in 1000 parts by weight of distilled water.

3. A commercially available mixture of hydroxycarbonates of rare earths which has on COj-free basis, calculated as oxides, the following composition is calcined for 3 hours at 400 ⁰ C in the air:

Weight percent

CeO _x

La ₁ O ₃

Nd ₁ O,

Pr ₁ O ₁

Sm ₁ O,

_13th

Yttrium and other rare earths

47

24.5

19.5

6.0

2.0

0.5

0.5

The carbonate content of the hydroxycarbonates of the rare earths, determined as CO ₂ and calculated as COj, is 60 Vo of the CO ₃ that can theoretically combine with the rare earth metals. After calcining, the CO ₃ content is determined by adding dilute hydrochloric acid to the rare earth compounds and measuring the COi that develops. The CO, content is now 37% of the amount that can theoretically combine with the existing rare earth metals to form carbonates.

4. The solution prepared in stage 2 is sprayed into the solution prepared in stage 1 until a pH 4.0 is reached. 100 parts by weight of that prepared in step 3 are then added to the solution Mixture of rare earth oxide carbonates too.

5. The ammonium carbonate solution is then added until the pH is 8.1 to precipitate the ruthenium chloride on the mixed rare earth oxide carbonates.

6. After the precipitation, the slurry is digested for 60 minutes at 70 ⁰ C.

7. The slurry is filtered and the filter residue on the filter with a solution of 100 parts by weight of ammonium carbonate washed in 2000 parts by weight of water.

8. The filter cake is stored for 12 hours at 125 ° C dried and then placed in a heated cylindrical vessel with connections for introducing of hydrogen at one end and to vent the exhaust gases from the other end.

9. The catalyst obtained in this way is ^{reduced at 200 °} C. until the reduction to ruthenium, recognizable by the formation of water, has ended.

Before the reduction, the filter cake can be formed into suitable shaped bodies such as 3.2 mm cylinders Length and 3.2mm diameter or other. Deform moldings and then with hydrogen to reduce.

The crystallite size of the oxide carbonates of the rare earths is 225 Å and that of ruthenium less than 80 Ä. The crystallite size of ruthenium is determined by the compounds of the rare Earth metals are brought into solution in dilute hydrochloric acid, whereupon the crystallite size of the

ίο residual metallic ruthenium due to Klein angular X-ray diffraction determined. The crystallite size of the rare earth compounds is also increased determined by the small-angle X-ray diffraction method in the presence of ruthenium, since the latter has so much smaller crystallite size that it does not interfere with this determination. For the purpose of In any case, it is only essential for the invention that the crystallite sizes of both compounds are below the limit specified above.

Example 2

1. 2 parts by weight of ruthenium are dissolved in 1000 parts by weight of water in the form of ruthenium chloride.

2. A second solution is made by dissolving 100 parts by weight of ammonium carbonate in 1000 parts by weight distilled water.

3. A commercially available mixture of hydroxycarbonates of rare earth metals with a carbonate content of 65% of theory ^it and the following composition, calculated on CO ₂ -free base as oxides, is calcined for 3 hours at 500 ° C:

Weight percent

CeO ₂ .

La ₂ O ₃ .

Pr ₈ O ₃ -

Nd ₂ O ₃

Sm ₂ O ₆

Eu ₂ O ₃

Gd ₂ O ₃

Pm ₂ O ₃
Tb ₂ O ₃ .
Dy ₂ O ₃
Ho ₂ O ₃
He ₂ O ₃ .
Tm ₂ O ₃
Yb ₂ O ₃
Lu ₂ O ₃ .

48

34 4

13 0.6 0.15 0.30 0.13

0.30

The powder obtained in this way has a carbonate content of 21% of the amount that is theoretically required to form carbonates with all rare earth metals.

4. The solution prepared in stage 1 is ^{heated to 75 °} C. with stirring and the solution prepared in stage 2 is added dropwise until the pH is 4.0.

5. Now 100 parts by weight of the in stage 3 produced finely divided mixture of rare earth carbonates slurried in the solution.

6. The ammonium carbonate solution is then added until the pH is 8.1 is reached.

7. After complete precipitation, the slurry is digested for 40 minutes at 75 ⁰ C.

8. The slurry is filtered and the filter residue, as in step 7 of Example 1, with ammonium carbonate solution washed. The filter cake is dried at 150 ° C. for 12 hours. i

9. A portion of the rare earth oxide carbonate powder prepared according to step 3 of this example is shaped into rectangular cylinders measuring 3.2 x 3.2 mm with the aid of the Stoke's pill press, and these cylinders are coated with a slurry of the filter cake dried according to step 8. The slurry is made to 15% ^solids and the balance water, such that the coated cylinder after the drying show a 20% weight gain, which is due to the added material.

The coated cylinders are ^{reduced at 225 °} C. with hydrogen. The crystallite size of the rare earth oxide carbonates obtained in this way is 290 Å. The crystallite size of ruthenium is less than 80 A.

The catalyst obtained in this way is suitable for the hydrogenation of Methylenedianiline to p-aminocyclohexylmethane or for the other hydrogenation and hydrogenation specified above Oxidation reactions.

B e i s ρ i e 1 3

1. A reaction vessel equipped with a stirrer is charged with 250 parts by weight of water. For this rhodium chloride is added in an amount corresponding to 5 parts by weight of rhodium. The rhodium chloride is dissolved in the water and the solution is heated to 65 ° C.

2. Separately, a solution of 100 parts by weight of ammonium carbonate in 1000 parts by weight of distilled water is prepared.

3. A commercially available mixture of rare earth hydroxycarbonates which is used during purification of rare earth salts is obtained by isolating a stream from which all Ingredients except cerium. Praseodymium and lanthanum have been removed has the following composition:

Weight percent

Cerium oxide ... 62

Praseodymium oxide. 19th

Lanthanum oxide 19

. All of these rare earths lie in the form of the partial decomposed carbonates before; However, the above analysis values relate to carbon dioxide-free Base. These rare earths have been converted into the hydroxycarbonates and form the raw material, from which the oxide carbonates used in this example are prepared by the following procedure will be: (a) After isolating the crude carbonates of cerium, lanthanum and praseodymium 1000 parts of these carbonates slurried in 10,000 parts of distilled water, whereupon enough Nitric acid is added to completely dissolve the carbonates, (b) Then through Spraying 10% ammonium carbonate solution into the solution while stirring at 50 ° C to remove the precipitate carried out until a pH of 7.5 is reached. (c) The carbonates are filtered off, dried and calcined at 200 ° C. to give the rare earth oxide carbonate used in this example.

4. The solution prepared in stage 2 is sprayed into the solution prepared in stage 1 until the pH is 3.8. 100 parts by weight of the mixture prepared in step 3 are then added to the solution from rare earth oxide carbonates.

5. One continues with the addition of ammonium carbonate solution continue until the pH has risen to 8.1 to add the rhodium chloride to the mixed · Precipitate rare earth oxide carbonates.

ίο 6. After the completion of the precipitation, the slurry becomes Digested at 65 ° C for 90 minutes.

7. The slurry is filtered and the filter residue on the filter with a solution of Washed 100 parts by weight of ammonium carbonate in 2000 parts by weight of water.

8. After filtering, the filter cake is dried at 125 ° C. and in the same manner as in step 8 of example 1 Reduced reduction vessel described after step 9 of Example 1.

The catalyst thus obtained is suitable for the hydrogenation of double bonds, such as for the hydrogenation of Ethylene to ethane, from benzene to cyclohexane, from dicyanobutene to adipic acid nitrile and from adipic acid nitrile to hexamethylenediamine. The catalyst is also suitable for hydrogenating benzonitrile Cyclohexyl cyanide and finally to aminomethylcyclohexane.

The carbon dioxide content of the mixed hydroxy carbonates of rare earths is 95% of theory before calcining and after calcining , 80% of theory. The crystallite size of the rare

Earth metal carbonate after calcining is 90 Å.

that of rhodium is less than 80 Å.

Instead of the rhodium given in step 1, platinum chloride or palladium chloride can be used in Use stoichiometrically equivalent amounts to prepare similar catalysts.

B e i s ρ i el 4

1. A solution of 2 parts of ruthenium in the form of the nitrate in 150 parts by weight is distilled Water produced.

2. There are 1100 parts by weight of a 10% solution. of ammonium carbonate in distilled Water produced.

3. A mixture of hydroxycarbonates of rare earth metals, which on a CO ₂ -free basis, expressed as oxides, has the following composition, is calcined for 3 hours at 800 ° C:

Weight percent

Cerium oxide '. . 43

Praseodymium oxide 5

'Samarium oxide 5

Europium oxide 5

Gadolinium oxide 3

Terbium oxide. 1

Dysprosium oxide: ..... 2

χ holmium oxide 2

Erbium Oxide ... 6

Thulium Oxide ... 3

Ytterbium oxide .. *. 4th

Lutetium oxide 4

Lanthanum Oxide 17

4. The solution prepared in step 1 is heated to 75 ° C. with stirring and slowly mixed with the in

109 649/134

Stage 2 prepared solution is added until the pH is 4.2.

At this point, 100 parts by weight of the finely divided mixture prepared in step 3 are made Rare earth oxide carbonates slurried in the solution.

5. It continues with the addition of ammonium carbonate, is up to the pH 7.8, after which the slurry is digested for 45 minutes at 75 ⁰ C.

6. The slurry is filtered and the filter residue with 500 parts by weight of 10% ^'er g Ammohiumcarbonatlösung washed.

7. The filter cake is ^{dried at 150 °} C. for 12 hours.

8. The dried filter cake is powdered to grain sizes up to a maximum of 74 μ and then ^{reduced at 225 °} C. with hydrogen.

The catalyst obtained in this way is generally suitable for hydrogenation.

The crystallite size of the calcined rare earth carbonates, on which the ruthenium is deposited is 300 Å, while the crystallite size of the Ruthenium is less than 80 A.

The carbon dioxide content of the rare earth hydroxycarbonates used in this example is 70% of theory before calcination and 5% of theory after calcination. The apparent density of the catalytic converters ■ föfs produced from the calcined at 800 ⁰ C Hydroxycärbonaten rare earth is 1.00 g / ml, and is therefore higher than that of carbonates which have been calcined at lower temperatures. This high density is particularly noticeable in work in which the hydrogenation slurry is drawn off through a dip tube. As a result of the higher density of the catalyst produced in this way, it is possible to pull off an upper layer of the liquid product that is relatively free of catalyst, so that less material has to be filtered.

A similar catalyst can be prepared with the difference that the rare earth hydroxy carbonates are calcined at 600 ⁰ C. After calcining at 600 ° C., the carbonate content is 36% of theory. Palladium nitrate can be used in place of ruthenium nitrate to produce an equally effective catalyst.

'"'; ■ '.Example

At 230 ^° C. and a hydrogen pressure of 210 atmospheres, 20 parts of p, p'-methylenedianiline are hydrogenated over 10 parts of the finely divided ruthenium supported catalyst according to Example 1 for 30 minutes in a pressure vessel.

The hydrogenation mixture is released from the catalyst filtered off and then distilled in vacuo. A completely saturated mixture of isomers is obtained p.p'-DKaminocyclohexyO-methane in one yield of 99.3% of the methylenedianiline used. The distillation product contains more than 45% of the trans, trans stereoisomers of p, p'-di (aminocyclohexyl) methane and is a solid at 25 ° C.

If the process of Example 5 is carried out using a ruthenium catalyst which has as a carrier cerium oxide which contains 45% of the theoretical _{amount of CO 2} for the formation of cerium carbonate, practically the same results are obtained.

Example 6

A stainless steel stirred autoclave equipped with a product discharge line so arranged is that the catalyst remains in the reaction vessel, p, p'-methylenedianiline with 2000 parts and 10 parts of the finely divided ruthenium supported catalyst prepared according to Example 2 charged.

The contents of the reaction vessel are heated to 225 ° C. with stirring ίο, and the pressure is reduced by introducing held by hydrogen at 300 at. More p, p'-methylenedianiline is added to the reaction vessel with such Speed fed that the residence time-60 minutes is, and the product is withdrawn at such a rate that the volume of the reaction mixture remains constant.

The product gives a completely saturated mixture of stereoisomers on vacuum distillation of pjp'-Di-iaminocyclohexyO-methane in excellent. nice yield. ' The distillation product consists of 48% of the trans, trans stereoisomers of ρ, ρ'-di (aminocyclohexyl) methane. .

If example 6 is carried out with the supported catalyst prepared according to example 3, one obtains the same excellent results. ■

B e i s ρ i e 1 7

According to Example 1, a catalyst is prepared by the process of the invention which contains 5% ruthenium on a carrier made of rare earth metal carbonates. For comparison purposes other 5% ruthenium-containing catalysts are prepared by similar processes, the have other catalyst supports.

These catalysts are used to hydrogenate ρ, ρ'-methylenedianiline to p, p'-di (aminocyclohexyl) methane (PACM) is used. The hydrogenation takes place in a high pressure bomb, in which the reactants are first introduced can be entered and into which hydrogen can be introduced during the reaction.

The bomb is in a shaking machine

and the contents are mixed evenly and quickly during the conversion by shaking. The bomb is charged with 100 parts of methylenedianiline, 50 parts of dioxane, 10 parts of ruthenium catalyst and 25 parts of ammonia. The reaction is carried out at 225 ^° C. and 350 atm. Hydrogen pressure. During the reaction, the hydrogen pressure is kept constant by temporarily adding hydrogen until no further hydrogen is absorbed. The reaction mixture is then discharged and distilled. The results are as follows:

Catalyst carrier

Silica-alumina ..

Silica gel

Aluminum oxide ......

Rare
Earth metal carbonates

Products, percent by weight

of the used

Methylenedianiline Forerun I PACM I residue

4.6

8.2.

1.5

0.8

90.3 90.2 91.7

98.8

5.0 1.6 7.8

0.4

Example 8

Example 7 is followed, but only with 450 parts Methylenedianiline and 10 parts of ruthenium catalyst

gate as an initial good. The hydrogen pressure in this example is 316 atm. Results:

Catalyst carrier

Activated carbon

Barium sulfate

Silicon dioxide

Alumina

Rare
Earth metal carbonates ...

Products, percent by weight

of the used

Methylenedianiline

Forward I PACM | Residue

4.7 0.6 0.7 1.8

0.3

67.6 87.2 90.4 73.6

99.3

27.7

12.2

8.9

25.6

0.4

Claims (2)

Patent claims: 1. Process for the preparation of platinum metal catalysts on basic carbonate carriers by impregnating basic metal carbonates with a Platinum metal salt solution, addition of a basic solution, filtering, washing, drying and reducing with hydrogen, characterized in that ammonium carbonate is added an aqueous platinum metal salt solution is added until the pH has risen to 3.8 to 4.2, then finely divided basic carbonates of rare earth metals are added, the CCX, content of which is about 20 to 95 percent by weight of the CO theoretically required for connection with all rare earth metals ₃ amount and the crystallite sizes do not exceed 400 Å, then the pH value is increased to 7.8 to 8.1 by further addition of ammonium carbonate, then the resulting slurry digests at a temperature above 50 ° C for at least 20 minutes , the slurry is filtered, the filter residue washes out and the washed filter residue is ^{calcined at about 125 to 500 0} C, preferably below 300 ° C, under such conditions that _{the carbonates of the rare earth metals have a CO 3} content of about 5 to 80 percent by weight of the for connection with all rare earth metals theoretically required CO ₃ content achieved. 2. The method according to claim 1, characterized in that one of the basic carbonates rare earth metals that have crystallite sizes of less than about 100 Å.