DE1075593B - Process for the preparation of catalysts for the synthesis of alcohols and alkydiols - Google Patents

Description

GERMAN

The present invention relates to improved catalysts for the synthesis of alkynols and alkynediols by converting aldehydes or ketones with an acetylene hydrocarbon.

In the main patent 1 013 279 is a "process for the preparation of catalysts for the synthesis of Alkynols from a carbonyl compound and an acetylene hydrocarbon. by knocking down Copper oxide and optionally bismuth oxide or another oxide which retards the formation of cuprene to a silica-containing carrier, which is characterized in that the so impregnated silica-containing carriers so long to a temperature of. 400 to 800 ° C is heated up in the surface layer Copper and optionally bismuth silicates are formed and the catalyst treated in this way does not form red copper acetylenide with acetylene at room temperature.

The inventive method is a further development of the method of the main patent and is characterized in that a silica-containing carrier is used which is produced thereby has been that a mixture of kaolin and a water-soluble, synthetic, organic, polymer Binder is processed into shaped bodies, these shaped bodies for the purpose of Axisbrennens the binder and for the purpose of converting the kaolin to montmorillonite in air to about 800 to 850 ° C and then to about 1000 to 1200 ° C to obtain a muilitic silica-containing carrier be heated.

The catalysts obtained using the above-mentioned kaolin carrier have, if they are used in the preparation of alkynols and alkynediols as described above, one significantly longer service life and increased mechanical strength, and they also make it possible to achieve good yields of the desired products with the slightest cupra formation.

As a water-soluble, synthetic, organic, polymeric binder used in the manufacture of the said improved kaolin carrier can be used, polyacrylic acid, alginic acid (polymannuronic acid), Pectic acid (polygallacturonic acid) and especially polyvinyl methyl ether and methyl cellulose as well as their water-soluble salts and their mixtures are mentioned. These binders are the Binders, such as glucose, cane sugar, syrup, molasses, gelatin, starch, which are commonly used in the manufacture Used by catalysts, superior as they can be more easily burned out and are carriers with higher porosity. The amount of binder to be mixed with the kaolin should be so large that that a mass is obtained which, if necessary by a process for the preparation

of catalysts for synthesis

of alkynols and alkynediols

Addendum to patent 1013 279

ίο Applicant:

General Aniline & Film Corporation,
New York, NY (V. St. A.)

^X 5 representatives:

Dr. W. Schalk and Dipl.-Ing. P. Wirth, patent attorneys, Frankfurt / M., Große Eschenheimer Str. 39

Claimed priority:

V. St. v. America December 30, 1594

Otto Friedrich Hecht, Easton, Pa. (V. St. A.),
has been named as the inventor

a pre-drying, in some way, like, through Stamping, spraying or pressing, can be deformed. Preferably the mass should when deformed will have a putty-like consistency.

During the burnout at temperatures of around 800 to 850 ° C, the synthetic organic is ashed Binder and burns out, so that fine pores remain in the ceramic material and this then has a large active surface. At this point in the process, the established Moldings mainly made of montmorillonite. By further heating, roasting and Burn out at temperatures from 1000 to 1200 ° C is, although the porosity and hence the amount of active surface area of the support is reduced

⁴ S is obtained, a product which has a high mechanical strength and is very resistant to abrasion.

The resultant multi-layer carrier is then used in the process of making those described above Catalysts are used as the silica support and this method is quite general in that the carrier is impregnated with the copper (and bismuth) compounds for as long as 400 to 800 ° C is heated until the desired topochemical

909730/500

see reaction is obtained by soft in the surface layer the formation of copper (and Bismuth) silicates ».

The invention is described in more detail by the following example. The parts are parts by weight.

example

1000 parts of kaolin LAl ₂ O ₃ · 2 Si O ₂ · 2 H ₂ O] were mixed with 500 parts of a 30% strength aqueous solution of a polyvinyl methyl ether (specific viscosity: 0.54 in 1% strength benzene solution at 25 ° C.) to form one putty-like consistency mixed. This mixture was then pressed through a press with holes about 4 mm in diameter and the resulting strands were cut into shaped pieces about 5 to 6 mm in length.

The moldings produced in this way were then dried in an oven at 80 to 90 ° C. to remove the water and then roasted for 5 hours at 800 to 850 ° C., whereby the kaolin in the presence of air over the metakaolin stage [Al ₂ O ₃ -2 SiO ₂ ] converted into montmorillonite [Al ₂ O ₃ ^ SiO ₂ ] and the polyvinyl methyl ether was completely burned out. This montmorillonite was then roasted for 1 hour in an electric oven at 1080 ° C., as a result of which a “semi-mullite” state is obtained. (According to the X-ray, this product already consists of mullite [3 Al ₂ O ₃ -2 Si O ₂ ] in terms of its structure, but the mechanical strength is still somewhere between montmorillonite and mullite.)

After this product had been slowly cooled to room temperature, 1000 parts of this ceramic product were dissolved with a solution of 387 parts of copper nitrate trihydrate and 180 parts of bismuth nitrate pentahydrate, which was dissolved in a mixture of 334 parts of nitric acid (70 ⁰ mg) and 250 parts of water were impregnated.

This product was then slowly dried by evaporating the water and the acid it is heated to 80 ° C for 42 hours, then heated to 500 ° C for 36 hours and roasted.

Finally, 1215 parts of catalyst were obtained, which after reduction (by 30 minutes Wetting ^ with 12% neutralized formaldehyde solution) and generation with acetylene was used in the alkynol synthesis according to the main patent. This In the synthesis mentioned, an improved catalyst has a significantly higher mechanical strength and a longer effectiveness than the catalyst used according to the main patent.

Further, although the copper-bismuth catalyst used in the above example may be more preferable If the catalyst is used, the process can also be carried out if the on a silicic acid Supported copper catalyst of U.S. Patent 2,232,867 is used and when these catalysts according to the invention, as described, are heated to 400 to 800 ° C. for so long that Copper silicate is formed on the surface layer and the catalyst thus treated does not contain red copper acetylide forms more when treated with acetylene at room temperature. The so obtained Otherwise, heat-treated catalysts are significantly superior to the same copper catalysts that are not have been heat-treated in the above-mentioned manner. As stated in U.S. Patent 2,300,969, can use the copper on the carrier instead of or together with bismuth as well Substances that prevent the formation of cuprene are used, and becomes such a catalyst, as described above, subjected to a heat treatment so that copper silicate in the surface layer and no more red copper acetylide is formed when the catalyst is treated with acetylene at room temperatures, so will obtain a product which as a catalyst for the present reaction is essentially the same catalyst which has not been subjected to such heat treatment. When working with the The preferred copper-bismuth catalyst described above has been shown to have the properties in the catalyst used relative aliquots of copper and bismuth are not very crucial. There were bismuth amounts of 25 to 100% of the amount of copper in the catalyst used, and these have been found to be satisfactory. As the amount of bismuth increases, Using the catalyst slows down the cuprene formation somewhat. With such a slowdown however, cuprene formation is also accompanied by a slight decrease in conversion, and it is therefore, it is preferable to use catalysts which have the lowest possible bismuth content.

Claims (1)

Claim: Process for the preparation of catalysts for the synthesis of alkynols from a carbonyl compound and an acetylene hydrocarbon by heating one with copper oxide and optionally bismuth oxide impregnated silica-containing carrier to 400 to 800 ° C up to Formation of copper and optionally bismuth silicates in the surface layer and so on treated catalyst at room temperature with acetylene does not form red copper acetylenide, according to Main patent 1 013 279, characterized in that a silica-containing carrier is used, which has been produced by using a mixture of kaolin and a water-soluble, synthetic, organic, polymeric binders-too. Moldings is processed, these moldings to burn out the binder and to convert the kaolin to montmorillonite the air to about 800 to 850 ° C and for the purpose of extraction a mullit-like silica-containing carrier to be heated to about 1000 to 1200 ° C. Considered publications:
U.S. Patent No. 2,3QO969. © 909 730/50 »2.60