DE1235295B - Process for the production of butynediol mixed with propynol - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4207KW PATENT OFFICE

EDITORIAL

Int. Cl .: C 07 C

German KL: 12 o -19/03

Number:
File number:
Registration date:
Display day:

G33420IVb / 12o
October 24, 1961
March 2, 1967

It is known that liquid aldehydes and ketones in the liquid phase with acetylenic hydrocarbons the general formula

R-C = CH

in which R stands for a hydrogen atom or a hydrocarbon radical, in the presence of an acetylide a metal of group 1 b of the periodic table or of mercury can be implemented. at Conducting this process on a large scale has proven to be copper acetylide as the preferred catalyst proven. However, copper acetylide loses its activity in use, and side reactions then occur which reduce the yield of alkynols and alkynediols.

US Pat. No. 2,300,969 describes the activity of the copper catalyst by addition to lengthen such connections that prevent the formation of cupra. In practice it has it was found that this effect lasts longer if the catalyst does not contain elemental copper, the is formed by the slow decomposition of copper acetylide. It was found that the presence of bismuth oxide, bismuth oxyiodide or cerium oxide in the catalyst this formation of metallic Copper from the acetylide slows down.

US Pat. No. 2,768,216 discloses a process for the preparation of catalysts for Formation of alkynols and alkynediols through the reaction of acetylene or acetylene hydrocarbons described with carbonyl compounds, with copper oxide and bismuth oxide on a silicic acid Support material are deposited and the silica-containing support thus impregnated then is heated to a temperature between 400 and 800 ° C for 15 to 100 hours. These catalysts have a much longer lifespan and are more effective than the known ones Catalysts.

US Pat. No. 2,840,618 discloses a particular catalyst for the production of alkynols and alkynediols, which are applied to a mullit-like silica-containing carrier whose X-ray shows a mullite structure and that of kaolin and a water-soluble organic Polymer, preferably polyvinyl methyl ether, has been produced as a binder, the organic binder is burnt out and the kaolin is converted into mullite via montmorillonite will.

All of these known supported catalysts have processes for producing butynediol
in a mixture with propynol

Applicant:

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

Representative:

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

Named as inventor:
Otto Friedrich Hecht,
Max Eugene Chiddix, Easton, Pa. (V. St. A.)

Claimed priority:

V. St. v. America October 25, 1960 (64 697)

but a copper content of 13 Vo, more copper cannot be recorded.

However, it has been found in the course of experiments that a higher copper content in the supported catalysts for the production of alkynols and alkynediols would be very favorable, as such catalysts are more effective.

The invention now relates to a process for the preparation of butynediol in a mixture with propynol by reacting formaldehyde with acetylene in the presence of a catalyst composed of copper and bismuth on silica as a support, which is characterized in that the reaction is carried out in the presence of a catalyst which has a continuous silica gel phase and contains an average of 10 to 15% copper and 2 to 7% bismuth, the copper content in the surface layer being 15 to 25%, which is obtained by handling silica gel for 5 to 1 minutes with an aqueous solution of copper nitrate and bismuth nitrate in aqueous nitric acid containing 10 to 15 ° / »copper and 2 to 7 ⁰ zo bismuth, at room temperature and heating the dry-looking blue gel, which contains no excess liquid, to 500 to 700 ° C. for 3 to 14 hours .

The inside of the catalyst used according to the invention contains 5 to 12 Vo of copper.

“Catalyst with continuous silica gel phase” is understood to mean a catalyst in which the Silica gel represents the "stationary phase". For the-

709 517/560

3 4

like uses useful silica gels, the impregnation was carried out in a container for z. B. those with a particle size of 2 to 3.4 mm, 5000 parts by volume, which consists of a round glass flask are commercially available and can accommodate the desired amount with a single opening and a verbun amount of copper. The impregnation of the air inlet, which made a uniform carrier possible, is expediently carried out in a device still described below, which allows cool or hot air to flow through, where the carrier is circulated and moved cylindrical rod, which made it possible to pour the solution onto the moving gel. Piston is sprayed or sprayed on with the help of a small electric ventilator and, in the case of a space-lator belt motor, to rotate. The impregnation temperature is completely absorbed. This Im- io solution was at room temperature in a thin impregnation is finished after about 5 to 10 minutes. Current poured over the moving gel. The and the impregnated, completely dry blue mixture was agitated until the whole impregnation gel is then ^{absorbed in a solution solution for 45 minutes to 1} hour and a half, which is dried from the blue temperature of 140 to 155 ° C, whereupon it turns color of the finely divided silica gel could be seen, the 3- to 14-hour burning for decomposition 15 This process lasted 5 to 10 minutes. Then the copper and bismuth salts and conditioning the impregnated gel from the piston herausder catalyst surface at 300 to 700 'C was taken on and 1 hour at 15O ⁰ C dried and closes. then fired ^{at 500 °} C. for 5 hours. Included

A device suitable for moving and circulating the finely divided 450 to 455 parts of a finished silica gel catalyst consists, for. B. obtained from ao of deep black color. An analysis was ere-INEM rotating spherical or cylindrical, that the catalyst / contained on average 12.3 ⁰ Zo container made of earthenware, stainless steel, glass or copper and 2.6 ° o bismuth,
another acid-resistant material. A separate part of a catalyst, which is attached to a shaft like the side of the container, was made from above, but was driven after a motor and rotation allowed. Drying at 150 ° C for 2 hours at 500 ° C and white . On the other side, the container has been fired at 700 ° C for 2 hours. Upon analysis of an inlet port for air or an inert gas, it was found that the average copper and exhaust ports for the volatiles, the content of the catalyst 11.58 ⁰ Zo and that obtained by the introduction of air or inert gas in average bismuth content 2.68 Vo amount; on its the inlet port can be removed. This volatile 30 outer surface contained the catalyst 24.28 ⁰ Zo copper substances can be liquefied with the help of an attached cooling _and 3.83 ⁰ Zo bismuth, while inside the catalyst and a collecting device also _the copper content 10.85 Vo and the bismuth are liquefied. The impregnation liquid has a content of 2.6 Vo. These analytical values show a second inlet opening, which is close to the inlet υ _{3Γ and} clearly that the rapid impregnation with opening for air or inert gas in a thin room temperature has the special effect that a flow over the moving gel directed. _s j _c h a larger one on the outside of the catalytic converter

After filling the finely divided silica gel with a copper concentration in its interior, the impregnation _{solution, prepared in the manner described above} , is either poured onto the moving gel catalyst at W C with a loo-shaped mold or in a thin stream over it - ₄ o aldehyde solution with a pH of 4.6 and one passed. As the finely divided silica gel, the solution ^ nitrogen-acetylene mixture absorbs rapidly with a total Very, care must be taken, _{printing of 14 k} ^ _{cm2 Curr nd & emer period of 12} that the impregnating liquid uniformly over enabled _to 24 hours. Analysis showed that the whole of the gel was distributed so that a uniform Cu, C, content was between 9.4 and 10.5%. This impregnation takes place. After adding the 45 catalyst (40 parts), when used in an impregnation solution, the mixture is agitated until all the liquid is soaked in the autoclave with 500 parts by volume of 20,000 pieces, which is reflected in the aldehyde with a pH of 4.6 at a temperature of blue color of the finely divided silica gel can be recognized _{by 10 (PC and a} total pressure of 14 kgZcm *. The impregnation is generally according to the following conversion values:
finished about 5 to 10 minutes. The gel is then 50
Further dried in the manner described above and after 6 hours
burned. a formaldehyde conversion of 41 to 44Vo,

Example after 12 hours

368 parts of a silica gel carrier with a stationary 55 formaldehyde conversion of 82 to 85 ⁰ Zo. Phase with a particle size of more than 2 mm

were impregnated with 500 parts of a solution consisting of the following grain In the above conversion, no minor components occurred: reactions of formaldehyde; the reaction weight product contained about 95 to 96 ⁰ zo butynediol and about 60 4 to 5 ⁰ zo propynol. The catalog was able to

Copper nitrate trihydrate 206 can be used and resulted in various picks

Bismuth nitrate pentahydrate 32 Try an average formaldehyde conversion

_. ,., _n ,, »« -ι. wandlune of 85Vo in 12 hours. The to-

_{These two} salts were mixed in a pH range suitable for _{the process}

^from 65 catalyst is between 4.0 and 6.5.

Nitric acid (ex. Pure 70 "/ o) 118 _{When the obj ge} catalyst having a lOVoigen

and water 144 formaldehyde solution having a pH of about 3.5 to

solved. 4.5 at 90 ⁰ C in an experimental device that it

allowed to determine the abrasion, was treated, so after 2 days still had 95 to 98% and after In 4 days, 92 to 94% of the original amount still has a particle size of more than 2 mm.

When using an appropriate catalyst, which with the help of pressed silicon dioxide and contained 12.6% copper and 2.8% bismuth, the values of this abrasion test were the same to 85% after 2 days and 53% after 4 days. This shows the greater mechanical stability of the silica gel support with stationary phase compared to the pressed silicon dioxide precipitate as another benefit.

Claims (2)

Claims: * 5 1. A process for the preparation of butynediol as a mixture with pnopinol by reacting formaldehyde with acetylene in the presence of a catalyst composed of copper and bismuth on silica as the carrier, characterized in that the reaction is carried out in the presence of a catalyst which has a continuous silica gel phase and contains an average of 10 to 15% copper and 2 to 7% bismuth, the copper content in the surface layer being 15 to 25%, which is obtained by treating silica gel for 5 to 15 minutes with an aqueous solution of copper nitrate and bismuth nitrate in aqueous nitric acid has been contains 10 to 15% copper and 2 to 7% bismuth containing, at room temperature and 3- to 14h heating the dry looking blue gel that no excess liquid obtained at 500 to 700 ⁰ C. 2. The method according to claim 1, characterized in that one carries out the reaction with a catalyst with a carrier of a silica gel with a Siebfekheit 6.5 to 15.5 stitches per square centimeter, wherein comparing the obtained blue gel for 1 hour at 150 ⁰ C and then heated ^{at 500 0 C for 5 hours.} Considered publications:
British Patent No. 784,638;
U.S. Patent No. 2768215. 709 517/560 2.67 © Bundesdruckerei Berlin