DE968543C - Cation exchanger - Google Patents

Description

(WiGBl. P. 175)

ISSUED MARCH 6, 1958

F 3032 IVcji2 d

Cation exchanges rather

It is known that artificial resins, in particular from polyhydric phenols or phenol-like Natural substances and aldehydes can be used with advantage as base exchangers. Resins from monovalent Phenols are practically unsuitable for the stated purpose because of their insufficient capacity.

It has now been found that such water-insoluble synthetic resins, which are composed of phenols and formaldehyde be prepared in a manner known per se in the presence of sulfites, the corresponding known Cation exchangers z. B. are significantly superior in terms of their capacity. The at the Reaction in the resin molecule entering ω-sulfonic acid groups make even resins from monohydric phenols excellent for cation exchange suitable.

The resins can be produced in various ways. For example, you can use the three components after an alkaline precondensation with an amount approximately equivalent to the amount of sulfite Amount of formaldehyde after adding further amounts of an aldehyde and optionally of Completely condense phenol in an acidic medium. This yielded phenol can be something other than that in the first work step to ω-sulfonic acid be implemented. But you can also start from pure r-oxy-4-methylbenzene-a> -sulfonic acid, which

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one by reacting equimolecular amounts of phenol, sulfite and formaldehyde and subsequent; Acidification has received, and this solution with any phenol suitable for resin formation and add further amounts of aldehyde, with condensation to the resin taking place under heating. In general phenols cannot be mixed with aldehydes in an acidic aqueous medium to form resin jelly . condense. Here the presence of the

ίο ω-sulfonic acid in addition to the phenols the acidic condensation.

If the creation of wide-pore gels is intended, the two-step process can be simplified, by mixing the three components in the correct mixing ratio for the end product combined and the reaction in the alkaline medium can go to the end, as it is in the course of the reaction adjusts by itself. In this case, the condensation of the phenol takes place in a simple manner with formaldehyde and sulphite to methylene sulphonic "acid together with the condensation to the resin performed. The jelly obtained can, if desired, subsequently become a narrow-pored one can be changed by removing an excess amount of salt before hardening only freed by soaking and then the action of acids, z. B. hydrochloric acid or acetic acid, suspends.

It is already known to use phenols and formaldehyde in the presence of sodium sulfite as resins Manufacture catalyst. However, the products have so far only been used for the production of pressing. masses.

example 1

As a cation exchanger with high capacity, for. B. a resin is used for water desalination, which was manufactured as follows:

275 parts of resorcinol are dissolved in 500 parts of water, successively with 125 parts of sodium sulfite and 100 parts by volume of formalin (30%) are added and the mixture is heated on the steam bath for 12 hours. To Cooling, the reaction product is concentrated with 114 parts by volume. Hydrochloric acid is added and 375 parts Formalin stirred intensively. The solution solidifies after a few times when heated to 85 ° Minutes to a transparent, homogeneous jelly. The jelly is chopped up and at 75 to 85 ° dried and hardened.

Example 2

A product with a capacity of is suitable as an Na exchanger for water softening and the like about 6% (calculated on CaO), which was produced as follows:

A solution of 22 parts of resorcinol in 20 parts of water is mixed with a solution of 20 parts of sodium sulfite mixed in 60 parts of water and slowly mixed with 16 parts by volume of formalin (30%) Stirring added. Then the solution is heated on the steam bath for 10 hours. Be in this mixture after the end of the heating, a further 22 parts of resorcinol were dissolved. After cooling to about 10 ° 60 parts by volume of formalin (30%) are introduced within 10 minutes with external cooling with water. The mass heats up strongly, forming a jelly that is dried and crushed will.

Example 3

As an H exchanger, e.g. B. for water desalination, a resin gel prepared as follows is suitable became:

A solution of 110 parts of resorcinol in 140 parts of water is treated with a solution of 63 parts of sodium sulfite in 160 parts of water and then intimately mixed at approximately 5 ⁰ with 170 parts by volume of formalin (3o ° / oig) with external cooling. The product heats up and solidifies into a jelly that is dried and crushed.

Example 4

A resin prepared as follows is suitable as a cation exchanger:

50 parts of a solution obtained by heating 410 parts of resorcinol, 250 parts of water, 187 parts of sodium sulfite and 170 parts of formalin (30%) for 15 hours are mixed with a solution of 20 parts of phlorohlucin in 70 parts of alcohol and then added to 10 to 15 ° quickly stirred with 29 parts of formalin (40 ⁰ mg). The solution heats up and solidifies at 42 °. After drying at 75 to 80 °, it is crushed.

Example 5 _vs.

If you use z. B. to soften well water from 22 ° d. H. a manufactured as follows Resin, it is loaded with 2.7% of its weight in CaO.

376 parts of phenol are in a solution of 504 parts of sodium sulfite in 1000 parts of water and 400 parts by volume of formalin (30%) entered and then refluxed for 12 hours. In the so obtained solution are at 90 to 100 ° a further 1128 parts of phenol, 540 parts of water and 120 parts Caustic soda ... dissolved and then-2000 parts by volume of formalin (3o%) at the boiling point with stirring in one hour. After boiling for about 3 hours, the solution solidifies a jelly which, after standing for 15 hours at 100 °, is crushed and dried at 75 to 80 ° will.

A resin that is produced in the same way without the addition of sodium sulfite from phenol and formaldehyde has been produced, has no exchange properties.

Example 6

Cations can be exchanged with a resin made as follows:

376 parts of phenol are dissolved in a solution of parts of sodium sulfite in 1000 parts of water and Parts of formalin (30%) entered and then refluxed for 8 hours. This solution is mixed with a solution of 1100 parts of resorcinol in parts of water. Then at io °

2000 parts by volume of formalin (3o ^fl / oig) entered, whereupon after a few minutes the mixture solidifies to a solid resin under heating. After standing for about half an hour at this temperature, the resin is dried at 75 to 80 ° and comminuted.

Example 7

If a resin prepared as follows is used for water softening, it is loaded with it about 3 percent by weight (calculated on CaO) of the hardness components.

940 parts of phenol and 340 parts of sodium sulphate are dissolved in 1400 parts of water and 1700 parts of formalin (40%) solved. This solution is heated to 90 to 100 ° for 40 hours. In the course of this Time freezes the solution; the resulting jelly hardens and is dried at 75 to 80 ° and crushed.

It is also already known to use sulfited quebracho extracts to condense with formaldehyde to form resins, which have cation-exchanging properties to have. Treatment of the starting material with small amounts of sodium sulfate or sodium bisulfite takes place in order to make the extracts completely water-soluble. With the present invention therefore there are no points of contact.

Claims (1)

PATENT CLAIM: Use of water-insoluble substances condensed from phenols and aldehydes in the presence of sulphites Synthetic resins in the form of gels as cation exchangers. Considered publications:
German Patent Nos. 368521, 392461;
British Patent Nos. 450308, 154Ϊ53, 154162. © 709 895/34 2.