DE1299878B - Process for the production of complex compounds from anion exchange resins and halogens - Google Patents

Description

1 2

It is known that anion exchange resins are chloromethylated in gel and then with the appropriate suitable halide form bromine and iodine chemically converts tertiary amine.

adsorb (see A ν e s t ο η and coworkers, Che- Special resins that can be used here,

Mistry and Industry, September 14, 1957, and are cited in U.S. Patent 2,591,573. Ziegler, Angewandte Chemie, 71, 1959, p. 283). 5 Other quaternary ammonium resins, with which certain resin-halogen combinations seem to be able to work, are plexes to be formed in the USA patents, in which adsorbed halogen is described as 2,630,427, 2,597,494 and 2,597,440. A specific representative example of the resin in association with the solid cationic ^{ions is that according to groups (R +} ) of the same in the form of polyhalide examples (ABC) of US Pat. No. 2,591,573, e.g. B. Br ₃ ^- (from Br ₂ to R ⁺ Br ^- ) and I ₃ "(strongly basic anion exchange resin made from J ₂ ^{io. To R +} J-). The chemically adsorbed The hydroxide form of this resin is subject to the beer Polybromide and polyiodide ions, as described by the passage of sodium chloride solution, e.g. by Ziegler, have only a very small amount or sea water, a conversion into the chloride form, no odor at all of the original halogen. Patents, however, contain oxidizing halogen, as can be seen from work 2 900 352, for example the resin produced according to Example 5 of its reactivity with known reduction compounds of this patent US Pat. No. 2,614,099, the adsorption of molecular chlorine is not known - and resins specifically described in Example 2 can become Find.

R ⁺ Cl ^- (ie, the resin in the chloride form) tries 20 Many suitable resins are available. In this way, no specific analogous complex is formed. Type I resins included
Resin in the chloride form (R ⁺ Cl ^- ) which, e.g. B. by

_{Immersion in chlorinated water} , with elemental chlorine _n “ηΐΤ

has been treated, the molecular chlorine - O ₆ H ₁ Ui ₂ - loses

easy even when left standing in the air at habitual 25,. . . , _{T TT}
borrowed temperatures and pressures or on expulsion aes lyps 11
wash with water or saline, whereas the +

Polybromid- Polyjodidform and the resin loading a -C ₆ H ₄ - CH ₂ -trächtliche have storage and wash resistance. Although chlorine can be trapped from the chloride form of resin 30 while the pyridine-type resins are based on pyridine when the resin is built into a source of the cationic groups. Holding a chlorine atmosphere, this is not always practical. The resins are usually available as grains or

It has now been found that complex compounds - uniform beads, usually in the hydroxide dung from anion exchange resins, the quaternary or chloride form in grain sizes from about 1.2 to Ammonium or pyridinium chloride or bromide 35 0.002 mm available. The chloride form is preferred; groups, but by treating with halogens one can also use other forms of the resin. or compounds of the halogens with one another, provided that only the anionic constituent is against can produce part if one is interchangeable on the chlorides chlorine and bromine ions, z. B. the of the mentioned anion exchange resins bromine chloride hydroxide, acetate, nitrate, bisulfate, sulfate, phosphate or at the same time bromine and chlorine or on the bromides 40 phat or fluoride form.

of the above-mentioned anion exchange resins with chlorine Normally those commercially available react

works. strongly basic anion exchange resins partially

The starting products are available in stores with free bromine and chlorine and are consumed first Chloride form available or can easily be irreversibly replaced by a part of this halogen, being substi-simpler Convert ion exchange into this form. 45 tution or addition reactions take place. Around The quaternary ammonium chlorides consist in achieving consistent adsorption results essentially from long chain-like and web-like, it is useful, if not necessary, the resin water-insoluble molecules that quaternary ammo by pretreating with chlorine, bromine, or both nium groups as fixed, d. H. non-exchangeable cat- conditioning to avoid the unstable (or reactive) possess ionic groups. "To burn away" (or to halogenate) these groups net are anions that can be obtained in a known manner in a resin, which in adsorption processes speaking treatment can be changed. consistently high yields of recoverable bromine Typical resins are supplied on a polystyrene framework. Appropriately, the resin, for. B. a commercial building, wherein crosslinking divinylbenzene units product in the chloride form, a reaction sequence the polymer is subjected to the necessary dimensional stability by first treating it with a solution of and impart water insolubility, while groups bromine and chlorine, e.g. B. acidified and chlorinated of the formula sea water, for the purpose of adsorption of oxidizing

+ Halogen, then with a reducing agent, e.g. B.

- Alkylene - NR ₁ R ₂ R ₃ sulfur dioxide in the presence of water, for the purpose

60 reduction of halogen treated and finally with

form the positively charged groups. R ₁ , R ₂ and R _{3 are} washed with brine to generate the chloride form and usually alkyl groups such as methyl or. The reaction sequence is repeated until ethyl groups, but alkylol groups can also represent a sufficiently reproducible halogen adsorption-oxyethyl group. You can also get so veration. Occasional washing with one agree that with the nitrogen atom a hetero-organic solvent, z. B. acetone, is purpose cyclic radical is formed, such as methylpiperidinium moderately to the resin of water-insoluble, but in or pyridinium. Resins of this type are available in solvent-soluble organic substances in pure form, to which a polystyrene-divinylbenzene copolymer is added, which could clog the pores of the resin.

3 4

Since seawater does not require a significant amount of bromine ions. The reaction (4) is valuable in itself (65 parts Br ~ per million) contains, the bromine content and can be used to chlorine from the aqueous of the seawater within the meaning of the invention in the solutions or from the gas phase, z. B. from radio adsorption on the resin suitable interhalogen form active chlorine vapor streams to wash out. When bringing this water or by washing out chlorine-containing gas streams, other naturally occurring bromide-containing resins are preferably moistened with water in order to acidify the chloride solution and add enough chlorine to facilitate contact between the phases. If instead of the bromine ion according to the following equation to oxidize the chloride form for this bromine to bromide form of the resin was to be used purpose is in the chlorine stream 2 Br ~ + Cl = Br + 2 Cl ~ f 1) ^{10 ton} ächst a the Chlorine equivalent amount of bromine ^{2 2 is} injected before the current is passed through the chloride form and to provide an excess of chlorine of the resin.

the at least about 50% of the by this process The method by which the halide form des

theoretically obtainable bromine corresponds. With other resin within the meaning of the invention with the corresponding

In words, one works with at least 1.5 times the amount of halogen treated, is irrelevant. the

preferably twice the stoichiometric reactants can batchwise or continuously

Amount of chlorine that would be required according to equation (1). need to be brought together, the resin

Larger amounts, e.g. B. 3 times this amount, can be in quiescent bed or in the fluidized bed

but usually cannot. The halogen can be liquid or vapor,

necessary. The previously customary methods of bromine 20 pure or with essentially inert carriers

extraction by oxidizing the bromide content of thin. Usually one works

Sea water only work with a slight over- under normal atmospheric conditions; the

One shot above the temperatures required according to equation (1) can, however, also be lower (0 ⁰ C)

stoichiometric amount or with an excess or higher (6O ⁰ C), the lower temperatures

up to about 15 ° / ₀ . The invention is not intended to be preferred to attack the halogens

agreed theoretical explanation for the apparent diminish on the resin.

Interaction between bromine and chlorine in the resin with adsorbed bromine chloride is depending on the

Formation of the new resin-halogen complexes. Concentration yellow to reddish yellow, while with bromine

bound; the mixture of bromine and chlorine loaded resin can be orange to depending on the degree of loading

however, as the interhalogen compound bromine chloride 30 is deep red. The resin-interhalogen complexes appear

consider which, according to the equation, can be kept indefinitely at ordinary temperatures

ρ 1/11 _ λ -o pi o \ ^sem · That they contain oxidizing halogen shows

JJr ₂ -1- U ₂ - ζβπ_ι \ Δ) _{in their effectiveness as an} oxidizing agent, and

forms, and one can assume that these inter- on this basis they can also be analyzed,

halogen compound with a chlorine ion (of the sea- 35 The resin-interhalogen complexes are suitable as

water or a chlorine ion group of the resin, bromine chlorinating agent. By treating ethy-

even) to complex bromine chlorine ions after the len with such a resin complex is obtained z. B.

Equation ethylene chlorobromide, which is used as a lead detergent in

Tetraalkyl lead anti-knock agents are useful.

BrCl + Cl = BrCL (3) ^ ₀ £) j _{e new} products are also suitable due to the

connects. oxidizing halogen character of the interhalogen

The proportion of the bromine complex anions adsorbed on the resin as disinfectant and germ-killing chlorides naturally varies with the amount of the medium and can therefore be used to produce drinking walls Br ₂ and Cl ₂ ; an equimolecular mixture of water or to disinfect the water from Br ₂ and Cl ₂ is stoichiometric 2 mol BrCl equi- 45 swimming pools are used,
valent. If the ratio of Cl ₂ to Br _{2 is} less than The resin-interhalogen complexes are especially 1, other polybromine are valuable in the resin complex for the recovery of bromine ions from aqueous chloride anions than BrCt, which here as a grain solution. They are considerably more effective than the plex compound of BrCl and Cl ~ is considered, the chloride form of the resin itself is adsorbed for the production of bromine, which is characterized by lower Cl contents through ion exchange. An explanation for this could be drawn, such as B. Br ₂ Cl- (which forms that the chlorine groups of the complex BrCl ₂ "when Br ₂ reacts with Cl- to form a complex compound of the resin easily exchanges for bromine ions or when BrCl reacts with Br-) , whereby Br ₂ Cl- and Br ₃ "are released

In the case of the resin components obtainable according to the invention from chlorine ions Cl- form,
plexes outweigh the groups based on 55

of bromine chloride (BrCl ₂ -) those on the basic example 1
location of bromine (Br ₂ Cl-), and with regard to the overall one works with a resin of type I, which halogen content outweighs the chlorine over which has a medium porosity, from pearls of a grain bromine, size from 0.15 to 0 , 3 mm consists of trimethylbenzyl

The resin-interhalogen complexes can also contain ammonium groups as cationic groups,

by taking the bromide form of a moisture content of 43 ° / ₀ and a total

Resin (R ⁺ Br-) immediately with chlorine after the exchange capacity (in the Cl ~ form) of 1.33 milli-

Equation has equivalent per milliliter of wet resin.

R + Br ~ 4- CL = R ⁺ BrCIr (4) ^ ^as * ⁿ ^ ^er chloride form present resin is in

²² 65 pretreated for one or more work cycles,

implemented, preferably at least the 4 parts by volume of seawater added to it

stoichiometric amount of Cl ₂ used. Which hydrochloric acid (up to a pH value of 4.5),

work with excess chlorine; However, this is 4 g of chlorine and 8 g of bromine per liter have been added.

After 16 hours, the resin is filtered off, transferred to a column and passed through gaseous sulfur dioxide completely discolored. Then the resin becomes more saturated by 16 parts by volume Saline solution and then washed with 4 parts by volume of water.

The resin pretreated in this way (in the chloride form) is converted into the bromine-chlorine complex as follows: 8 liters of seawater (65 parts of bromine per million) are acidified to pH 4.3 with hydrochloric acid. Then 5 g (0.07 mol) of gaseous chlorine are passed in and 11 g (0.07 mol) of liquid bromine are then added and the solution is stirred until the bromine is dissolved. 200 ml of the pretreated resin are stirred with this solution for 4 hours at room temperature and filtered off. The resin treated in this way contains oxidizing halogen in amounts of 55.5 mg Br ₂ per milliliter and 21.0 mg Cl ₂ per milliliter.

The following experiments demonstrate the remarkable ability of resin-interhalogen complexes to adsorb bromine ions. A stock solution which contains 10.3 mg of bromine ions per milliliter and is prepared by mixing 125 ml of 37% hydrochloric acid, 42 ml of 69% sulfuric acid, 13 ml of 48% ^{hydrobromic acid and making} up to 11 with seawater is prepared as follows treated: 10 ml each of the bromine-chlorine resin complex prepared as above are stirred with 25, 50 or 450 ml of the stock solution for 1 hour at room temperature and then filtered off, washed with 100 ml of distilled water and analyzed for bromine that can be washed out. The results are as follows:

attempt

Volume of

treated

Bromide solution

ml

25th

50

450

Total bromine leachable from the resin, mg / ml

initially

55.5
55.5
55.5

at the end

amount adsorbed

79.6 108.0 163.2

24.1

52.5

107.7

35

40

Practically the same results are obtained if the resin-interhalogen complex is left at rest begins and lets the bromide solution flow through this bed.

In the experiments TSTr. 1 and 2 will be the solution Bromine is almost completely removed by the resin. In experiment no. 3, the bromine uptake obviously stops on when the resin is saturated with the bromine ions of the solution; however, the total bromine load is three times as big as the initial one.

The adsorption of bromine ions by the resin-interhalogen complexes prepared according to the invention (which results in tripling the bromine loading under the above conditions) is particularly noteworthy in view of the presence of sulfate and Chlorine ions in the solution, which also have a high affinity for the resin groups. In comparison in addition, the chloride form of the resin adsorbs only a maximum amount under practically the same conditions of about 26 mg of bromine ions per milliliter.

Example 2

Example 1 is used with 8 liters of seawater with a pH of 4, to which 3.95 g (0.056 mol) of chlorine and 7.68 g (0.049 mol) of bromine are added. The amount of chlorine is at least sufficient to convert all of the bromine, including the initial bromine ion content of 0.52 g (0.0033 mol, calculated as Br ₂ ), into bromine chloride BrCl.

The resin treated in this way contains oxidizing halogen corresponding to 56.8 mg bromine chloride per milliliter (i.e. 39.4 mg bromine per milliliter and 17.4 mg chlorine per milliliter).

Just like the resin-interhalogen complex according to Example 1, this product also easily takes bromine ions by adsorbing up to 60 mg / ml under practically the same conditions.

Example 3

10 ml of anion exchange resin saturated with water according to Example 1 in the bromide form are introduced into a column as a cylindrical bed with a depth of 9 cm and a cross-sectional area of 1.1 cm ^2. A water-saturated mixture of chlorine and air with a chlorine content of about 0.1 percent by weight is passed through this bed at a flow rate of 15.5 l / minute at room temperature. The initially colorless resin gradually turns yellow-orange in color when chlorine is adsorbed, and no chlorine can be found in the exhaust gas when tested with potassium iodide starch paper. In 15 minutes the resin adsorbs up to 1 millimole of Cl ₂ per milliequivalent per milliliter of resin, which corresponds to the conversion of the bromine ion groups Br ~ of the resin into the bromide chlorine ion BrCLr.

Claims (1)

Claim: Process for the preparation of complex compounds from anion exchange resins, the quaternary Contain ammonium or pyridmium chloride or bromide groups by treating with Halogens or compounds of the halogens with one another, characterized in that the chlorides of the anion exchange resins mentioned are used Bromine chloride or bromine and chlorine at the same time, or chlorine on the bromides of the anion exchange resins mentioned, can act.