DE2740534A1 - Heavy ion-exchange resin for continuous processes - prepd. by halogenation before introduction of ion-exchange gps. - Google Patents

Abstract

An organic, halogenaed, polymeric ion-exchangers, for use in continuous ion-exchange process, is prepd. by halogenating the polymeric carrier and then introducing the ion-exchange gps. The process is not limited to the expensive, unstable monohalovinyl cpds., but can be applied to the (co)polymers of the gel or macroporous types. Pref. >1 halo atom can be introduced. The ion-exchanger has higher density and good stability to osmotic and hydromechanical stress. Heavy ion-exchangers of greater capacity can be obtd. The (co)polymer partic. contains aromatic (esp. 6C) rings, partic. derived from styrene or divinylbenzene. The raw material for the halogenation may already carry precursor gps. for the ion-exchange gps., e.g. chloro- or bromo-(m)ethyl gps., which are later converted to amine or ammonium salts, or carboxylic, sulphonic or phosphoric ester gps., which can later be saponified. Halogenation is pref. with Cl2 or SO2Cl2, or with Br2 in presence of Fe powder or of a metal chloride.

Description

Process for the production of ion exchangers for

continuous ion exchange processes and ion exchangers therefor The invention relates to organic, polymeric halogen-containing ion exchangers for continuous ion exchange processes as well as ion exchangers for continuous Ion exchange processes as such.

In the case of fully continuous ion exchange systems, such as e.g. in the German data codes 20 04 844, 20 25 035> 12 80 761, 17 27 172, 17 27 171 and the German patent applications P 19 18 986 and P 26 27 592.3 are described, it is advantageous if the difference in density between the loading solution and the regeneration solution, on the one hand and the ion exchanger on the other hand is as large as possible. With the continuous In the process, the ion exchanger trickles down from above in a fluidized bed down through both the working and the regeneration column, contrary to that of Liquids flowing through the columns from bottom to top (loading solution or Regeneration solution).

This means that, given the same particle size, the ion exchangers are the same Column diameter and at a given rate of descent of the ion exchange beads, the difference in density between ion exchanger and solution; the upflow velocity of the solution and thus the throughput per unit of time. ApFerative means this is that columns operated with heavy ion exchangers are otherwise identical Design data require a smaller diameter. For the ion exchanger this means that nan tei can remain smaller grain diameters if one accordingly the density of the ion exchangers increases.

This aspect is important in that it is up to today has not succeeded in making stable, the requirements of continuous ion exchange processes really satisfactory ion exchange particles with an effective grain size about 1.5 mm available.

There are already ion exchangers from German Offenlegungsschrift 22 18 126 for continuous exchange processes with densities greater than 1.15 gXcm3 (anion exchangers) or greater than 1.40 g / cm³ (cation exchanger) known. After that, however, there are only ion exchangers based on chlorostyrene. However, the present invention resides inter alia The object is based on a generally useful process for the production of ion exchangers for continuous ion exchange processes.

According to the invention for continuous exchange processes Ion exchangers produced by using the organic, as a carrier of the ion exchange group previous polymer halogenated and prior to the introduction of the ion exchange groups then introduces the ion exchange groups.

On the way according to the invention it is possible to implement the expensive and to avoid unstable monohalovinyl compounds of DT-OS 22 18 126. According to the invention can rather, for the production of heavy ion exchangers for continuous ion exchange processes the same polymers or copolymers be used as they are for conventional ion exchangers, both for those of the "gel type" as well as the macroporous type are offset. Another The advantage of the inventive method is that there is more than one burdening Halogen atom per repeating unit of the polymer, e.g. per aromatic ring and / or aliphatic constituents of the exchanger backbone. In addition, the ion exchangers produced according to the invention are notable in addition to higher density due to excellent stability towards osmotic and hydromechanical Loads from and are in this respect in favor of continuous ion exchange processes particularly suitable.

Halogenation is flat in a particularly advantageous embodiment only on a carrier polymer already containing the exchange precursor groups or table polymer made. This has therefore proven to be particularly cheap proven, because it results in the production of heavy halogen-containing ion exchangers high exchange capacity, i.e. without adversely affecting the exchange properties succeed. This is especially true if more than one halogen atom per recurring polymer unit, e.g. per aromatic ping. This preferred procedure is therefore in particular for the multiple Halogen substitution per repeating unit, e.g. per aromatic ping, the otherwise it is often used at the expense of the exhaustion capacity. This applies to both for both chlorine and Prom substitution.

Exchanger precursor groups are, for example, halogen-containing groups, in particular chloromethyl, chloroethyl, frommethyl or bromoethyl groups, which then after halogenation of the carrier polymer or copolymer, e.g. for Production of anion exchangers, in the usual way into the amine or ammonium salt be convicted. Examples of further precursor troops before their conversion the exchange structure is halogenated in the ion exchange group, are, for example, carboxylic acid tested, the saponification of which leads to weakly acidic cation exchangers receives sulfonic acid esters and phosphonic acid esters, which lead to strongly acidic cation exchangers or those with groups of different acid strengths can be saponified.

The exchanger backbone can, in particular, preferably contain aromatic pings Contain C6 pings as a component of the polymer or copolymer. These Aromatic rings are then usually derived from the one used during polymerization or

Mixed polymerization used or shared styrene or divinylbenzene made available.

The halogenation takes place with or without catalysts. for chlorination is usually done in such a way that elemental chlorine is used in a chlorinated hydrocarbon swollen polymer beads in the presence of catalysts such as Fe powder or Iron (III) chloride is chlorinated or the chlorine is obtained by reaction with sulfuryl chloride in the presence of aluminum chloride and disulfur dichloride.

The halogenation of the aliphatic framework is carried out with elementary Chlorine worked under UV radiation.

The bromination is usually carried out with Br2 in the presence of metal powder like Fe powder, or of metal chlorides like iron (III) chloride and aluminum chloride.

As already stated, there can be up to one or more than one halogen atom to be introduced. Most of them contain only one bromine atom per recurring unit Ion exchangers already heavy enough for continuous processes that are multiple Bromination then leads to particularly heavy ion exchangers. Basically the same applies to the chlorinated ion exchangers Here, too, there are more than one chlorine atom per ion exchanger containing repeating unit particularly preferred.

The invention therefore also relates to ion exchangers for continuous ion exchange processes which, according to the invention, contain more than one halogen atom, preferably chlorine and / or bromine atom per repeating unit, in particular per aromatic ring included. The use of such ion exchangers for continuous Ion exchange processes have particular advantages due to their high density themselves.

Example 1 a) Polymer according to DT-AS 15 69 285 in a mixture from 25.3 g of divinylbenzene (commercially available 60 Sig) and 354.7 g of styrene are 46 g of linear Polystyrene dissolved. After adding 4.0 g of dibenzolyl peroxide and 0.9 g of azoisobutyronitrile the solution is bead-polymerized in 900 ml of water containing 2 g of gelatin at 50 to 90C.

The polymer is then cured at 110 ° C. in a drying cabinet and dried.

200 g of the polymer are in a three-necked flask with 600 ml Treated 1,2-dichloroethane for 60 minutes with stirring, the Ykthylenechlorid is then sucked off and the process repeated twice with 300 ml each for 30 minutes, it the mixture is made up with a further 300 ml of ethylene chloride Room temperature cooled down.

b) bromination before chloromethylation 200 g of the described under a), extracted, suspended in 300 ml of 1,2-dichlorothane polymer are at room temperature 2 g of Fe powder are added, then 45 are added dropwise over 2 hours ml (approx. 137 g, approx. 50 mol%) of bromine were added at room temperature. It will be 4 hours stirred at 300 C, then slowly (approx. 100 C / h) heated up to 800C and more Stirred for 3 hours at 800 ° C., then cooled. It is 4 times with 300 ml of 1,2-dichloroethane washed out, then topped up with another 300 ml.

c) Chloromethylation The chloromethylation is according to DT-PS 10 10 738 carried out, namely 260 g of AlCl3, 150 ml of 1,2-dichloroethane, 45.8 g of paraformaldehyde and 189 ml Methvlal to use.

It is stirred for 30 min at room temperature, then for 2 hours at 600C. It is then cooled and washed twice with 300 ml 1,2-dichloroethane each time, then 4 more times with 600 ml of water each time.

(Note: The water washes are omitted in the later examples "Bromination / chlorination after chloromethylation", here after "washes." filled up with 1,2-dichloroethane with 300 ml each of the same. The water washes there followed the 1,2-dichloroethane washes after the bromination).

d) Amination The washed out, brominated and chloromethylated LI0O ml of water, 1.6 g of NaOH and 172 g of dimethanolamine are added to the balls, the mixture is stirred at room temperature and at 6000 for 2 hours each. Then it will be while distilling off the ethylene chloride gradually heated to 980C, then is cooled, the liquid sucked off and 600 ml of 15% HCl added.

The mixture is stirred for a further 30 minutes, then washed neutral with deionized water.

This gives 740 ml of the chloride form of a strongly basic anion exchanger Type TI with a density of 1.208 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Br content: in the polymer 2.38%, in the exchanger 15.3b Z Moisture content: 41.9 z Capacity according to DIN 54 402: Active strongly basic capacity (AKRB): 0.91 eq / l Strong base capacity (KRB): 1.06 eq / l Usable capacity (NK): 0.55 eq / l Example 2 Bromination after chloromethylation (75 mol t) 200 g of the extracted polymer described in Example 1 are as indicated there chloromethylated, washed out and only then (in contrast to Example 1) with 67.5 ml of bromine (approx. 75 mol%) after adding 2 g of Fe powder dropwise over the course of 4 hours added, then refluxed for a further 10 hours.

The reaction mixture is cooled, the liquid is suctioned off, the Chloromethylated and brominated spheres are mixed twice with 600 ml of 1,2-dichlorothane each time and then washed out 5 more times with Berlin tap water, the last wash water suctioned off, amination as described in Example I.

This gives 675 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.26 g / ml and the following additional characteristics: Microscopic Image: 100 r, whole balls.

Pr content: 16.92%; Moisture content: ie, 7 "capacity according to DIN 54 402: Active strong basic capacity (ACFP): 0.01 eq / l strong bunny capacity (KRB): 1.10 eq / l Usable capacity (NK): 0.50 eq / l Example 3 Bromination according to the chloromethylation (200 mol 1) 200 g of the polymer described in Example 1 are extracted as indicated there, then chloromethylated and then how described in Example 2, brominated.

In contrast to Example 2, 4 Fe powders are added and in the course 180 ml (200 mol%) of Prom were added dropwise over a period of 2 hours. After slowly heating up (10 OC / 0.5 h) is refluxed for 20 h, cooled, filtered off with suction and including amination Proceed as in example 1.

This gives 755 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.44 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Br content: 37.19%; Moisture content: 32.9% capacity according to DIN 54 402: Active strong base capacity (AKRB): 0.70 eq / l strong base Capacity (KRB): 1.02 eq / l Usable capacity (NK): 0.40 eq / l Example 4 Bromination after the chloromethylation (100 mol X) strong base anion exchanger type T.

200 g of the polymer described in Example 1 are as there indicated extracted and then chlorinated.

For bromination, 2 g of Fe powder are added and 90 ml (100 mol of S) Bromine was added dropwise in the course of 2 h. It is heated slowly (100C / 0.5 h) and Maintained under Rilchflub for 10 h, cooled, filtered off with suction and twice with 300 ml of ethylene chloride each time and washed out and vacuumed 5 times with Berlin tap water.

A mixture of 400 ml Berlin tap water is used for amination 1.6 g of NaOH and 340 ml of aqueous, 40% trimethylamine solution were added, for 2 h Room temperature and stirred for 2 h at 600C. The ethylene chloride is then gradually heated distilled off, cooled, acidified with 00 ml of 15% HCl, stirred for 30 min, Sucked off and washed neutral with deionized water.

This gives 720 ml of the chloride form of a strongly basic one Anion exchanger from Tvp I with a density of 1.25 g / ml and the following additional characteristics: Microscopic Image: 100 f whole balls.

Br content: 22.11%; Moisture content: 39.8% capacity according to DIN 54 402: AKRB: 0.41 eq /; KRB: 1.17 eq / l; NK: 0.37 eq / l.

Example 5 Bromination after chloromethylation (100 mol%) Weak basic anion exchanger.

200 g of the Polvmerisats described in Example 1 are as there indicated extracted and then chloromethylated. The bromination takes place as in example 4.

For amination, a mixture of 400 ml Berlin tap water, 240 ml of approx. 50% NaOH solution and 180 ml of onomethylethanolamine are added, 2h at Room temperature and stirred for 2 hours at 600C. Then the ethylene chloride is gradually heated distilled off, cooled, filtered off with suction and washed neutral with deionized water.

This gives 640 ml of the free base of a weakly basic anion exchanger with a density of 1.245 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Br content: 21.73% Moisture content: 54.3% capacity according to DIN 54 402: Active strong basic capacity (AKRB): 0.11 eq / l weak basic capacity Capacity (KWB): 1.30 eq / l Total capacity (TK): 1.41 eq / l Example 6 Changed Basic structure, bromination after chloromethylation (100 mol%) of strongly basic anion exchangers Tvp II.

a) Polymer: According to Example 1, paragraph a) are in a mixture from 12.7 g divinylbenzene (commercially available 60%) and 367.3 g styrene 47 g linear Dissolved polystyrene and then proceed as described there.

200 g of the bead polymer obtained are described as in Example 1 extracted and chloromethylated.

The bromination then takes place as in Example 4, the amination as in example 1.

This gives 739 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.316 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Br content: 25.33% Moisture content: 35.1% capacity according to DIN 54 402: AXRB: .75 eq / l KRB: 1.01 eq / l NK: 0.45 eq / l example 7 Changed basic structure, bromination after chloromethylation (100 mol%) more strongly basic Anion exchanger Tvp TI.

a) Polymer: According to Example 1, paragraph a) are in a mixture from 25.3 g divinylbenzene (commercially available 60 gig) and 354.7 g styrene 95 g linear Dissolved polystyrene and then proceed as described there.

200 g of the bead polymer obtained are described as in Example 1 extracted and chloromethylated.

The bromination then takes place as in Example 4, the amination as in example 1.

This gives 680 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.310 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Br content: 26.79% Moisture content: 35.5 s capacity according to DIN 54 402: AKRB: 7 eq / l KRB: 0.98 eq / l NK: 0.40 eq / l Example 8 Modified basic structure, Bromination after chloromethylation (100 mol%) of strongly basic anion exchangers Type II.

a) Polymer: According to Example 1, paragraph a) are in a mixture from 31.7 g divinylbenzene (commercially available 60%) and 548.3 g styrene 15.7 g linear Dissolved polystyrene and then proceed as described there.

200 g of the bead polymer obtained are described as in Example 1 extracted and chloromethylated.

The bromination then takes place as in Example 4, the amination as in example 1.

This gives 700 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.345 g / ml and the following additional characteristics: Br content: 10.96% moisture content: 28.4 a capacity according to DIN 54 402: AKRB: 0.76 eq / l KRB: 1.10 eq / l NK: 0.55 eq / l Example 9 Chlorination of the polymer with Cl2 gas Strongly basic anion exchanger type II.

200 g of the polymer described in Example 1 are as there specified extracted.

Chlorination: C12 gas dried with sulfuric acid is mixed with a Rate of 7 g / h for 8 h at 25 0C through the suspension of the extracted Polimerisatkugelchen in 1,2-dichloroethane passed after this with 2 g Fe powder has shifted. Then the temperature is slowly increased (10 ° C / 0.5 h) and the gas flow is reduced to approx. 11 g / h increased. After reaching 800C are, will be another 45 min stirred at this temperature with further introduction. Then it is cooled and Washed out 4x with 300 ml each of 1,2-dichloroethane, topped up with 300 ml.

Chloromethylation and amination are carried out as in Example 1.

This gives 640 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.153 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Cl content: in the polymer: 23.31%; in the exchanger: 14.00% moisture content : 43.3% capacity according to DIN 54 402: AKRB: 0.77 eq / l KRB: 0.88 eq / l NK: 0.59 eq / l Example 10 Chlorination of the polymer with SO2Cl2 Strongly basic anion exchanger Type II.

200 g of the polymer described in Example 1 are as there specified extracted.

Chlorination: The suspension of the extracted polymer beads 5 g of AlCl3 (anhydrous) are added and the mixture is stirred over the course of 3 h a mixture of 148 ml SO2Cl2 and 1.5 ml S2C12 was added dropwise at room temperature. Then the temperature is slowly (100C / 0.5 h) up to 800C and left at 800C for 2 h.

It is then cooled and 4 times with 300 ml of 1,2-dichloroethane each time washed out, last topped up with 300 ml.

Chloromethylation and amination are carried out as in Example 1.

This gives 540 ml of the chloride form of a strongly basic anion exchanger Type II with a density of 1.186 g / ml and the following additional characteristics: Microscopic Image: 100 Z whole balls Cl content: in the exchanger: 19.0% Moisture content: 33.1% capacity according to DIN 54 402: AKRB: 0.51 eq / l KRB: 0.67 eq / l NK: 0.28 eq / l Example 11 Chlorination with SO2C12 after chloromethylation (200 mol%) weak basic anion exchanger.

200 g of the polymer described in Example 1 are as there indicated extracted and chloromethinated.

Chlorination: The suspension of the extracted and chlorinated Polymer beads in 1,2-dichloroethane are mixed with 10 g of AlCl3 (anhydrous). While stirring, a mixture of 296 ml of S02Cl2 and 3.0 ml of S2Cl2 is added over the course of 2 hours added dropwise at room temperature. Then it is slowly heated (100C / 0.5 h) and 10 refluxed h. It is then cooled, suctioned off and twice with each 300 ml 1,2-dichloroethane, then washed out 5 times with 600 ml Berlin tap water each time and sucked off.

The amination is carried out as described in Example 5.

This gives 580 ml of the free base of a weakly basic one Anicnene exchanger with a density of 1.21 g / ml and the following additional key data: Micropic image: 100% whole balls.

Cl content: 24.45% Moisture content: 35.3% capacity according to DIN 54 502: Active strong basic capacity (AKPB): 0.09 eq / l weak basic capacity (KWB): 1.30 eq / l Total capacity (TK): 1.39 eq / l Example 12 Chlorination with SO2Cl2 after chloromethylation (300 mol%) Strongly basic anion exchanger Type II.

200 g of the polymer described in Example 1 are as there indicated extracted and chloromethylated.

Chlorination: the spheres suspended in 300 ml of 1,2-dichloroethane 15 g of AlCl3 (anhydrous) are added, then at room temperature under Stirring a mixture of 444 ml SO2C12 and X, 5 ml S2Cl2 added dropwise over the course of 3 h. The mixture is then slowly heated (10 ° C./0.5 h) and refluxed for 10 h.

It is then cooled, filtered off and twice with 300 ml 1,2-dichloroethane, then washed out and vacuumed 5 times with 600 ml Berlin tap water each time.

The amination is carried out as described in Example 1.

This gives 740 ml of the chloride form of a strongly basic one Anion exchanger Type II with a density of 1.305 g / ml and the following additional characteristics: Microscopic Image: 100% whole balls.

Cl content: 31.03 S Moisture content: 35.3 s Capacity according to DIN 54 402: AKRB: 0.42 eq / l KPB: 0.69 eq / l NK: 0.32 eq / l Example 13 highly acidic Cation exchanger, gel-type bromination before chlorosulfonation.

200 g of a styrene / divinylbenzene copolymer crosslinked with 8.5% by weight divinylbenzene are swollen in 600 ml of 1,2-dichloroethane for 2 h.

Bromination: 1 g of Fe powder is added to the swollen polymer, with stirring, 45 ml (50 mol%) of bromine are added dropwise in the course of 1.5 hours. then is slowly heated (10 ° C / 0.5 h) and refluxed for 4 h. Then it will be cooled, suctioned off and washed 4 times with 300 ml of 1,2-dichloroethane each time, suctioned off.

Chlorosulfonation: It is made up with 600 ml of 1,2-dichloroethane and with stirring at room temperature for 2 hours with 200 ml of chlorosulfonic acid offset. The mixture is stirred for a further 8 h at room temperature, then slowly heated (10 ° C / 1.0 h) to 80 ° C, then 1.5 h at 800C stirred. Then it cools down, suctioned off and washed 4x with 400 ml 1,2-dichloroethane each time, made up with 600 ml.

Dilution: The suspension obtained is mixed with 200 g of NaCl, 1.5 l of Berlin tap water are slowly added dropwise with guidance; Then it will be, after adding 2 g of Fe powder to these, about half of the liquid in each case sucked off in the flask and refilled with 600 ml of water each time. Last will a mixture of 100 ml of 50% aqueous sodium hydroxide solution and 300 ml of deionized water slowly dripped in, the alkaline solution slowly heated, the ethylene chloride distilled off, cooled and washed neutral with deionized water.

This gives 815 ml of the Na form of a strongly acidic cation exchanger with a density of 1.40 g / ml and the following additional characteristics: Microscopic Image: 98% whole balls.

Rr content: 13.20 s Moisture content: 37.9 s Capacity according to DIN 54 403: Strong acid capacity (KRS3: 2.05 eq / l Usable capacity (NK): 1.30 eq / l Example 14 Strongly Acid Macroporous Cation Exchanger Bromination After Chlorosulfonation.

Polymer: Fine solution of 33 g of linear polystyrene in a mixture from 88.6 g of divinylbenzene (commercially available, 60%) and 291.4 g of styrene is obtained as in Example 1a) described bead-polymerized and extracted.

Chlorosulfonation: In the course of 2 h at room temperature under Stirring 200 ml of chlorosulfonic acid were added dropwise, stirring was continued for 5 h at room temperature, sucked off and washed 4 x with 300 ml of ethylene chloride each time, sucked off.

Bromination: Fs is made up with 400 ml of 1,2-dichloroethane, with 2 g Fe powder are added and 90 ml of bromine are added dropwise over the course of 2 hours. Then it will be heated slowly (10 ° C / 0.5 h) and refluxed for 28 h. After cooling down, Sucking off and washing with 400 ml 1,2-dichloroethane each time, the dilution is analogous Example 13 carried out.

This gives 705 ml of the sodium form of a strongly acidic, macroporous Cation exchanger with a density of 1.37 g / ml and the following additional characteristics: Microscopic picture: 100% whole spheres Br content: 6.57 s Moisture content: 42.0 s capacity according to DIN 54 403: Strong acid capacity (KRS): 2.02 eq / l usable Capacity (NK): 1.31 eq / l

Claims (6)

Claims 1. Process for the production of organic, polymeric halogen-containing ion exchangers for continuous ion exchange processes, d a d u r ch g e n n nz e i c h n e t that the organic, as a carrier of the ion exchange group intended polymer halogenated and prior to the introduction of the ion exchange groups then introduces the ion exchange groups. 2. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that the halogenation after the introduction of the ion exchange precursor groups he follows. 3. The method according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that the intended as a carrier of the ion exchanger groups Polymer contains aromatic rings, in particular C6 rings. 4. The method according to any one of claims 1 to 3, d a -d u r c it should be noted that the intended as a carrier of the ion exchange groups Polymer with a content of 1 halogen atom, preferably more as one halogen atom per aromatic ring of the polymer is halogenated. 5. The method according to any one of claims 1 to 4, d a -d u r c h e k e k e n n n e i n e t that the halogenation causes chlorine and / or bromine atoms be introduced. 6. Halogen-containing ion exchangers for continuous ion exchange processes, it is noted that they have more than one halogen atom in particular Chlorine and / or bromine atom per recurring unit of the polymer or copolymer include.