DE2626492A1 - METHODS FOR CLEANING UP INDUSTRIAL WASTE - Google Patents

Description

CLBA-GElGY AG ₁ Basel, Switzerland W? [... ^ / """V""" * ^ »« JL— t V ^ t

Case 1-9947 / +

GERMANY Process for the purification of industrial waste water

The present invention relates to a new method for cleaning industrial waste water, in particular for decolorizing in the textile, fiber, paper and leather industry, brightener and dye production accumulating wastewater, such as residual liquor, mother liquor, rinsing and washing water.

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-S-

One of the major environmental problems in industrialized areas is the pollution of rivers and lakes. Since the dirt can also come from industrial plants, the cleaning of industrial wastewater is increasing nowadays Meaning. However, this wastewater treatment proves to be extremely difficult, especially when it comes to disposal comes from organic, poorly biodegradable substances dissolved in water. In the context of this issue is therefore for the decolorization and cleaning of products in the dye, fiber, textile, paper and leather industries Sewage an urgent need.

For cleaning strongly colored and contaminated wastewater, which e.g. during the production and use of dyes and dyeing auxiliaries arise, various processes have already been proposed. So is for example known to collect dye or washing wastewater in large collecting basins and the dye and auxiliary agent residues by adding to precipitate suitable flocculants and separate them by sedimentation, flotation or filtration. These procedures however, cause difficulties in that the volumes of water to be treated are large and the sedimentation or the separation of the flakes from the purified water is associated with great technical effort.

It is also known to use activated carbon for cleaning, in particular for decolorizing industrial waste water.

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the. The use of granulated activated carbon, for example, often turns out to be unsuitable because of the absorption capacity of the activated carbon is too low for organic dyes dissolved in water and impurities present in waste water.

From the USA patent specification 3 716 483 it is also known that one can industrial waste water with the help of highly dispersed, organic polymers, which in a dried state present, can clean. However, this method has the disadvantage that, for example, the removal of anionic dyes from aqueous liquors is only possible to a satisfactory extent at higher temperatures and relatively low pH values.

It has now been found, surprisingly, that industrial wastewater can be cleaned quickly and adequately achieved when this is brought into contact with a polymeric adsorbent material, which is in a solvated, preferably in a hydrated gel state. This adsorption material consisting of polymer gel stands out compared to the corresponding unsolvated or hydrated materials through increased absorption capacity and speed for substances dissolved or dispersed in water

The adsorption material to be used according to the invention is particularly suitable for cleaning ionic, i.e. anionic or cationic substances or liquors containing mixtures thereof, in particular for the removal of anionic

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see or cationic dyes, optical brighteners, Dyeing or textile auxiliaries, surfactants, tanning agents or mixtures thereof.

With the aid of the adsorptive polymer gels, however, not only incompletely drawn out dyeing, lightening and treatment liquors can be removed from the substances mentioned above largely free, but also the corresponding, non-ionic textile or dyeing auxiliaries and / or non-ionic Waste liquors containing dyes or brighteners as well as liquors diluted by rinsing water, mostly mixtures contain dyes and detergents, clean to a satisfactory extent.

Thanks to the wide range of applications of the adsorption material used according to the invention, it is possible to achieve a saving of fresh water, which is now more and more urgently required, through partial to complete recirculation of residual or waste liquors. Irrespective of the equipment used, this primarily concerns the waste water from the dye, fiber, textile, paper and leather industries arising in connection with dyeing, washing and tanning processes. This can, for example in the case of dyeing of the usual dyeing machines, such as those used for the ^v ärbung of loose fiber material of slubbing, yarn and woven or knitted fabrics, as well as from winding devices, for example from a width washing machine, originate.

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Sewage treatment is conveniently carried out at O bi.s 130 ⁰ C. However, it is preferably carried out between 0 and 100 ^° C., in particular between 10 μm, d 70 ^° C. If desired, the wastewater can also be cleaned under pressure or vacuum. The pH of the liquor can vary within wide limits, for example between 2 to 12. However, pH corrections, for example to a value of 2 to 7, in particular 3 to 5 ', can, depending on the nature of the polymer used as the adsorbent material, the Facilitate and accelerate cleaning processes.

The inventive method can be discontinuous, be carried out semicontinuously or continuously, the latter two variants being preferred. In principle, the following three methods are suitable for the purposes of the invention:

a) so-called Ruhr process, whereby the to be cleaned Water in a vessel or a series of vessels is stirred with the adsorbent and then separated;

b) so-called fluidized bed process, in which the adsorbent is kept in suspension by the flow of the liquor to be cleaned;

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c) so-called fixed bed process, wherein the liquor to be cleaned through a filter-like arranged Adsorption material is performed.

If the fixed bed process c) is used from these three process variants, the following are particularly suitable three device variants:

1. The treatment apparatus, e.g. dyeing device, is firmly connected to the adsorber device.

2. The adsorber device is movable and can be coupled with any treatment apparatus as required.

3. The wastewater from the treatment liquors is combined in a suitable container and then passed together through the adsorption material.

Suitable polymeric adsorbents in the gel state in the sense of the invention, both natural and regenerated or volls3 ^T nthetische polymers can be considered. They are preferably synthetic plastics that are non-ionic or, in particular, groups that form ionic salts in water, such as anionic, water-solubilizing groups, e.g. sulfonic acid, carboxylic acid or phosphonic acid groups or onium groups, e.g. ammonium, sulfonium or phosphonium groups

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have pen. The polymers in question should generally have an average molecular weight greater than 500 and a specific surface area greater than 30, in particular

80 - 250 m / g.

The polymer gel concentration generally depends on the type and concentration of the substances to be removed and is usually 0.1 to 50 g / l, based on the dry weight of the adsorbent. The polymers used as adsorption materials are microporous gels in a state of Primary swelling, whereby primary swelling means the amount of liquid, e.g. water or organic solvents which, for example, is not removed from a swollen fiber by conventional mechanical means, e.g. centrifugation can be. In particular, this gel state is characterized in that the specific surface of the polymer

material with the usual drying to values below 5 m / g dry polymer sinks and the material loses its high absorption capacity. Under normal drying is here understood that the swelling liquid at temperatures above its solidification point by evaporation or evaporation Will get removed. The minimum residual moisture required to maintain the gel state is in usually between 5 to 25%, based on the dry polymer material.

However, in the context of the method according to the invention also included dehydrated polymer gels that are below

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Preservation of a large specific surface, e.g. through Freeze drying or solvent exchange drying can be prepared.

The gel state is achieved, for example, by placing the polymer in a water-miscible, organic or inorganic solvent, e.g. aqueous nitric acid, sulfuric acid or sodium;: hodanide solution dissolves and the polymer solution in a suitable coagulating liquid, preferably water, or else E.g. ethanol enters, which is miscible with the polymer solvent, but not itself a solvent for the polymer represents, but the polymer solvates. In certain cases, however, the polymer gels can also be used directly as they are formed of the polymers are incurred.

Suitable, water-miscible, organic solvents for the preparation of the polymer solution include dimethylformamide, Diethylformamide, dimethyl acetamide, ethylene carbonate, Dimethyl sulfoxide, 7-butyrolactone, tetrahydrofuran, Acetone, dioxane, methanol, ethanol, propanol, isopropanol, butanol and called thioglycolic acid.

The polymer solution can be coagulated directly into the wastewater medium or separately. In the latter case, will the polymer gel is preferably freed from the solvent and coagulant and then brought into contact with the sewage.

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The gel state can also be obtained by spray coagulation will. The polymer solution is sprayed into spray mist entered the coagulating fluid, the coagulating fluid can also be in vapor form. Another way to achieve the gel state is that you the polymer solution is atomized within the coagulant liquor.

Those transferable to the required gel state Plastics can be of the most varied of known classes of belong to semi-synthetic and fully synthetic polymers. These include polycondensates, polymers and polyadducts into consideration, which can be both thermosetting plastics and thermoplastics. Suitable semi-synthetic plastics are e.g. cellulose esters, such as cellulose nitrate, cellulose acetate, Cellulose triacetate, cellulose acetobutyrate, cellulose propionate, cellulose ethers, such as methyl cellulose, ethyl cellulose and Benzyl cellulose as well as starch derivatives such as acetyl starch. They are advantageously fully synthetic Thermoplastics, which are used as filament cables, nonwovens, fiber waste, sponges, loose fibers, fiber tape or fiber plugs as well can be used as beads, granules or as amorphous particles.

As examples of possible thermoplastics are mentioned here:

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Polyacrylonitrile, polyamide, linear polyesters such as polyethylene terephthalate, polyolefins such as aluminum-modified Polypropylene. Polystyrene and polyurethanes.

According to the invention, for example, wet spinning processes manufactured, synthetic fibers as adsorption material for the purification of diluted wastewater containing dyestuffs, in particular by cationic and / or anionic marriages Dyes used in polluted wastewater.

These wet-spun fibers can be used in undrawn, partially stretched or fully stretched and are usually by rinsing treatments from Spinnbadchemika-15.en freed.

Particularly suitable adsorption materials are synthetic Fiber materials in the gel state, the single fiber has a linear density of 0.2 to 20 denier, preferably 0.5 to 5 denier.

Adsorber materials behave very favorably comminuted, e.g. cut or torn, gel-moist tow with, for example, fiber lengths of 1 to 100 mm, preferably 1 to 10 mm. If desired, the tow can be refined by grinding.

As preferred synthetic, organic fiber materials according to the present invention in the gel state can be used, are:

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Synthetic polyamides, especially those made from adipic acid and hexamethylenediamine, from ε-caprolactam or from ω-aminoundecanoic acid;

anionically modified polyamides, such as polycondensation products from 4,4'-diamino-2,2'-diphenyldisulfonic acid or 4,4'-diamino-2,2'-diphenylalkanedisulfonic acid with polyamide-forming Starting materials, polycondensation products from monoaminocarboxylic acids or their amide-forming derivatives or dibasic carboxylic acids and diamines with aromatic dicarboxysulfonic acids, e.g. condensation products from £ _ -caprolactam or hexamethylene diammonium adipate with potassium 3,5-dicarboxybenzenesulfonate;

Cellulose ester fibers, such as cellulose 2 1/2 acetate fibers or triacetate fibers;

linear polyester fibers, e.g. by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane as well as copolymers of terephthalic and isophthalic acid and ethylene glycol;

acid modified polyester fibers, such as polycondensation products of aromatic polycarboxylic acids, e.g. terephthalic acid or isophthalic acid with polyhydric alcohols, e.g. ethylene glycol, and 1,2- or 1,3-dihydroxy-3- (3-sodium sulfopropoxy) propane, 2,3-dimethylol-1- (3-sodium sulfopropoxy) butane, 2,2-bis (3-sodium sulfopropoxyphenyl) propane or 3,5-dicarboxybene

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zolsulfonic acid or sulfonated terephthalic acid, sulfonated 4-methoxy-benzenecarboxylic acid or sulfonated diphenyl-4,4'-dicarboxylic acid;

polymeric or copolymeric acrylonitrile materials, the acrylonitrile content of the copolymers generally being at least 507 _{% of} the copolymer. As comonomers are used in addition to the acrylonitrile typically include other vinyl compounds, such as vinylidene chloride, vinylidene cyanide, vinyl chloride, methacrylates, Methylvinylp3 ^T ridin, N-pyrrolidone Viny!, Vinyl acetate vinyl alcohol, acrylamide, acrylic acid, vinyl or styrene.

The adsorption capacity of the polymer gels mentioned can be determined by the choice of the monomers required for their production or comonomers controlled and by admixing suitable additives, e.g. open-chain or cyclic, if necessary polymerized amines or ammonium salts, to be increased to the polymer solution. Through these additions can not only increase the adsorption properties, but also the solvation or hydration capacity of the polymer gel be improved.

If it is a polymer material that is obtained by a process such as that used for production of textile fiber cable is common, it is not necessary that the fiber-like material have a high

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Has strength or uniformity. This makes it possible to choose the comonomers and / or spinning liquid additives much freer than this for the production of textile fibers with corresponding textile-technological requirements applies.

If it is a matter of tow which is also or in particular processed for textile use, then expanded the area in which these materials can be used in the hydrated gel state.

As dyes, those to be used with the according to the invention Adsorption material can be removed from the wastewater, both water-soluble and water-dispersible, anionic or cationic dyes or optical brighteners come into consideration. The adsorption material is preferably suitable for the removal of water-soluble, especially cationic and anionic dyes or optical brighteners.

The anionic dyes according to the invention are removed, they are dyes whose anionic character is due to the formation of metal complexes alone and / or acidic substituents that cause water solubility

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Vf-

is conditional. As such, causing the water solubility, acidic substituents come carboxylic acid groups, phosphonic acid groups, acylated sulfonic acid imide groups, such as alkyl or aryl disulfimide or alkyl or aryl carbonyl sulfimide groups, Alkyl or arylimide groups, sulfuric acid (half) esters and especially sulfonic acid groups.

The anionic dyes can belong to a wide variety of dye classes. For example, oxazine, Tripheny! Methane, xanthene, nitro, acridone, stilbene, perinone, Called naphthoquinone imine, phthalocyanine, anthraquinone and azo dyes. The latter can be metal-free, metallizable or metal-containing mono-, dis- and polyazo dyes, including the formazan dyes, in which the Metallatoru a 1: 1 or 1: 2 complex, especially 1: 2 chromium or 1: 2 cobalt complexes that are two the same or two different Molecules containing azo dye complexed to a chromium or cobalt atom. These dyes can be in the molecule also have so-called reactive groups, which enter into a covalent bond with the fiber material to be dyed.

In the case of the cationic dyes, which are obtained from the wastewater with the aid of the polymer gel to be used according to the invention can be removed, the common salts and metal halides, for example zinc chloride double salts, are generally used of the known, cationic dyes, de-

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ren cationic character of a carbonium, oxonium, Sulfonium and especially from an ammonium group. Examples of such chromophoric systems are: methine, azo, azomethine, Hydrazone, azine, oxazine, thiazine, diazine, xanthene, Acridine, polyaryl methane, V7ie diphenylmethane or Triphenylmethane, as well as coumarin and azo dyes, which contain an indolinium, pyrazolium, triazolium, tetrazolium, Oxadiazolium, thiodiazolium, oxazolium, thiazolium, pyridinium, Have pyrimidinium or pyrazinium ring. Arylazo, phthalocyanine and anthraquinone dyes can also be used which carry an external ammonium group, for example an external cyclammonium or alkylammonium group.

The method according to the invention is not only suitable for decolorizing textiles or paper or Fiber or leather dyeing, but also does a good job when it comes to leftovers remove anionic or cationic optical brighteners from washing and bleaching liquors.

The optical brighteners can belong to any class of brightener. The anionic brighteners are especially stilbene compounds, coumarins, benzocoumarins, pyrazines, pyrazolines, oxazines, dibenzoxazolyl or dibenzimidazoly compounds or naphthalic acid imides, which have at least one acidic group in the molecule, such as carboxylic acid or pre-

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preferably has a sulfonic acid group and is fiber-reactive could be. In the case of cationic brighteners, it is primarily optical brighteners of the methine, azamethine, Benzofuran, benzimidazolyl, coumarin, naphthalimide or Pyrazole series.

To the water-insoluble, non-ionic dyes, which can also be removed according to the invention include disperse dyes, vat dyes, sulfur dyes, water-insoluble optical brighteners as well as organic and inorganic pigments.

Another advantage of the to be used according to the invention Adsorption material is based on the fact that it is partially In addition to the dyes, there is also an elimination of nonionic, anionic and cationic surfactants and dyeing aids substances from aqueous residual liquors are permitted. Such auxiliaries are in the book "Tenside-Textilhilfsmittel-Waschrohstoffe" by Dr. Kurt Lidner (published by Wissenschaftlicher Verlagsgesellschaft Stuttgart, 1964) is described in more detail.

The adsorbent can also help where there is the elimination of anionic, synthetic Tanning agents, in particular tanning agents which carry one or more sulfo groups in the molecule, is. A more detailed description these compounds can be found, for example, in "Ullmans Encyclopedia of Industrial Chemistry", Volume 11; Pp. 595-598.

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By a suitable choice of the adsorption material ^ can according to the invention the waste water up to 100% of the pollution be withdrawn. Retention effects of up to 50 g and, in specific cases, up to 150 g of residues, i.e. dye, optical brightener, adjuvant, tanning agent, achieved per 100 g of dry adsorbent material will. In cases in which it is not possible to completely decolorize or remove the R.ect materials by treating the Pv.es t fleet once with aera adsorption material To achieve this, it is advisable to repeat the cleaning process. Through a recirculation can the adsorption material used can also be reduced to a minimum.

The inventive treatment of the contaminated, liquid media with the polymer gels can optionally also only Be part of a cleaning or recovery process. Drinking water preparation as well as certain wastewater treatments can be carried out over several stages, with one of the work stages, the polymer gels mentioned can be used as adsorbers.

After the impurities have been adsorbed, the adsorption capacity of the polymar gels can be partially or completely recovered , for example by extraction with suitable solvents.

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In the examples, percentages are percentages by weight and parts are parts by weight.

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Example 1 .

5 1 of a 32 ° C warm, green-colored liquor containing 0.2 g / l of a dye of the formula

Cl

0.05 g / l of a dye of the formula

CH,

CH,

Vh-Ch ₂ - / \

I CH "

0.1 g / l of a dye of the formula

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N = N

1.0 g / 1 of a dyeing auxiliary of the formula

(4) ^C 18-22 ^H 37-45- ^N:

χ + y = 35

(CH ₂ CH ₂ O) _x H - (CH ₂ CH ₂ O) H

as well as 1.0 g / l 80% acetic acid, 2 g / l sodium sulfate solution and 1.5 g / 1 sodium acetate solution, 12 g (based on dry weight) are added over 3 minutes with thorough stirring Polymer gels made from a polyamide 6.6 "Ultra deep dyeing" Type, (Du Pont Nylon 848) treated. The polymer gel, which is produced by dissolving the polymer in formic acid and coagulating it in a mixture of water and formic acid (1: 1) has a specific surface area of 165 m / g, determined according to the BET method. After the adsorber material has been separated off by filtration, the liquor is completely discolored.

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Example 2

A polyacrylonitrile tow, wet spun from dimethylformamide and consisting of filaments with 3 denier single titer, is cut in the hydrated state and comminuted to an average length of 1 mm. The ilatei-ial has a specific surface area, determined by the BET method, of 210 m ² / g.

5.4 g of this pulp, the 2 g of dry polyacrylonitrile correspond to, are stirred into a 1.6 1 aqueous liquor at room temperature, the 0.5 g / l of a dye the formula

(5)

CN = N- / \ -N - CH _o CH,

ZnCl.

contains. After a contact time of 2 minutes, the liquor is filtered off separated from the polyacrylonitrile pulp. After this treatment, the liquor contains only 0.1 g / l of the above Dye.

The same result is achieved if the treatment of the liquor is carried out at 40 or 80 ⁰ C.

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Example 3

75 g of a polyacrylonitrile cable spun from aqueous sodium rhodanide solution are placed in a glass tube from 20 mm inside diameter filled. The hydrated piece of cable corresponds to 30 g dry fiber material. Its specific

The surface area, determined by the BET method, is 195 m 2 / g.

The adsorption column prepared in this way is now used by An aqueous liquor of 35 ° C passed down, which contains 5 g / l of the blue dye of the formula (5). The adsorber column turns blue while the liquor flowing through is completely decolorized. In the case of the liquor inflow, the loading concentration is of the adsorber 120% dye, calculated on dry polyacrylonitrile.

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Example 4

A U-shaped tube is continuously on a

Thigh side evenly with hydrated polyacrylonitrile

Spinning cable (specific surface 125 m / g) loaded, the resulting cable package pushed steadily through the pipe and the cable pulled off the other leg of the pipe. ^{A 50 °} C. warm liquor which contains 0.12 g / l of a blue dye of the formula (5) is allowed to flow in countercurrent through the adsorption material for a contact time of 15 seconds. The treated liquor flowing out is completely colorless. Loading concentration of the adsorber 21% dye.

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Example 5

Four stirred tanks set up in the corners of a square and connected by pipelines are each equipped with 20 l of water and 1 kg of the polyacrylonitrile pulp described in Example 2 charged. By 3 of the 4 connected in series Stir kettle now becomes an orange-colored 55 ° C warm dyeing wastewater that still contains 0.03 g / l of a dye the formula

Η-Η- / Λ

N-CH ₉ -CH ₉ -N ^ I ^{2 2} \ = J

CH ₂ CH ₃

Cl

and 0.02 g / l of a commercially available disperse dye, consisting of 42% of a dye of the formula

CH ₃ CONH

15% sulphite waste liquor and 43% of a naphthalenesulphonic acid

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contains, directed. The average residence time of the liquor is 10 seconds per stirred tank. The fleet flows first from stirred tank I to II and from there to III and finally into a collecting vessel. As soon as the fleet from the third RUhrkessel no longer emerges colorless, the fourth RUhrkessel, which contains fresh adsorption material, is attached to the third stirred tank connected so that the liquor is completely decolorized again. The loading concentration of the adsorber from stirred tank I is 33% dye.

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Example 6

100 l of one has a pH of 10.6 and a TOC content of 67 mg / 1, gray-blue-colored wastewater with 2.77 g / l dissolved solids, containing 14 percent by weight a reactive dye, are at room temperature and with a contact time of 20 seconds per unit weight of adsorbent material passed through a cleaning column which with 500 g (based on dry weight) of a polymer gel (specific surface 165 m / g) made of polyamide 6.6 from Type "Ultra deep dyeing", (Du Pont Nylon 848), is loaded. After passing through the column, the liquor is colorless and has a TOG content of only 32 mg / l.

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Example 7

100 g of a copolymer of 92% acrylonitrile and 8% vinyl acetate are dissolved in 900 g of dimethylformamide. 200 g of this polymer solution are then introduced into 2 liters of cold water via a hollow needle with an internal diameter of 0.6 mm as a thin jet, which is vigorously stirred in a high-speed mixer. A polymer gel is obtained with a predominant particle size of 0.05-0.2 mm, which is separated from the water by filtration. Determined by the ΒΞΤ method, the specific surface area of the polymer gel is 102 m Ig.

3 g of this adsorption material, containing 0.51 g of dry polyacrylonitrile, are added to 0.5 l of a liquor at 20 ^° C. which contains 0.12 g / l of a blue dye of the formula (5). After stirring vigorously for 2 minutes and separating off the adsorber, the liquor only contains 0.045 g / l of the dye.

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In Example 7, instead of the adsorption material mentioned, that in column 2 of the table below is used specified polymer gels, so can by an analogous procedure, as described in Example 7, in the column 3 of the table specified liquors are decolorized at the temperatures listed in column 4 »In column 5 is the Duration of the decolorization in minutes, in column 6 the residual dye concentration and in column 7 the percentage adsorber loading is shown.

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1. 2 3 4th .5 6th 7th -D ¹ column Polymer gel Containing liquor ⁰ C duration
i.Min. g / i % I 8 9 parts of the copolymer 0.24 g / l of a dye of the formula (5) 20th 2 0 J 92% acrylonitrile " I. 8% vinyl acetate j 1 part of copolyraerisate I. 757. Acrylic acid J 20% acrylonitrile ' j 5% acrylamide ~ [ spes. Surface: 180 m / g Copolymer 0.33 g / l of a dye of the formula 20th 2 0.31 3 γ— ■ 92% acrylonitrile 'Ό 8% vinyl acetate ₂ spec. Surface: 135 m / g 0 NH ₂
Jl SO "H J » T _CH (8) ί 0 NH - / V-CH ₃ 8 parts of the copolymer ^ - SO ₂ NHCH ₂ CH ₂ OH 20th 2 0.08 * 38 * 92% acrylonitrile 0.33 g / l of a dye of the formula (8) 8% vinyl acetate ro 2 parts N, N = dimethyldode- cylamine ₂ ro spe?, o surface: 155 m / g cn , χι
j do. 25th 2 .0.13 3fr
CD 0.3 g / l of a dye of the formula (5) ro •

* Shows in comparison to Example 9 the improved adsorber effect by the Addition of the amine in the production of polymer gel.

'. 2 3 ZnCIo © 4th 5 • 6th • 0 7th Τ. O p o Polyznergel Containing liquor 3 ⁰ C Daut-, % in min. : O i 9 parts of the copolymer 0.24 g / l of the dye of the formula (5) 927> acrylonitrile 0.05 g / l of a condensation product 20th 2 87o vinyl acetate Ν, Ν-dimethyllaurylamine and epi- 1 part of the copolymer chlorohydrin the end 75% acrylic acid 0.07 20% acrylonitrile 5% acrylamide * ■ 0.4 £ spec. Surface: 180 m / g 0 * -. "- J do. 0.5 g / l N- (2-ethyl-2-phenyl) -aethyl-pyri- 30th 2 O
t dinium chloride 0.4 14th basic modified poly 3.5 g / l of a dye of the formula (8) 75 1 0 • 42 ' acrylonitrile, (Acrilan B 49) spec ο surface: 85 rrr / g . P.5 do. do. 20th 2 42 ... Ό basic dyeable poly 0.1 g / l of a dye of the formula (9) 45 2 42 amide, (Du Pont Nylon 844) • speZa surface: 110 m2 / g ^CH 3 ° .S _ ro j C-N-N- / V-N (CHOo cn k l_ j & \ / * J im K) cn I. CD ^C 2 ^H 5 J K)

E.g.

Polymer gel containing liquor

duration

i.Min.

mg / 1

17th

α
α
rs ■

18 19

Polyamide 6,6, (Du Pont Nylon 848) «spec. Surface: 165 m / g

Cellulose-2 1/2 acetate spec. Surface: 35 m ^ / g fiber pulp made of hydrated polyacrylonitrile ^ spec. Surface: 210 m / g 3 g / l of a dye of the formula (10)

1 g / l of a dye of the formula (11)

N = N

N = N-

/ "AN (C ₉ H, OH)

'2 4' 2

0.05 g / l of a dye of the formula (5)

0.05 g / l of an optical brightener of the formula (12)

20th

32 20

CH ₃ SO ₄ ©

2 2

0.2

1 2 3 of a dye of the formula (13) SO ₃ H • SO ₃ H Q • © 4th 3 20th 5 • 1 6th 7th Bs ρ ο Polymer gel 0 .— Cu - 0 0 - Cu - ( 0 NH-CH ₂ CH ₂ CH ₂ N (CHj) ₃ CH ₃ So ₄ Q ⁰ C duration
i.Min. mg / 1 % 20th Viscose «
spec. Surface: 38 m / g Containing liquor ) NH-COCH
S. of a dye of the formula (1)
of a dye of the formula (14) 40 1 0.2 11 0.9 g / l 0 NH-CH ₃ V 21 basic colorable
Polyester, (Dacron 64) "
spec. Surface: 55 m / g 0 45 0.07 g / l
0.01 g / l - (D
hO
CD
JO-
CD
KJ '

Il

Example 22

9 parts of a copolymer of 92% acrylonitrile and 8% vinyl acetate are used together with 1 part of primary octadecylamine dissolved in 60 parts of dimethyl acetamide.

300 g of this polymer solution are sprayed with air from a spray gun under water at room temperature. To obtain a fibrous polymer with an average particle size of 0.02 to 0.15 mm, which is separated by filtration from water or water-dimethylacetamide mixture and rinsed with 40 ⁰ C hot water. Determined by the BET method, the specific surface area of the polymer gel is 153 m ² / g.

5 g of this adsorption material, containing 1.6 g of the dry copolymer, are added to 1 liter of a liquor at 25 ^° C., the 0.5 g of the blue direct dye of the formula

(15)

0 - Cu - 0

HO.S 0 - Cu - 0

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contains. After stirring vigorously for 5 minutes and separating off the adsorber, the liquor contains only 0.06 g / l of dye. The loading of the adsorber with dye is 27.5% dye, based on the dry adsorption material.

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" 2b -

Example 23

300 g of the polymer solution from Example 22 are atomized with air from a spray gun at room temperature. The spray cone is directed at an acute angle against the spray cone of a second spray gun, from which water at room temperature is atomized. When the two spray cones meet, the polymer coagulates in the finest, amorphous form. The coagulate is collected in a glass tube, ^{rinsed with 40 °} C. warm water and filtered off. A polymer gel with an average particle size of 0.01-0.1 mm is obtained. Determined by the BET method is

specific surface area of the polymer gel 185 m / g.

In the same decolorizing process as described in Example 22, a liquor is obtained which only has traces of dye contains. The loading of the adsorber is 31.3% dye, based on the dry adsorption material,

A similar result is obtained when the polymer solution is not poured into a water spray cone, but against water vapor is atomized.

609882/1031

Claims (1)

Claims 1. A method for cleaning industrial waste water, characterized in that it is treated with a polymer Adsorbent brings into contact, which is in a solvated Gel condition. 2. The method according to claim 1, characterized in that the wastewater in the textile, fiber, paper or leather · industry or dye or brightener production are contaminated liquors. 3. The method according to any one of claims 1 or 2, characterized in that the waste water is anionic or cationic Substances or mixtures thereof are liquors. 4. The method according to any one of claims 1 to 3, characterized in that the waste water is anionic or cationic Contain dyes, optical brighteners, textile or dyeing auxiliaries, surfactants, tanning agents or mixtures of such substances. 5. The method according to any one of claims 1 to 4, characterized in that the waste water mixtures of anionic 609882/1031 and / or cationic dyes with anionic, cationic or nonionic auxiliaries and / or nonionic Contain dyes. 6. The method according to any one of claims 1 to 5, characterized in that the cleaning according to a fixed bed process is carried out. 7. The method according to any one of claims 1 to 6, characterized in that the cleaning of the waste water is carried out ^{at 0 to 100 0 G.} 8. The method according to claim 7, characterized in that the cleaning at a temperature between 10 and 70 ° C is carried out. 9. The method according to any one of claims 1 to 8, characterized characterized in that the adsorbent material is in a hydrated gel state. 10. The method according to any one of claims 1 to 9, characterized in that the polymer gels have an average Molecular weight greater than 500 and a specific upper 9 have an area greater than 30 ηΓ / g. 60988.2 / 103 1 11. The method according to any one of claims 1 to 10, characterized in that the adsorbent polymer gels from
Synthetic plastics exist, which can be anionically or cationically modified. 12. The method according to claim 11, characterized in that that the polymer gels consist of fully synthetic thermoplastics. 13. The method according to claim 12, characterized in that the polymer gels produced in wet spinning processes synthetic fibers represent. 14. The method according to claim 13, characterized in that the fiber material made of synthetic polyamides, anionic modified polyamides, polymeric or copolymeric acrylonitrile, cellulose esters, linear polyesters or acid modified Polyesters are made. 15. The method according to any one of claims 13 and 14, characterized in that the single fiber has a titer of
0.2 to 20 denier. 16o method according to any one of claims 13 to 15, characterized characterized in that the polymer gels are used in the form of tow. 609882/1031 2626A92 17- The method according to any one of claims 13 to 16, characterized characterized in that the polymer gels are polymeric or copolymeric acrylonitrile tow in the hydrated gel state represents. 18. The method according to any one of claims 1 to 17, characterized characterized in that the polymer gels are crushed Form can be used. 19. The method according to claim 18, characterized in that the polymer gels in the form of cut or torn Spinning tow with fiber lengths of 1 to 10 mm can be used. 20. The method according to claim 18, characterized in that the polymer gels are used in the form of ground fibers will. 21. The method according to any one of claims 1 to 12, characterized characterized in that the polymer gels are used as a fiber fleece will. 22. The method according to any one of claims 1 to 12, characterized characterized in that the polymer gels are used as amorphous particles. 609882/1031