DE2451698A1 - METHODS FOR CLEANING UP INDUSTRIAL WASTE - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basel

CBA-GEIGY

Case 1-9088 / + [according to qerejcht

GERMANY . ] J | _t / t

Process for cleaning industrial waste water

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

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One of the major environmental problems in industrialized areas is the pollution of rivers and lakes. Since the dirt also comes 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 the removal of organic, non-biodegradable substances dissolved in water is possible. As part of this There is therefore a problem with the decolorization and cleaning of in the dye, textile, paper and leather industries there is an urgent need for waste water.

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 waste water in large collecting basins and the dye and auxiliary residues to be precipitated by adding suitable flocculants and separated by sedimentation, flotation or filtration. However, these methods have the disadvantage that the volumes of water to be treated are large and so are 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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turn around. The use of activated charcoal alone generally proves to be unsuitable because of its absorption capacity the activated carbon is too low for organic dyes dissolved in water and for impurities in the waste water is.

It has now been found, surprisingly, that you can quickly and adequately clean industrial Wastewater is achieved when it is brought into contact with an adsorbent that has been pretreated with precipitation agents Contains carrier and activated carbon. This adsorbent alone distinguishes itself from activated carbon, for example increased absorption capacity of dissolved or dispersed in water Fabrics.

The new adsorbent is particularly suitable for removing anionic or cationic substances or their mixtures, in particular for removing residues of anionic or cationic dyes, optical brighteners, Dyeing auxiliaries, tanning agents, detergents or mixtures thereof.

With the help of the new adsorption material, however, not only incompletely drawn out dyeing, lightening and treatment liquors to a large extent from the substances mentioned above, but also not the corresponding Residual liquors containing ionic auxiliaries and liquors diluted by rinsing waste water, which are mostly mixtures of "dyeing

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contain substances and detergents, clean to a satisfactory extent.

Cationic substances can also be found in the wastewater

₅ are eliminated by treating the adsorbent material according to the invention to be used in addition with an aromatic anionic material. Suitable aromatic organic substances are above all organic anionic dyes and optical brighteners. These generally contain aromatic rings and preferably also sulfonic acid groups.

Thanks to the wide range of applications of the new adsorption material, 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, 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 are used for staining of loose fiber material of slubbing, yarn and woven or knitted fabrics "as well as from cleaning devices, for example, originate from a _s-width washing machine.

The wastewater to be cleaned is, if necessary, after a pH correction, e.g. to a value of 2 to 7, especially 3 to 5 or 3 to 4 "preferably in undiluted Shape in

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Brought into contact with the new adsorbent material. In principle, three methods are suitable for this purpose:

a) so-called stirring process, xtfobei that too cleansing water in a container with the Adsorbent is stirred and then separated from one another;

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

c) So-called filtration process, the liquor to be cleaned through a filter-like Adsorption material is performed.

If these three procedural variants result in the Filtration method c) used, the following three apparatus variants are particularly suitable:

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

2. The filter device is movable and can be coupled to any treatment apparatus as required.

3. The wastewater from the treatment liquors are combined in a suitable container and then filtered together.

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The cleaning of the waste water is expediently carried out at 10 to 150 ^° C. However, it is preferably carried out between 30 and 130 ^° C. and in particular 30 and 100 ^° C. and the waste water can optionally be cleaned under pressure.

For the production of the adsorption material, the carrier pretreated with precipitation agents is usually used, preferably cellulosic material mixed with activated carbon. Both components will take advantage of this for a long time mixed until a homogeneous intimate mixture is formed. The activated carbon is expediently used as the carrier material in large quantities from 2 to 95%, preferably 10 to 70%, calculated on the weight of the adsorbent material. The activated carbon can be used in granulate or granular form (grain size 0.5 to 4 mm) as well as powder. Activated carbon powder is preferably used, which as a rule has a particle size of less than 0.5 mm, preferably less than 0.12 mm having.

For example, inorganic fillers are used as carrier materials for the production of the adsorbent, non-ionic synthetic plastics, but especially cellulosic materials. These carrier materials can also be used in the form of their mixtures.

The cellulose-containing substances to be used as carrier materials are appropriately bleached or unbleached spruce sulfite cellulose, kraft

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Cellulose, waste in a suitable form or around peat, wood pulp, wood flour, cork flour, tree bark or grain waste. The waste is broken down on suitable machines, for example on a hydraulic pulper. The cellulose can be in the form of granules, filter paper or paper pulp.

Synthetic plastics can also be used as carrier materials which are free of ionogenic-salt-forming groups in water, i.e. which are neither in Water acidic dissociating groups, such as sulfonic acid, carboxylic acid or phosphonic acid groups, or onium groups, such as ammonium, sulfonium or phosphonium groups.

Such nonionic plastics can belong to the most varied of known classes of semi-synthetic and fully synthetic plastics. Among these, polycondensates, polymers and polyadducts come into consideration, which can be both thermosets and thermoplastics. Suitable semi-synthetic polymers include cellulose esters such as cellulose nitrate, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, cellulose propionate, cellulose ethers such as methyl cellulose _s Äethyl cellulose and benzyl cellulose. It is advantageous to use fully synthetic thermoplastics that are used in fiber or granulate form. Examples are: linear polyester or polyolefin fibers, as well as polystyrene or polyurethane foam granules.

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There are also water-insoluble condensation polymers z "B" from urea or melamine and formaldehyde in Consideration, these plastics are preferably in a form with a large specific surface, e.g. in form finely structured agglomerates of almost spherical particles.

Suitable inorganic fillers for the production of the adsorption material are above all so-called white Fillers such as titanium dioxide, silicon dioxide (quartz, Diatomaceous earth, kieselguhr), zinc oxide, aluminum hydroxides, barium sulfate or carbonate, calcium carbonate or sulfate, Magnesium carbonate5 dolomite, aluminum silicates or hydrosilicates, Mica, slate flour, calcium silicates, magnesium silicates (talc, asbestos flour), clays and types of kaolin such as White earth, china clay, china clay, white bolus, also silica, silica gel, silica and fuller's earth.

In principle, basic, nitrogen-containing, polymeric compounds are suitable as precipitation agents. These are from the substrate mainly by the adsorptively bound and practice in combination with the activated carbon at the same time to the waste materials in question, such as dyes, optical brighteners, surfactants, detergents or ₅ tannins a precipitating or retenierende effect of cellulose. Polymers which have basic nitrogen atoms capable of forming salts have proven to be suitable in this regard.

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Examples of such polymers are water-soluble or water-dispersible basic aminoplasts such as formaldehyde-dicyandiamide condensation products. It is useful to use condensation products from formaldehyde, dicyandiamide and Urea or an alkylene polyamine with a total of 2 to 18, preferably with 2 to 8 carbon atoms and 2 to .5 amino groups worked.

The alkylene polyamines are

for example, ethylenediamine, propylenediamine, Butylenediamine, pentylenediamine, hexamethylenediamine, diethylenetriamine *, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, Tripropylenetetramine, dihydroxydipropylenetriamine, Dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, - Dipentylenetriamine, tripentylenetetramine, tetrapentylenepentamine, dihexamethylenetriamine, trihexamethylenetetramine and tetrahexamethylene pentamine. as well reaction products of epichlorohydrin with alkylene or polyalkylene amines or imines such as reaction products of epichlorohydrin with diethylenetriamine or triethylenetetramine or ethyleneimine or polyethyleneimine are used.

Suitable basic aminoplasts are above all formaldehyde-dicyandiamide-ethylenediamine or formaldehyde-urea -Dicyandiamide condensation products. Preferred Products are, for example, by condensation of 2 moles of formaldehyde with 1 mole of the reaction product of 2 moles of dicyandi

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amide with 1 mole of ethylenediamine or the corresponding salt such as hydroetiloride or ammonium chloride. More basic Aminoplasts are made by condensation of 1 mole each of urea, dicyandiamide and formaldehyde in the presence of Acid, such as hydrochloric acid or by condensation of 3 to 4 moles of dicyandiamide with 7 moles of formaldehyde und.l moles of the tetrahydrochloride made of triethylenetetramine. Further products can be obtained by condensation of 1 mole of dicyandiamide with 2 to 2.2 mol of formaldehyde, 0.6 to 1 mol of ammonium chloride and 0.05 to 0.5 mol of ethylenediamine are obtained.

Of particular practical interest as a precipitation agent However, the polyamide polyamines are polymerized by reaction, preferably dimerized to trimerized Fatty acids with polyamines are obtained, expediently in such a ratio that the resulting Polyamide resin has an atnine value in the range of about 200 to 650 mg of potassium hydroxide per gram of polyamide polyamine. As polyamines that can be used for the preparation of the polyamide polyamines, aromatic polyamines or use especially aliphatic polyamines, which can also contain heterocyclic structures, such as imidazolines. Polymeric fatty acids which are advantageously present in such polyamides are made by polymerization of one or more unsaturated long chain aliphatic or aromatic-aliphatic acids or their esters or other derivatives that easily convert into the acid

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Transferable are preserved. Suitable examples of such polymeric fatty acids are described in British patents 879,985 and 841,554 ". These polyamide polyamines" can be used alone or in combination with the aforementioned dicyandiamide condensation products will.

In the case of the polymeric unsaturated ones used here Fatty acids are advantageously aliphatic, ethylenically unsaturated di- to trimeric fatty acids. Preferably "The polyamide polyamines are made from polyalkylene polyamines and aliphatic, ethylenically unsaturated di- to trimeric fatty acids, which differ from monocarboxylic acids with Derive 16 to 22 carbon atoms. These Monocarboxylic acids are fatty acids with. at least one, preferably 2 to 5 ethylenically unsaturated bonds, representatives of this class of acids are e.g. oleic acid, Hiragonic acid, elaostearic acid, licanic acid, arachidonic acid, Clupanodonic acid and especially linoleic and linolenic acid. These fatty acids can be obtained from natural oils, in which they mainly occurring as glycerides, are obtained ·.

The di- to trimeric fatty acids are given in a known manner by dimerization of monocarboxylic acids Kind received. The so-called dimeric fatty acids always have a trimeric and a small monomeric content Acids.

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The dimerized to trimerized ones are particularly suitable Linoleic or linolenic acids «The technical products of these Acids usually contain 75 to 95 percent by weight of dimeric acid, 4 to 22 percent by weight of trimeric acid and 1 to 3% by weight of monomeric acid. The molar ratio of dimeric to trimeric acid is accordingly about 5: 1 to 36: 1.

Formed fatty acids or esters which are used for the production of the reactive polyamides can also be epoxidized, for example by reaction with peracetic acid, performic acid or with hydrogen peroxide and formic acid or acetic acid. Suitable epoxidised 'fatty acids and esters are described in British Patent Specifications 810 348 and 811 797th

Polyamides which can be used according to the invention can also be condensation products of polymeric fatty acids with polyamines as described in British Patent Nos. 726 570 and No. / 847 028, these Products with epoxy resins can be implemented by reacting polyhydric phenols with polyfunctional ones Halohydrins and / or glycerol dichlorohydrin are formed and are described in U.S. Patents 2,585,115 and 2,589,245 are.

Also reactive forms of polyamide obtained by condensation polymerisation at high temperatures from a

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Reaction mixture, the polymeric fatty acids (prepared according to British Patent Nos. 878,985 and 841,544), monomeric fatty acids and lower polyalkylene polyamines can be used in the present invention.

Suitable polyamide resins that can be used to make the adsorbent materials are, for example in British Patent Nos. 726 570, 810 348, 811 797, 847 028, 865 656 and 1 108 558.

Other precipitation agents are the polymers of alkylene imines with advantageously 2 to 4 carbon atoms which have an average molecular weight (Mw) of 500 to lOO'OOO, practical 500-80 ¹ OOO OOO, more preferably 10 ¹ to 40 ¹ OOO. These polymers have a Brookfield viscosity at 20 ⁰ C 500-20 ¹ OOO centipoises (cp) in the rule. Particularly suitable alkyleneimines are ethyleneimine, propyleneimine, 1,2-butyleneimine and 2,3-butyleneimine. Of all alkyleneimines, the ethyleneimine is preferred.

To produce a particularly powerful Adsorbent, which is mainly made up of cellulosic! material consists, precipitation agents which consist of two components are also suitable. Such precipitants. are obtained in a simple manner by means of polymer precipitation in the presence and absence made of carrier material.

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... 14 -

This polymer precipitation is preferably carried out by the aforementioned polymeric polycationic Precipitant in aqueous medium with a polyanionic Polymer falls. In this way, polymer associates that are sparingly soluble in water are formed, which on the present carrier material can be knocked down. If the polymer precipitation takes place in the absence of carrier material, so the resulting polymer associates are then applied to the carrier material in a suitable form.

Polyanionic polymeric precipitants which have proven to be particularly useful are optionally substituted homopolymers or copolymers the aliphatic a: ß-ethylenically unsaturated carboxylic acids, advantageously in the form of their alkali metal salts, especially the sodium and potassium salts or in the form of their ammonium salts, optionally in a mixture with corresponding ones proven free polycarboxylic acids.

Primarily used are water-soluble, optionally substituted by alkyl or halogen homopolymeric acrylic acids, for example homopolymers from the following monomers: acrylic acid, methacrylic acid, <x -ethy! acrylic acid, α-isopropyl acrylic acid, α-butyl acrylic acid and α-chloroacrylic acid. Water-soluble ones are particularly preferred Homopoly

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mers of acrylic or methacrylic acid with an average molecular weight of 20,000 to 1,000,000, in particular those with an average molecular weight of 50,000 to 150,000.

Suitable copolymeric aliphatic α: β- ethylenically unsaturated carboxylic acids are above all copolymerization products of acrylic acid and methacrylic acid, but then also copolymerization products of acrylic acid or methacrylic acid with a further substituted acrylic acid mentioned above.

Other polyanionic copolymerization products are made by copolymerization of acrylic or methacrylic acid with other water-soluble or water-insoluble, vinyl group-containing, copolymerizable comonomers obtained. Examples of water-soluble comonomers that may be mentioned are:

a) comonomers containing sulfonic acid groups, such as styrene sulfonic acid;

b) comonomers containing carboxylic acid groups, such as Crotonic acid;

c) comonomers containing carboxamide groups and their N-hydroxyalkyl derivatives, such as acrylic acid amidej Methacrylic acid amide, N-hydroxymethyl, N-ß-hydroxyethyl, N-Y-hydroxypropyl-, N, N-bis-

ß-hydroxyethyl acrylic acid amide, N-hydroxyniethyl, N-ß-hydroxyethyl, N-T-hydroxypropyl and N, N ~ bis-ß-hydroxyätyhl ~ niethacrylsäureamid;

d) water-soluble, especially sulfonated derivatives of ß-hydroxyalkyl acrylic acid amides or methacrylic acid amides, which, for example, by condensation of acrylic acid or methacrylic acid halides, especially chlorides, with reaction products of alkanol amines and chlorosulfonic acid obtained;

e) copolymerizable aldehydes, such as acrolein or crotonaldehyde.

Examples of suitable water-insoluble comonomers are:

i) Acrylic or methacrylic acid alkyl esters with up to 12 carbon atoms in the alkyl radical, which optionally can be further substituted, especially by hydroxyl groups, such as methyl acrylate or methacrylate, -ethyl ester, -ß-hydroxyethyl ester, -n.butyl ester and -dodecyl ester;

Ii-) vinyl esters of aliphatic, 1 to 12 carbon atoms containing carboxylic acids or mixtures of such carboxylic acids, such as vinyl acetate, vinyl formate, vinyl butyrate or Vinyl esters of a carboxylic acid mixture having 9 to 11 carbon atoms;

iii) Viny! benzenes, such as styrene, chlorostyrene or Me thy! Styrene.

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As polyanionic (^ polymerization products also copolymers of dibasic carboxylic acids and their functional derivatives such as maleic acid, maleic anhydride, Maleic acid monoalkyl esters and amides, fumaric acid, itaconic acid, Citraconic acid can be used with aliphatic or araliphatic olefins.

The polyanionic polymers mentioned can be prepared in an aqueous manner in a manner known per se Solution or suspension under the action of catalysts, preferably radical-forming catalysts, such as Hydrogen peroxide, ammonium persulfate, potassium persulfate or organic peroxides, e.g. dibenzoyl peroxide or then using ammonium persulphate and sodium hydrogen sulphite, be made. It is expediently carried out at a temperature between 40 and 100.degree.

Carboxyalkylated cellulose derivatives can be used as further polyanionic precipitants. Particularly Carboxymethylcellulose, which is usually in the form of its water-soluble alkali metal salts such as Sodium or potassium salts are used. Such carboxymethyl cellulose derivatives suitably have a degree of substitution (DS) of 0.4 to 2; carboxymethyl cellulose salts are preferred with DS = 0.7 to 1.2. (Definition of the degree of substitution DS according to the Enc. Of Polym. Sei. And Technol. Volume 3, page 468). The amount of polyanionic precipitants used advantageously varies between 10 and 200% by weight,

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based on the polycationic polymer. Preferably be 20 to 100% by weight of the polyanionic agent is used.

For the production of particularly high-performance adsorption material A combination of the above-mentioned polycationic precipitants has proven to have high retention Polymers or polymer associates with salts of polyvalent metals such as aluminum sulfate, aluminum chloride, Iron sulfate, ferric chloride, magnesium sulfate, magnesium chloride and calcium chloride have proven beneficial.

Such combinations have proven to be particularly advantageous for cleaning wastewater which contains dyes, optical brighteners, dyeing auxiliaries, surfactants, tannins,
It has been shown to contain detergents or mixtures of such substances. In particular, wastewater, which mixtures of
anionic and cationic dyes

or mixtures of anionic and / or cationic dyes with anionic, cationic, non-ionic auxiliaries and / or contain organic or inorganic salts, successfully cleaned.

The metal salts are preferably used in the hydrated form of the corresponding neutral or basic metal oxides. This is conveniently done by adding inorganic or organic bases to the aqueous solution
the above-mentioned metal salts. As inorganic

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Bases are preferred alkali metal hydroxides, e.g .: sodium hydroxide, Potassium hydroxide and aqueous ammonia, as organic bases mainly alkylamines such as: methylamine, di- or Trimethylamine, ethyl, diethyl or triethylamine and alkanolamines - such as mono-, di- or triethanolamine - are used.

The amount of metal salts used advantageously fluctuates between 10 to 300% by weight, based on the amount of used precipitation agent. Preference is given to using 50 to 200% by weight of the metal salt, based on the set amount of precipitant used.

Particularly suitable precipitation agents are polymer associates of polymers containing basic nitrogen atoms with a polyanionic polymer in combination with hydrate oxides of polyvalent metals.

The pretreatment of the carrier material with precipitation agents is expediently carried out in an aqueous suspension, for example at room temperature (20 ° C.). However, it can also take place at elevated temperature to 100 ⁰ C. The amount of precipitation agents used varies advantageously between 0.5 and 70% by weight _, based on the carrier material.

For this purpose, 10 to 50% by weight are preferably used. In the case of the cellulose-containing carrier material, e.g. the cellulose or waste is used as a preparation for the pretreatment is converted into a form suitable for this, in particular into a fiber suspension. For this, the duration the pre-treatment depending on the chosen temperature conditions

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vary between a few minutes and several hours. The pretreated cellulose is then mixed with activated carbon, mixed with particularly fine powdered activated carbon and then suitably processed into filter materials using known methods.

As dyes that are removed from the wastewater with the adsorption material to be used according to the invention Both water-soluble and water-dispersible, anionic or cationic dyes or optical dyes can be used Brighteners come into consideration. The adsorption material is preferably suitable for removing water-soluble, in particular anionic dyes or optical brighteners.

The anionic dyes that are removed according to the invention are dyes, their anionic character due to the formation of metal complexes alone and / or acidic substituents caused by the water solubility is conditional. As such, the water solubility causing acidic Substituenteii, come carboxylic acid groups, Phosphoric acid groups, acylated sulfonic acid imide groups, such as Alkyl or aryl disulfimide or alkyl or aryl carbonyl sulfimide groups and especially sulfonic acid groups.

The anionic dyes can be of the most varied Belong to dye classes. For example, oxazine, Triphenylmethane, xanthene, nitro, acridone, stilbene, perinone, naphthoquinoneimine, phthalocyanine, anthraquinone and

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Called azo dyes. The latter can be metal-free, metalizable or metal-containing mono-, dis- and polyazo dyes, including the formazan dyes in which the metal atom is a 1: 1 or 1: 2 complex, in particular 1: 2 chromium or 1: 2 cobalt complexes forms the two same or two different molecules azo dye complex contain bound to a chromium or cobalt atom. These dyes can also contain so-called reactive ■ Groupings which enter into a covalent bond with the fiber material to be dyed.

In the case of the cationic dyes, which are removed from the waste water with the aid of the agent to be used according to the invention are, in general, the common ones Salts and metal halides, for example "zinc chloride double salts of the known cationic dyes, whose cationic character comes from a carbonium, oxonium, sulfonium and, above all, from an ammonium group. Examples of such chromophoric systems are: methine, azomethine, hydrazone, azine, oxazine, thiazine, diazine, Xanthene, acridine, polyary methane such as diphenyl methane or triphenylmethane, as well as coumarin and azo dyes, the one indolinium, triazolium, tetrazolium, oxadiazolium, Thiodiazolium, oxazolium, thiazolium, pyridinium, 'pyrite nidinium or pyrazinium ring. Further can be arylazo, phthalocyanine and anthraquinone dyes that have an external ammonium group, for example a carry external cyclammonium or alkylammonium group.

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. The method according to the invention is suitable

not only for decolorizing residual liquors in textile, paper or leather dyeing, but also affords In addition, they are also useful when it comes to removing residues of anionic or cationic optical brighteners Remove washing and bleaching liquors. Particularly favorable results are obtained in those cases in which the optical brighteners to be eliminated have an anionic character.

The optical brighteners can belong to any class of brightener. The anionic brighteners act it is in particular stilbene compounds, coumarins, benzocoumarins, pyrazines, pyrazolines, oxazines, dibenzoxazolyl or dibenzimidazolyl compounds or naphthalic acid imides which contain at least one acidic group in the molecule, e.g. Have carboxylic acid or preferably a sulfonic acid group -and fiber-reactive. In the case of the cationic brighteners, it is primarily optical brighteners the methine, azamethine, benzofuran, benzimidazolyl, coumarin, naphthalimide or pyrazoline series.

Another advantage of the adsorption material to be used according to the invention is based on the fact that it is partially In addition to the colorants, there is also an elimination of non-ionic, anion-active and cation-active surfactants and dyeing auxiliaries from aqueous residual liquors are permitted. Such Auxiliaries are in the book "Tenside-Textile Auxiliaries-Washing Raw Materials" from

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Dr. Kurt Lidner (published by Wissenschaftlicher Verlagsgesellschaft Stuttgart 1964) described in more detail. Anion-active compounds are of particular practical interest of the alkylarylsulfonic acid type. Most notably The retention capacity is pronounced in the case of anionic compounds of the alkylarylsulfonic acid type, in which the Alkyl part has 10 to 14 carbon atoms.

The adsorbent can also

Provide help where there is a need to eliminate anionic synthetic tanning agents, especially those found in the molecule carries one or more sulfo groups, acts. A more detailed description of these connections can be found e.g. in "Ullman's Encyckopädie der technischen Chemie" volume 11; Pp. 595-598.

By suitable choice of the adsorption material, up to 1007 _{o of} the pollution can be removed from the waste water according to the invention. Retention effects of up to 20 g or even up to 50 g of residual material, ie dyestuff, optical brighteners, auxiliaries, detergents, tanning agents, per 100 g of adsorption material can be achieved. In cases in which it is not possible to completely decolorize or remove the residual materials by treating the residual liquor with the adsorption material once, it is advisable to repeat the cleaning process.

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The same measure (recirculation) can also reduce the adsorption material used to a minimum be reduced.

A particularly economic advantage of the invention The adsorbent to be used lies in the fact that it, together with the residual materials, after the cleaning process which are predominantly removed from the wastewater in solid form, dried in a simple manner and then fed to the incineration can be.

In the following manufacturing instructions and examples, percentages are always percentages by weight.

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Manufacturing regulations Precipitation agent

A. 34 kg of dicyandiamide are combined with 18 kg of urea and 5.5 kg of ammonium chloride in 75 kg of 30% hydrochloric acid refluxed for 6 hours. Then 80 kg of 37.4% aqueous formaldehyde solution are added and the whole was stirred at 75 to 85 ° C. for 6 hours. After the condensation has ended, the solution is mixed with 10 kg of glacial acetic acid offset. '

B. - A mixture of 533 g of ethylenediainine dihydrochloride and 673 g of dicyandiamide is added in small portions over the course of about 2 hours, while stirring, to a flask which is immersed in a heating bath at 250 to 255 ° C. This produces an easily stirrable melt ..- The mixture is stirred for one hour at an inner temperature of 250 to 255 ⁰ C according to. When the mixture is impressed and when it is subsequently stirred, ammonia is split off. Subsequently, the Innentemperätur is lowered to about 155 ⁰ C, whereupon 147 g of glacial acetic acid can be incorporated within about 5 minutes. The internal temperature is lowered to about 115 ^° C. by further cooling and 107 g of paraformaldehyde are introduced in about 15 minutes. The internal temperature is then allowed to ^{drop to 100 °} C. and 363 g of 37% strength aqueous are added. Formaldehyde solution added within about 5 minutes ". Now

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heated for about 10 to 15 minutes in a simmering
Water bath, whereby a thickening of the reaction mixture
enters, allows 500 g of water at about 90 ⁰ C to flow in
and continued to heat in the boiling water bath for a total of 2 hours. A clear solution results after about 20 minutes. The internal temperature is lowered to about 50 ^° C., neutralized by adding sodium hydrogen carbonate, and the reaction product is dried at 50 to 60 ^° C. under reduced pressure. An almost colorless, solid residue is obtained which is clearly soluble in boiling water.

Pretreatment of the carrier material with a precipitation agent

C. A suspension of 10 kg of bleached spruce sulfite cellulose in 300 kg of water is mixed with 2.5 kg of the above-described aqueous solution of dicyandiamide +
Urea + formaldehyde condensation products according to regulation A added. The whole mass is stirred ^{at 30 to 40 ° C. for 2 1/2 hours.} The pretreated cellulose is then filtered off and dried. The 10 kg of cellulose
contain 170 g of the condensation product A absorptively bound.

p_ ^ If the 10 kg bleached spruce suIfit gelulose is replaced in regulation C through 10 kg of waste in the form of a fine suspension and carries out the pretreatment as described under C

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copied with a product in accordance with regulation B, see above adsorptive cellulose is also obtained.

E. If the spruce-suIfit cellulose is replaced by Kraft cellulose in regulation C, further adsorptive cellulose is obtained.

F. If the 2.5 kg of precipitant A are replaced by 1 kg of Versamid 140 in procedure C. Polyamide polyamine with an amine value of 350 to 400 mg KOH / g, an effective cellulose filter material is obtained.

G. - If the precipitation agent is replaced in rule C. A by a combination of 200 g Versamid 140 with 200 g FeClo "βΗ ^ Ο, one also obtains adsorptive substances

Cellulose.

H. A suspension of 10 kg of bleached spruce sulfite cellulose in 100 kg of water is mixed with 800 g of 50% polyethyleneimine with an average molecular weight of 30,000 to 40,000. The whole mass is mechanically kneaded for 20 minutes. This mixture is then dried ^{at 90 ° C. in a vacuum oven.}

I. A slurry of 10 kg of finely chopped waste is stirred in 300 kg of water with 1 kg of Versamid 140 for 3 hours at a temperature of 20 to 25 ° C. To

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During this time, the fine suspension is pressed down to 30 kg. The filter cake is dried ^{at 80 to 90 ° C. in a vacuum oven.} The dry mass is crushed and stirred into 300 kg of water. A 10% AlCl solution is allowed to run in and, after 20 minutes, 2 liters of aqueous ammonia solution (25%) are added to the aqueous suspension. The mass is again pressed down to 30 kg and dried ^{at 90 ° C. in a vacuum oven.}

J._ If the polyethyleneimine is replaced in Regulation H by a combination of 800 g of 50% polyethyleneimine with 1025 g of A1 ₂ (SO,) ₃ -18H ₂ O, further suitable adsorptive cellulose is obtained. '

K. A suspension of 10 kg of bleached spruce sulfite cellulose in 500 kg of water is mixed with 1 kg of Versamid. The slurry is stirred during 300 minutes at 20 ⁰ C. 33.5 of a 17o aqueous solution of a polymethyacrylic acid with an average molecular weight of 80,000 to 100,000, adjusted to pH 6.1 with sodium hydroxide solution, are stirred into this suspension over a period of 20 minutes. The mass is stirred briefly and 6.67 l of a 107% AlCl ₃ solution are added. The pH of this suspension is then _{adjusted to 9 S 5 with a 107 0} strength aqueous ammonia solution, stirred for about 60 minutes and the pre-pressed

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dealt cellulose material to 30 kg. The on this Cellulose that has been pretreated in this way is used in this moist state for intimate mixing with activated charcoal powder.

L. A slurry of 10 kg of bleached spruce-sulphite-cellulose-e .in. 500 kg of water are mixed with 1 kg of Versamid 140. The slurry is gerlihrt for 300 minutes at 20 ⁰ C. 67.0 liters of a 1.5% strength carboxymethylcellulose sodium salt solution (DS approx. 0.8) are stirred into this suspension over a period of 20 minutes. The mass is then briefly stirred and pressed on a suction filter to a weight of approx. 30 kg.

M. The cellulose pretreatment is the same as in Regulation L, but 1 kg of Versamid 140 is replaced by 1 kg of polyethyleneimine with an average molecular weight of 30,000 to 40,000 and the 67.0 l of a 1.5% carboxymethyl cellulose solution by 67.0 1 of a 1% strength aqueous solution of a polymethacrylic acid with an average molecular weight of 80,000 to 100,000.

N. 50 g of fuller's earth are suspended in 600 ml of water and stirred at room temperature with 5 g of Versamid 140 for 2 hours. Then a 10 ml solution of 1.67 g of polymethacrylic acid in sodium hydroxide solution is added. from

509821/0 829

average molecular weight 80,000 to 100,000 in 200 ml of water, added dropwise within 30 minutes. The suspension is stirred for a further hour and with 33 ml of 10% aqueous aluminum chloride solution added. The suspension is then adjusted to pH 9.5 with ammonia water.

0. 10 g of polyethylene glycol terephthalate fibers of 3 mm staple length are suspended in 2 l of water, 1 g of Versamid 140 is added at room temperature and the mixture is stirred for 2 hours. A solution of 0.33 g of polymethacrylic acid (average molecular weight 80,000 to 100,000) in 40 ml of water, which has been adjusted to a pH of 6, is then added over the course of 30 minutes. The fiber suspension is then stirred for a further hour and 6.6 ml of a 10% strength aqueous aluminum chloride solution are added. The suspension is finally adjusted to pH 9.5 with ammonia water.

P. A suspension of 46.5 g of diatomaceous earth in 2000 ml of water is mixed with 115.4 ml of a 13% strength, aqueous, colloidal solution of Versamid 140 while stirring. The suspension is continued for 5 hours at a temperature of 23 ⁰ G. Then 500 ml of a 1% strength aqueous solution of polymethacrylic acid (average molecular weight 80-100,000) are stirred in over the course of 3 minutes. 97 ml of a 10% strength aqueous aluminum chloride solution are added to the suspension, with constant stirring. The pH of the suspension is then measured using a 10% sodium hydroxide

509821/0929

solution set to 9.5. The carrier material pretreated in this way is then pressed down to 212.1 g on a vacuum suction filter. The dry content of the adsorbent material is 67.87 g.

R. If you replace the 46.5 g of diatomaceous earth with the same amount of diatomaceous earth in regulation P- and carry out the pretreatment according to regulation P, the final pH of the suspension being adjusted to 6.0 by means of a 107% sodium hydroxide solution, 172.7 g of the moist adsorbent material are obtained in this way. The dry content of the adsorption material is 66.2 g.

S. If the 46.5 g of diatomaceous earth in rule R are replaced by the same amount of asbestos and the pretreatment is carried out according to rule R, 337.2 g of the moist adsorption material are obtained. The dry content of the material is 65.2 g.

Ί \ _ If you replace the 46.5 g of diatomite in regulation R. through a mixture of 23.25 g of asbestos and 23.25 g of bleached sulfite cellulose and carries out the pretreatment according to If regulation R is carried out, 304.2 g of the moist adsorption material are obtained. The dry content of the adsorbent is 67.9 g.

U. If the kieselguhr in regulation R is replaced by 46.5 g of an insoluble condensation polymer made from urea

2 "

and formaldehyde (specific surface area greater than 22 m / g) and

509821/0929

if the pretreatment is carried out in accordance with regulation R, then 323.4 g of the moist adsorbent obtained.- The dry content of the material is 66.8 g.

V. If the 33.5 1 polymethacrylic acid solution is replaced in procedure K by 40 1 of a 1% aqueous solution of an acrylic acid / methacrylic acid dodecyl ester copolymer (10: 1), thus 47.6 kg of the moist adsorption material are obtained. The dry content of the adsorbent is 11.4kg.

OAiGINAL WSPECTED

509821/0929

W. Adsorbent

Pre-treated cellulose (dry content 8 g), produced according to instruction K, in 400 ml of water at room temperature with 2 g of finely powdered activated charcoal for 2 minutes intensely stirred. The resulting homogeneous mixture is poured onto a round glass frit of 60 mm diameter and drained to a volume of about 120 ml. The filter cake is then lightly pressed and filled with 100 ml Glass spheres 3 mm in diameter coated.

Further good adsorbents which can be used in the following examples are obtained when using adsorbent material manufactured according to one of the regulations C to J or L to V.

509821/0929

example 1

A dark brown dye solution containing 0.1 g per liter of a "dye of the formula

OH HO HO

N = N- / ^x > and

1: 2 mixed chromium complex

contains and has a pH value of 4, is compared at a temperature of 90 to 95 ° C and a flow rate of 3 liters per hour over 10 g of one Filters of the combination given in the following table 1

Settlements directed. The decolorized quantities of filtrate in liters are given in the third column of Table 1.

Table 1

Vers.No. used filter material Completely ent
colored amount of filtrate
■ for »Tit-prn 1 10 g adsorbent material
manufactured according to regulation tW 15.0 2 10 g pre-treated cellulose
manufactured according to regulations
K- 0.1 3 "8 g of untreated cellulose
Z g activated carbon powder 2.0 10 g of untreated cellulose 0 5 10 g activated carbon powder 9 *

* Throughput speed .0.3 1 / hours ⁵⁰⁹⁸ 21/0929

Example 2

A dark brown-colored residual liquor adjusted to pH 4, which still contains 0.1 g per liter of a dye the formula given in Example 1 and 0.15 g per liter of a dyeing aid consisting of

907. a compound of the formula

^C 20 ^H 41 ~ ^N [(CH ₂ CH ₂ O) ₁₅ H] ^ and

107o of a compound of the formula

τ pu r \\ rr I

C ₁₈ H ₃₇ -N

^J 2

contains, is passed through a filter of the compositions indicated in Table 2 at a temperature of 90 to 95 ⁰ C and a flow rate of 3 liters per hour for comparison. The decolorized amounts of filtrate in liters are given in the third column of Table 2. - - '-

Table 2

Vers.No. used filter material Completely ent
colored amount of filtrate
in liters 6th
7th
8th
I.
j 9
I η
j 10 g adsorbent material
manufactured according to regulation W
10 g of cellulose material
made in accordance with regulation K
8 g uri-treated cellulose
2 g alcohol powder
10 g of untreated cellulose
10 ι- / ikf; iv charcoal powder 3.0
. 0.1
1.7
0
0.7 *

-k TXi rc? hj at a speed of 0.3 l / hour

BATH ORIGINAL

"509821/0929

. Ex iel 3

A dark blue dye solution containing 0.05 g per liter of the dye of the formula

0 Wed

O BrNHC-C = CH,

SO ₃ H

and Ο.05 g per liter of the dye of the formula

CH ₃ O,

UU ^

CH,

NC ₂ H ₄ -OH. CH ₃

ZnCl,

contains and has a pH value of 4, is compared at a temperature of 90 to 95 ° C and a throughput speed of 3 liters per hour over 10 g of a filter in the following. Table 3 given Compositions headed. The decolorized amounts of filtrate in liters are given in the third column of Table 3. '·. - - ■■

• 509821/0 92 ^! 9

Table 3

Vers.No. Used filter material G Adsorbent material
according to regulation W • Regulation D. Completely
discolored
Amount of filtrate
in liters 11 10 OQ OQ Adsorbent material
Act of charcoal powder manufactured Regulation F. 10.7 12th OO CM OQ OQ Adsorbent material
Activated carbon powder according to Regulation H 5.0 13th to co G
G Adsorbent material
Act of charcoal powder according to Regulation I. 11.0 14th 8th
■ 2 G
G Adsorbent material
Activated carbon powder according to Regulation J 11.9 15th 8th
2 G
G Adsorbent material
Activated carbon powder according to Regulation L. 9.8 16 8th
2 G
G Adsorbent material
Act of charcoal powder according to Regulation M. 9.1 17th 00 CM G
G Adsorbent material
Activated carbon powder according to Regulation N 12.2 18th 8th
2 OQ OQ Adsorbent material
Act of charcoal powder according to Regulation 0 22.5 19th 8th
2 G
G Adsorbent material
Activated carbon powder according to Regulation P. 11.3 20th 8th
2 OQ OQ Ads orration material
Activated carbon powder according to pre-treated cellulose produced
according to regulation K 5.6 21 8th
2 G according to untreated cellulose
Activated carbon powder 7.6 22nd 10 OQ OQ untreated cellulose. 0.1 23 00 CM G 3.5 24 10 0

609821/0929

Example 4

A dark blue-colored residual liquor, adjusted to pH 3.5, which still 50 mg / 1 of the anionic dye of the formula

O
H NH 2 ₃ H. O Br
It I ¹ Y ^^ - SO > ~ NHC-C = CH r f Il
O NH /
So ₃ H

and 50 mg / l of the cationic dye of the formula

C-N = N

Γ \

NC ₀ H ₇ -OH I 2 4 CH ₃

ZnCl,

• together with 0.5 g / l of a dyeing aid consisting of part of a quaternary salt of a polyethoxylated one Fatty amine and two parts of a sulfated polyethoxylated tallow fatty acid amide, and

0.15 g / l of another auxiliary consisting of part of a quaternary salt of a polyethoxylated one Fatty amine and part of a sulfated polyethoxylated Fe, ttamin, 509821/0929

in dissolved form, is comparatively at a temperature of 90-95 ⁰ C and a flow rate yon 3 liters per hour for each 10 g of a filter, of the composition given in Table 4 below, routed The decolorized of filtrate in liters are from the third Column can be seen.

Table 4

Vers.No. Used filter material Completely
discolored
Filtrate amount
in liters 25th 10 g of adsorbent material produced
according to regulation W 3.8 26th 10 g of pretreated cellulose produced
according to regulation K 0.2 27 8 g of untreated cellulose
2 g activated charcoal powder 2.5 28 10 g of untreated cellulose 0

509821/0929

. - 40 -

Example 5

In a stirred vessel, 5 l of a dark blue Residual liquor of the same composition as in Example 3 described, submitted. For this residual liquor, each of those indicated in column 3 of Table 5 below pH values are set, the adsorption materials listed in column 2 of Table 5 are stirred with stirring added. The remaining liquor is then decolorized at the temperatures indicated in column 4 of the table. at each attempt is made after a contact time of 15 minutes a sample is taken from the vessel, which is filtered through a folded filter and the sample indicated in column 5 Residual dye concentration in the filtrate determined.

509821/0929

Table 5

Vers.No. Adsorption material used pH 3.5 ⁰ C Rest color
fabric con
centering
in mg / 1 29 4 g adsorption material according to
Regulation R
1 g activated charcoal powder 3.5 • 80 3 30th 4 g adsorption material according to
Regulation R
1 g activated charcoal powder 3.5 30th 5 31 4 g adsorption material according to
Regulation S · -.
1 g activated charcoal powder '3.5 80 5 32 4 g adsorption material according to
Regulation S
1 g activated charcoal powder 3.5 30th 8th 33 4 g adsorption material according to
Regulation T
1 g activated charcoal powder 3.5 -80 4th 34 4 g adsorption material according to
Regulation T
1 g activated charcoal powder 5.0 30th 4th 35 4 g adsorption material according to
Regulation T
1 g activated charcoal powder 7.0 80 0 36 4 g adsorption material according to
Regulation T
1 g activated charcoal powder 80 0.5

509 8 21/09 29 ■

Claims (23)

Claims 1. A method for cleaning industrial wastewater, characterized in that the wastewater with a Bringing adsorbent into contact, which contains a carrier pretreated with precipitation agents and activated carbon. 2. The method according to claim 1, characterized in that the wastewater in the textile, paper or leather industry or dye or brightener production are residual liquors. 3. The method according to claim 1 or 2, characterized in that the waste water dyes, optical brighteners, Contain dyeing auxiliaries, surfactants, tanning agents, detergents or mixtures of such substances. 4. The method according to any one of claims 1 to 3, characterized in that the waste water is anionic or cationic Dyes or mixtures thereof or mixtures of anionic and / or cationic dyes with anionic, cationic, Contain non-ionic auxiliaries and / or salts. 509821/0929 5. The method of claims 1 to 4, characterized in that the sewage treatment at 10 to 150 ⁰ C is performed for one. 6. The method according to any one of claims 1 to 5, characterized in that the adsorbent is in the form of a filter is present. 7.. Method according to one of Claims 1 to 6, characterized characterized in that the carrier is nonionic synthetic plastics, cellulosic materials, inorganic fillers or mixtures of such carrier materials. 8 .. The method according to claim 7, characterized in that the carrier is a cellulose-containing material. 9. The method according to any one of claims 1 to 8, characterized in that the precipitation agent is a basic is nitrogen-containing polymer. 10. The method according to claim 9, characterized in that the basic polymer is a polyamide polyamine from a polymer Fatty acid and a polyamine. 11. The method according to claim 10, characterized in that the polyamide polyamine has an amine value in the range of 200 509821/0929 has up to 650 mg of potassium hydroxide per gram of polyamide polyamine. 12. The method according to claim '9, characterized in that the basic polymer is soluble or dispersible in water Is aminoplast. 13. The method according to claim 9, characterized in that the basic polymer is a polyalkyleneimine with an average Molecular weight is from 500 to 100,000. 14. The method according to any one of claims 1 to 8, characterized in that the precipitation agent is a polymer associate of a polymer containing basic nitrogen atoms with a polyanionic polymer. 15. The method according to claim 14, characterized in that the polyanionic polymer is an optionally substituted homo- or copolymer of an aliphatic α : ß- ethylenically unsaturated carboxylic acid. 16. The method according to any one of claims 1 to 8, characterized in that the precipitation agent is a combination is composed of a polymer containing basic nitrogen atoms and a salt of a polyvalent metal. 509821/0929 17. The method according to any one of claims 1 to 8, characterized in that the precipitation agent from the product a polymer containing basic nitrogen atoms and is a salt of a polyvalent metal prepared in the presence of an inorganic or organic base has been. 18. The method according to any one of claims 1 to 8, characterized in that the precipitation agent is a polymer associate a basic, nitrogen-containing polymer with a polyanionic polymer in combination with a salt of a polyvalent metal. 19. The method according to any one of claims 1 to 8, characterized in that the precipitation agent is a polymer associate of a basic, nitrogen-containing polymer with a polyanionic polymer in combination with hydrated Is oxides of a polyvalent metal. 20. Adsorbents for the purification of industrial wastewater> characterized in that it contains a carrier pretreated with precipitation agents and activated carbon. 21. Adsorbent according to claim 20, characterized in that it contains the activated carbon in amounts of 2 to 95% by weight, 509821/0929 calculated on the weight of the adsorbent. 22. Adsorbent according to claim 21, characterized in that the amount of activated carbon is 10 to 70% by weight, be is based on the weight of the adsorbent. 23. A method for producing the adsorbent according to any one of claims 20 to 22, characterized in that that the activated carbon is mixed with a carrier which has been pre-treated with precipitation agents. 509821/0929