EP0000674A1 - Method for breaking up emulsions and means for carrying out this method. - Google Patents

Method for breaking up emulsions and means for carrying out this method. Download PDF

Info

Publication number
EP0000674A1
EP0000674A1 EP78400055A EP78400055A EP0000674A1 EP 0000674 A1 EP0000674 A1 EP 0000674A1 EP 78400055 A EP78400055 A EP 78400055A EP 78400055 A EP78400055 A EP 78400055A EP 0000674 A1 EP0000674 A1 EP 0000674A1
Authority
EP
European Patent Office
Prior art keywords
chosen
aluminum
bentonite
reagent
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP78400055A
Other languages
German (de)
French (fr)
Other versions
EP0000674B1 (en
Inventor
Johann Heidenreich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technime Sa SA
TECHNIME S A SA
Original Assignee
TECHNIME S A SA
Technime Sa SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TECHNIME S A SA, Technime Sa SA filed Critical TECHNIME S A SA
Publication of EP0000674A1 publication Critical patent/EP0000674A1/en
Application granted granted Critical
Publication of EP0000674B1 publication Critical patent/EP0000674B1/en
Expired legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/05—Coalescer

Definitions

  • the present invention relates to a process for breaking emulsions and suspensions and the means enabling this process to be implemented. It is particularly useful in the field of industrial wastewater treatment.
  • the principle of the invention is based on the formation of micro-crystals of aluminum derivatives at the active sites of an adsorbent substance, in particular a bentonite. This formation of micro-crystals makes it possible to limit the swelling of the adsorbent substance in water.
  • emulsion means for convenience not only any emulsion, but also any suspension.
  • aqueous solutions of metal salts have the drawback of forming, with most of the emulsified systems, a coalesced phase, that is to say a creaming phenomenon of the dispersed phase is manifested, a circumstance which makes it difficult to phase separation.
  • the use of these metal salts always requires neutralization of the reaction mass because there is formation of acids by hydrolysis.
  • the powders in particular used for the purification of waste water, and in particular those described in the German patent applications published before examination DOS No. 2,507,733 and DOS No. 2,527,987, consist essentially of adsorbent substances and metallic salts. They have many drawbacks. In particular, the salts must not have hygroscopic properties, which would lead to a premature reaction between the various constituents of the powders, and would result in a notable loss of reactivity. The powders cannot be used, in continuously operating processes, on an industrially profitable basis. In particular the operating methods given in Example 2 of DOS No. 2,507,733 according to which a mixture of aluminum sulphate (12.5 kg) and -suspension is carried out in water (100 1). kaolin (12.5 kg) before proceeding to the purification of waste water (10 m3), does not allow a continuous treatment to be carried out as soon as the said mixture gives a gel, the active sites of the kaolin having no micro -crystallization.
  • the powders finally raise the problem of formation of dust with, in a large number of cases, the danger of silicosis for the personnel, and their use involves installations of a large size because of their low solubility in the reaction mass.
  • the invention aims to overcome the drawbacks of the prior art, and to provide a method for breaking emulsions useful in particular in the field of purification of industrial waste water, which uses special means, namely useful reagents comprising active earths and aluminum or an aluminum salt, the active earths having been treated so that their swelling in water is limited by the formation of micro-crystals at their active ranges.
  • a reagent according to the invention it is recommended to use one part by weight of a reagent according to the invention for 2 to 6 parts by weight of emulsified oil.
  • a reagent according to the invention it is recommended to use 1 part by weight of a reagent according to the invention for 2 to 6 parts by weight of emulsified oil.
  • 0.5 to 8 kg of reagent according to the invention will be used for 1 m 3 of emulsion or suspension; Within this range, the amount of reagent used depends on the nature of the emulsion or the suspension to be treated.
  • adsorbent substances a) which are suitable mention may in particular be made of bentonites and active earths such as clayey earths and alkaline earths. Of course, it is possible to use mixtures of said substances.
  • the adsorbent substances a) which are suitable are mainly remarkable for their ion exchange capacity and have active plaques or sites. According to the invention, these areas or sites cause the formation of microcrystals, by a local concentration of the metal salts in solution. aqueous, from a limit concentration which is still lower than the saturation concentration.
  • the preferred adsorbent substances according to the invention are bentonites, in particular moderate, calcium and magnesium bentonites, optionally in combination with another active earth.
  • a suspension (A) of 7.5 parts by weight of sodium bentonite is produced in 92.5 parts by weight of a mixture consisting of CaCl 2 (1 part by weight), of MgCl 2 ( 1 part by weight) of alumina hydrate (1 part by weight) and distilled water (89.5 parts by weight), and a suspension (B) obtained by dispersion in 62.5 parts by weight of distilled water, 37.5 parts by weight of the reagent of Example 8 according to the invention, the suspension B comprising 15 parts by weight of the sodium bentonite entering the suspension A.
  • the viscosity of A and of B is measured at by means of a consistometric cut having a diameter of 2.5 mm of flow opening according to the French standard AFNOR NF-T-30-014.
  • B which contains twice as much sodium bentonite as A has a viscosity which is approximately 3 times lower than that of A.
  • the dissolved salts modify the state of the electrical charges in the reaction mass and contribute to the coagulation of the dispersed phase.
  • an acid reagent it is advantageous to prepare it according to a manufacturing method which comprises mixing the bentonite with an acid, in particular hydrochloric acid, and adding to the resulting mixture of metallic aluminum, in particular under powder form.
  • the hydrochloric acid reacts with metallic aluminum, to give AlCl 3 .
  • metallic aluminum can be replaced by AlCl 3 , Al 2 O 3 , Al (OH) 3 .
  • the presence of a bentonite or other active earth prevents any leakage of gaseous aluminum chloride outside the mixture: the gas solidifies on the active areas of the earth and forms the micro-crystals mentioned above .
  • a basic reagent is obtained by mixing the bentonite with a base, in particular NaOH, KOH then by adding Al, AlCl 3 , Al 2 0 3 or Al (OH) 3 .
  • the reagent according to the invention can contain metals or metal salts.
  • the metal salts mention may especially be made of ferric chloride, calcium chloride, magnesium chloride, etc. These salts offer the advantage of adapting the reagent to the types of industrial waste water.
  • the active earth can be treated with sulfamic acid to obtain a reagent applicable to waters polluted by nitrites.
  • Example 5 The procedure is as indicated in Example 5, but replacing the metallic aluminum with an equivalent amount of A1 2 0 3 or Al (OH) 3 to avoid the release of H 2 resulting from the action of NaOH on Al. obtains a reagent as effective as that of Example 5.
  • Example 6 The procedure is as indicated in Example 6 but replacing the metallic aluminum with an equivalent amount of Al 2 O 3 or Al (OH) 3 . A reagent is obtained as effective as that of Example 6.
  • the reagent is prepared according to the methods given in Example 4 with regard to the order of introduction of the ingredients. This reagent is diluted with water at the time of use, for example as indicated above to obtain suspension B.
  • This example concerns the passage of a cutting emulsion based on mineral oils having an initial pH of 10.
  • This example concerns the breaking of a rectification emulsion based on synthetic oils with ultra-fine dispersion in the continuous phase of initial pH 8.5.
  • This example concerns the breaking of a wire drawing emulsion based on semi-synthetic oils and soapy substances with an initial pH of 9.5.
  • This example relates to the treatment of a rectification emulsion based on synthetic oils and nitrites of pH 7.5 using the reagent of example 7.
  • This example concerns the treatment of pickling waste water with metal salts with an initial pH of 3.5.
  • the object of the invention namely the breaking of emulsions and suspensions, advantageously applies in the treatment of oily emulsions and waste water.
  • the reagents according to the invention have been found to be very effective in the tanning industry, tanneries, slaughterhouses, in the food industry, in the cosmetics industry, in the treatment of waste water, in the paint industries. , papers, textiles, industrial dyers and laundries.
  • Such an installation which can be mounted on a truck or a trailer to treat waste water from various industries at the rate of one to several hours per week or per month, includes an automatic priming pump (1), a chamber (2 ) acting as primary breaking reactor, a second chamber (3) acting as secondary breaking reactor, a flocculation reactor (4), a pump (5) for dosing the reagent according to the invention, a pump (6 ) for dosing the flocculant, a container (7) serving as a flocculant reservoir, a filter (8) allowing the automatic separation of the purified water from the sludge, a receptacle (9) for collecting the sludge and a container (10) serving as a reservoir for the breaking reagent according to the invention.
  • the primary breaking reactor (2) can be a device of the "cycl8ne" type.

Landscapes

  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

La présente invention concerne un procédé de cassage d'émulsions et suspension, utile notamment dans le domaine de l'épuration des eaux résiduaires industrielles, ledit procédé étant caractérisé en ce que l'on traite sous agitation les émulsions et les suspensions à traiter, au moyen d'un réactif liquide choisi parmi l'ensemble constitué par les solutions et dispersions aqueuses comprenant: a) une substance adsorbante, notamment une bentonite, et b) de l'aluminium ou un dérivé d'aluminium notamment A1C13, A12O3,A1(OH)3, ledit réactif liquide étant obtenu à partir d'eau, des produits a) et b), et d'une substance choisie parmi les acides et les bases, de façon que des micro-cristaux de dérivés d'aluminium soient associés aux sites actifs de a).The present invention relates to a process for breaking emulsions and suspension, useful in particular in the field of the purification of industrial waste water, said process being characterized in that the emulsions and suspensions to be treated are treated with agitation. means of a liquid reagent chosen from the group consisting of aqueous solutions and dispersions comprising: a) an adsorbent substance, in particular a bentonite, and b) aluminum or an aluminum derivative in particular A1C13, A12O3, A1 ( OH) 3, said liquid reagent being obtained from water, products a) and b), and from a substance chosen from acids and bases, so that micro-crystals of aluminum derivatives are associated to the active sites of a).

Description

La présente invention concerne un procédé de cassage des émulsions et des suspensions et les moyens permettant de mettre en oeuvre ce procédé. Elle est notamment utile dans le domaine de l'épuration des eaux résiduaires industrielles.The present invention relates to a process for breaking emulsions and suspensions and the means enabling this process to be implemented. It is particularly useful in the field of industrial wastewater treatment.

Le principe de l'invention repose sur la formation de micro-cristaux de dérivés d'aluminium au niveau des sites actifs d'une substance adsorbante en particulier une bentonite. Cette formation de micro-cristaux permet de limiter le gonflement de la substance adsorbante dans l'eau.The principle of the invention is based on the formation of micro-crystals of aluminum derivatives at the active sites of an adsorbent substance, in particular a bentonite. This formation of micro-crystals makes it possible to limit the swelling of the adsorbent substance in water.

Dans ce qui suit le terme "émulsion" désigne par commodité non seulement toute émulsion, mais également toute suspension.In what follows the term "emulsion" means for convenience not only any emulsion, but also any suspension.

Jusqu'à présent, pour le cassage des émulsions, notamment dans le traitement des eaux résiduaires industrielles, on utilisait soit des solutions aqueuses de sels métalliques, soit des poudres.Hitherto, for the breaking of emulsions, in particular in the treatment of industrial waste water, either aqueous solutions of metal salts or powders have been used.

Les solutions aqueuses de sels métalliques ont l'inconvénient de former, avec la plupart des systèmes émulsionnés, une phase coalescée, c'est-à-dire qu'il se manifeste un phénomène de crémage de la phase dispersée, circonstance qui rend difficile la séparation des phases. De plus, l'utilisation de ces sels métalliques exige toujours une neutralisation de la masse réactionnelle car il y a formation d'acides par hydrolyse. Il existe aussi des systèmes dispersés qui résistent à l'action des sels métalliques et qui ne peuvent, par suite, être séparés.The aqueous solutions of metal salts have the drawback of forming, with most of the emulsified systems, a coalesced phase, that is to say a creaming phenomenon of the dispersed phase is manifested, a circumstance which makes it difficult to phase separation. In addition, the use of these metal salts always requires neutralization of the reaction mass because there is formation of acids by hydrolysis. There are also dispersed systems which resist the action of metal salts and which cannot therefore be separated.

Les poudres, notamment utilisées pour l'épuration d'eaux résiduaires, et en particulier celles décrites dans les demandes de brevet allemand publiées avant examen DOS n° 2 507 733 et DOS n° 2 527 987, se composent essentiellement de substances adsorbantes et de sels métalliques. Elles présentent de nombreux inconvénients. En particulier, les sels ne doivent pas posséder des propriétés hygroscopiques, ce qui amènerait une réaction prématurée entre les différents constituants des poudres, et aurait pour conséquence une perte de réactivité notable. Les poudres ne sont pas utilisables, dans les procédés fonctionnant en continu, de façon industriellement rentable. En particulier les modalités opératoires données à l'exemple 2 de la DOS n° 2 507 733 selon lesquelles on met en suspension dans de l'eau (100 1) un mélange de sulfate d'aluminium (12,5 kg) et-de kaolin (12,5 kg) avant de procéder à l'épuration d'eau résiduaire (10 m3), ne permettent de réaliser un traitement en continu dès lors que ledit mélange donne un gel, les sites actifs du kaolin ne présentant pas de micro-cristallisation.The powders, in particular used for the purification of waste water, and in particular those described in the German patent applications published before examination DOS No. 2,507,733 and DOS No. 2,527,987, consist essentially of adsorbent substances and metallic salts. They have many drawbacks. In particular, the salts must not have hygroscopic properties, which would lead to a premature reaction between the various constituents of the powders, and would result in a notable loss of reactivity. The powders cannot be used, in continuously operating processes, on an industrially profitable basis. In particular the operating methods given in Example 2 of DOS No. 2,507,733 according to which a mixture of aluminum sulphate (12.5 kg) and -suspension is carried out in water (100 1). kaolin (12.5 kg) before proceeding to the purification of waste water (10 m3), does not allow a continuous treatment to be carried out as soon as the said mixture gives a gel, the active sites of the kaolin having no micro -crystallization.

Les poudres soulèvent enfin le problème de formation de poussières avec, dans un grand nombre de cas, le danger de silicose pour le personnel, et leur emploi implique des installations d'un grand encombrement en raison de leur faible solubilité dans la masse réactionnelle.The powders finally raise the problem of formation of dust with, in a large number of cases, the danger of silicosis for the personnel, and their use involves installations of a large size because of their low solubility in the reaction mass.

L'invention a pour but de pallier les inconvénients de l'art antérieur, et de proposer un procédé de cassage des émulsions utile notamment dans le domaine de l'épuration des eaux résiduaires industrielles, qui fait appel à des moyens particuliers, à savoir des réactifs utiles comprenant des terres actives et de l'aluminium ou un sel d'aluminium, les terres actives ayant été traitées de façon que leur gonflement dans l'eau soit limité par la formation de micro-cristaux au niveau de leurs plages actives.The invention aims to overcome the drawbacks of the prior art, and to provide a method for breaking emulsions useful in particular in the field of purification of industrial waste water, which uses special means, namely useful reagents comprising active earths and aluminum or an aluminum salt, the active earths having been treated so that their swelling in water is limited by the formation of micro-crystals at their active ranges.

Le procédé préconisé selon l'invention pour le cassage des émulsions est caractérisé en ce que l'on traite, sous agitation les émulsions et suspensions à traiter, au moyen d'un réactif liquide choisi parmi l'ensemble constitué par les solutions et dispersions aqueuses comprenant :

  • a) une substance adsorbante, et
  • , b) de l'aluminium ou un dérivé d'aluminium, notamment A1C13, Al2O3, Al(OH)3,

ledit réactif étant obtenu à partir d'eau, des produits a) et b), et d'une substance choisie parmi les acides et les bases, de façon que des micro-cristaux de dérivés d'aluminium soient associés aux sites actifs de a).The process recommended according to the invention for the breaking of emulsions is characterized in that the emulsions and suspensions to be treated are treated with stirring, using a liquid reagent chosen from the group consisting of aqueous solutions and dispersions including:
  • a) an adsorbent substance, and
  • , b) aluminum or an aluminum derivative, in particular A1C1 3 , Al 2 O 3 , Al (OH) 3 ,

said reagent being obtained from water, products a) and b), and from a substance chosen from acids and bases, so that micro-crystals of aluminum derivatives are associated with the active sites of a ).

De façon avantageuse, on préconise d'utiliser une partie en poids d'un réactif selon l'invention pour 2 à 6 parties en poids d'huile émulsionnée. D'une manière générale, on utilisera 0,5 à 8 kg de réactif selon l'invention pour 1 m 3 d'émulsion ou de suspension ; & l'intérieur de cette fourchette la quantité de réactif utilisée est fonction de la nature de l'émulsion ou de la suspension à traiter.Advantageously, it is recommended to use one part by weight of a reagent according to the invention for 2 to 6 parts by weight of emulsified oil. In general, 0.5 to 8 kg of reagent according to the invention will be used for 1 m 3 of emulsion or suspension; Within this range, the amount of reagent used depends on the nature of the emulsion or the suspension to be treated.

Parmi les substances adsorbantes a) qui conviennent, on peut notamment mentionner les bentonites et les terres actives telles que les terres argileuses et les terres alcalino-terreuses. Bien entendu, il est possible d'utiliser des mélanges desdites substances. Les substances adsorbantes a) qui conviennent sont principalement remarquables par leur capacité d'échange d'ions et comportent des plages ou sites actifs. Ces plages ou sites provoquent, selon l'invention, la formation de micros- cristaux, par une concentration locale des sels métalliques en solution aqueuse, à partir d'une concentration limite qui reste encore inférieure à la concentration de saturation. D'un autre côté, il existe une valeur de seuil, avec une dilution progressive du réactif dans la masse réactionnelle, les forces de cohésion entre la terre porteuse et les micro-cristaux seront progressivement réduites au fur et à mesure que les sels cristallisés passent en solution. De cette manière, les terres actives se régénèrent et regagnent leur pouvoir d'adsorption afin de pouvoir agir sur la phase dispersée comme agents de coagulation.Among the adsorbent substances a) which are suitable, mention may in particular be made of bentonites and active earths such as clayey earths and alkaline earths. Of course, it is possible to use mixtures of said substances. The adsorbent substances a) which are suitable are mainly remarkable for their ion exchange capacity and have active plaques or sites. According to the invention, these areas or sites cause the formation of microcrystals, by a local concentration of the metal salts in solution. aqueous, from a limit concentration which is still lower than the saturation concentration. On the other hand, there is a threshold value, with a progressive dilution of the reagent in the reaction mass, the cohesion forces between the carrier earth and the microcrystals will be gradually reduced as the crystallized salts pass in solution. In this way, the active earths regenerate and regain their adsorption power in order to be able to act on the dispersed phase as coagulation agents.

Les substances adsorbantes préférées selon l'invention sont les bentonites, notamment les bentonites modique, calcique et magnésienne, éventuellement en association avec une autre terre active.The preferred adsorbent substances according to the invention are bentonites, in particular moderate, calcium and magnesium bentonites, optionally in combination with another active earth.

Afin d'illustrer le caractère très spécifique des réactifs préconisés selon l'invention on a effectué des essais comparatifs en ce qui concerne le pouvoir gonflant des terres actives habituellement utilisées selon les techniques antérieurement connues, et des mêmes terres actives préparées selon l'invention. Ces essais ont été résumés ci-après.In order to illustrate the very specific nature of the reagents recommended according to the invention, comparative tests were carried out with regard to the swelling power of the active earths usually used according to previously known techniques, and of the same active earths prepared according to the invention. These tests have been summarized below.

Pour disposer d'une dispersion suffisamment fluide on réalise une suspension (A) de 7,5 parties en poids de bentonite sodique dans 92,5 parties en poids d'un mélange constitué de CaC12 (1 partie en poids), de MgC12 (1 partie en poids) d'hydrate d'alumine (1 partie en poids) et d'eau distillée (89,5 parties en poids), et, une suspension (B) obtenue par dispersion dans 62,5 parties en poids d'eau distillée,de 37,5 parties en poids du réactif de l'exemple 8 selon l'invention, la suspension B comprenant 15 parties en poids de la bentonite sodique entrant dans la suspension A. On mesure la viscosité de A et de B au moyen d'une coupe consistométrique ayant un diamètre de 2,5 mm d'ouverture d'écoulement selon la norme française AFNOR NF-T-30-014.To have a sufficiently fluid dispersion, a suspension (A) of 7.5 parts by weight of sodium bentonite is produced in 92.5 parts by weight of a mixture consisting of CaCl 2 (1 part by weight), of MgCl 2 ( 1 part by weight) of alumina hydrate (1 part by weight) and distilled water (89.5 parts by weight), and a suspension (B) obtained by dispersion in 62.5 parts by weight of distilled water, 37.5 parts by weight of the reagent of Example 8 according to the invention, the suspension B comprising 15 parts by weight of the sodium bentonite entering the suspension A. The viscosity of A and of B is measured at by means of a consistometric cut having a diameter of 2.5 mm of flow opening according to the French standard AFNOR NF-T-30-014.

Pour la moyenne de trois essais on a les valeurs suivantes :

  • A : temps d'écoulement : 47 s viscosité : 17 cP
  • B : temps d'écoulement : 33 s viscosité : 6 cP
For the average of three tests we have the following values:
  • A: flow time: 47 s viscosity: 17 cP
  • B: flow time: 33 s viscosity: 6 cP

Ainsi B qui renferme deux fois plus de bentonite sodique que A a une viscosité qui est environ 3 fois inférieure à celle de A.Thus B which contains twice as much sodium bentonite as A has a viscosity which is approximately 3 times lower than that of A.

Les sels dissous modifient l'état des charges électriques dans la masse réactionnelle et contribuent à la coagulation de la phase dispersée.The dissolved salts modify the state of the electrical charges in the reaction mass and contribute to the coagulation of the dispersed phase.

La résultante des actions des terres adsorbantes et des sels permet le cassage des émulsions et contribue à l'épuration des eaux résiduaires industrielles.The result of the actions of adsorbent earths and salts allows the breaking of emulsions and contributes to the purification of industrial waste water.

Pour obtenir un réactif acide, il convient de façon avantageuse de le préparer selon un mode de fabrication qui comprend le mélange de la bentonite avec un acide, notamment l'acide chlorhydrique, et l'addition au mélange résultant d'aluminium métallique, notamment sous forme de poudre. L'acide chlorhydrique réagit avec l'aluminium métallique, pour donner AlCl3. Bien entendu l'aluminium métallique peut être remplacé par AlCl3, Al2O3, Al(OH)3. La présence d'une bentonite ou d'une autre terre active empêche toute fuite de chlorure d'aluminium gazeux à l'extérieur du mélange :le gaz se solidifie sur les plages actives de la terre et forme les micro-cristaux mentionnés ci-dessus. De même on obtient un réactif basique en mélangeant la bentonite avec une base, notamment NaOH, KOH puis en ajoutant Al, AlCl3, Al2 0 3 ou Al(OH)3.To obtain an acid reagent, it is advantageous to prepare it according to a manufacturing method which comprises mixing the bentonite with an acid, in particular hydrochloric acid, and adding to the resulting mixture of metallic aluminum, in particular under powder form. The hydrochloric acid reacts with metallic aluminum, to give AlCl 3 . Of course, metallic aluminum can be replaced by AlCl 3 , Al 2 O 3 , Al (OH) 3 . The presence of a bentonite or other active earth prevents any leakage of gaseous aluminum chloride outside the mixture: the gas solidifies on the active areas of the earth and forms the micro-crystals mentioned above . Likewise, a basic reagent is obtained by mixing the bentonite with a base, in particular NaOH, KOH then by adding Al, AlCl 3 , Al 2 0 3 or Al (OH) 3 .

Outre la terre adsorbante et l'aluminium A1C13, A1203 ou Al(OH)3, le réactif selon l'invention peut comporter des métaux ou des sels métalliques. Parmi les sels métalliques, on peut notamment mentionner le chlorure ferrique, le chlorure de calcium, le chlorure de magnésium, etc. Ces sels offrent l'avantage d'adapter le réactif aux types d'eaux résiduaires industrielles. Dans le même ordre d'idées, on peut traiter la terre active avec de l'acide sulfamique pour obtenir un réactif applicable aux eaux polluées par les nitrites.In addition to the adsorbent earth and the aluminum A1C1 3 , A1 2 0 3 or Al (OH) 3 , the reagent according to the invention can contain metals or metal salts. Among the metal salts, mention may especially be made of ferric chloride, calcium chloride, magnesium chloride, etc. These salts offer the advantage of adapting the reagent to the types of industrial waste water. Similarly, the active earth can be treated with sulfamic acid to obtain a reagent applicable to waters polluted by nitrites.

D'autres avantages et caractéristiques de l'invention seront mieux compris à la lecture qui va suivre d'exemples de préparation nullement limitatifs des réactifs et des exemples également non limitatifs d'utilisation desdits réactifs.Other advantages and characteristics of the invention will be better understood on reading which will follow from examples of preparation which are in no way limitative of the reagents and examples which are also nonlimiting of use of said reagents.

Exemple 1Example 1

Figure imgb0001
Figure imgb0001

Remplir le réacteur avec l'acide chlorhydrique, diluer jusqu'à 25 % environ avec de l'eau, ajouter la bentonite, agiter à l'homogénéité ; ajouter au sein de la masse réactionnelle l'aluminium, agiter jusqu'à la fin de la réaction ; ajouter le chlorure de fer, agiter à l'homogénéité ; compléter enfin avec de l'eau jusqu'à une quantité de 1 kg d'eau.Fill the reactor with hydrochloric acid, dilute to about 25% with water, add bentonite, stir to homogeneity; add aluminum to the reaction mass, stir until the reaction is complete; add iron chloride, stir to homogeneity; finally complete with water to a quantity of 1 kg of water.

Exemple 2Example 2

Figure imgb0002
Figure imgb0002

Remplir le réacteur avec l'acide chlorhydrique, diluer avec de l'eau jusqu'à 25 % environ, ajouter la bentonite, agiter à l'homogénéité ; ajouter à la masse réactionnelle l'aluminium, agiter jusqu'à la fin de la réaction ; ajouter successivement le chlorure de fer, le chlorure de calcium et le chlorure de magnésium, agiter à l'homogénéité ; laisser refroidir ; compléter enfin avec de l'eau jusqu'à une quantité de 1 kg d'eau.Fill the reactor with hydrochloric acid, dilute with water to about 25%, add the bentonite, stir to homogeneity; add aluminum to the reaction mass, stir until the reaction is complete; successively add iron chloride, calcium chloride and magnesium chloride, stir to homogeneity; let cool ; finally complete with water to a quantity of 1 kg of water.

Exemple 3Example 3

Figure imgb0003
Figure imgb0003

Remplir le réacteur avec l'acide chlorhydrique, diluer avec de l'eau jusqu'à 25 % environ, ajouter la bentonite et l'alumine, agiter à l'homogénéité ; ajouter à la masse réactionnelle l'aluminium, agiter jusqu'à la fin de la réaction ; ajouter le chlorure de fer, agiter à homogénéité ; laisser refroidir ; ajouter enfin l'eau restante.Fill the reactor with hydrochloric acid, dilute with water to about 25%, add bentonite and alumina, stir to homogeneity; add aluminum to the reaction mass, stir until the reaction is complete; add the iron chloride, stir to homogeneity; let cool ; finally add the remaining water.

Exemple 4Example 4

Figure imgb0004
Figure imgb0004
Figure imgb0005
Figure imgb0005

Remplir le réacteur avec l'acide chlorhydrique, diluer avec de l'eau comme indiqué ci-dessus, ajouter la bentonite, l'argile et l'alumine, agiter à l'homogénéité ; ajouter à la masse réactionnelle l'aluminium ; agiter jusqu'à la fin de la réaction ; ajouter successivement le chlorure de fer et le chlorure de calcium, agiter à homogénéité ; laisser refroidir ; ajouter enfin l'eau restante.Fill the reactor with hydrochloric acid, dilute with water as indicated above, add bentonite, clay and alumina, stir to homogeneity; add aluminum to the reaction mass; shake until the end of the reaction; successively add iron chloride and calcium chloride, stir to homogeneity; let cool ; finally add the remaining water.

Exemple 5Example 5

Figure imgb0006
Figure imgb0006

Remplir le réacteur avec l'hydroxyde de sodium, diluer avec de l'eau jusqu'à 25 % environ, ajouter la bentonite, agiter à homogénéité ; ajouter l'aluminium, agiter jusqu'à la fin de la réaction ; laisser refroidir ; ajouter enfin l'eau restante.Fill the reactor with sodium hydroxide, dilute with water to about 25%, add bentonite, stir to homogeneity; add aluminum, stir until the reaction is complete; let cool ; finally add the remaining water.

Exemple 5bisExample 5a

On procède comme indiqué à l'exemple 5 mais en remplaçant l'aluminium métallique par une quantité équivalente de A1203 ou de Al(OH)3 pour éviter le dégagement de H2 résultant de l'action de NaOH sur Al. On obtient un réactif aussi efficace que celui de l'exemple 5.The procedure is as indicated in Example 5, but replacing the metallic aluminum with an equivalent amount of A1 2 0 3 or Al (OH) 3 to avoid the release of H 2 resulting from the action of NaOH on Al. obtains a reagent as effective as that of Example 5.

Exemple 6Example 6

Figure imgb0007
Figure imgb0007

Remplir le réacteur avec l'hydroxyde de sodium diluée avec de l'eau jusqu'à environ 25 %, ajouter la bentonite et le talc, agiter à homogénéité ; ajouter au sein de la masse réactionnelle l'aluminium, agiter jusqu'à la fin de la réaction ; ajouter le chlorure de magnésiu- agiter à l'homogénéité ; ajouter enfin l'eau restante.Fill the reactor with sodium hydroxide diluted with water to about 25%, add bentonite and talc, stir to homogeneity; add aluminum to the reaction mass, stir until the end of the reaction; add the magnesium chloride to agitate to homogeneity; finally add the remaining water.

Exemple 6biaExample 6bia

On procède comme indiqué à l'exemple 6 mais en remplaçant l'aluminium métallique par une quantité équivalente de Al2O3 ou Al(OH)3. On obtient un réactif aussi efficace que celui de l'exemple 6.The procedure is as indicated in Example 6 but replacing the metallic aluminum with an equivalent amount of Al 2 O 3 or Al (OH) 3 . A reagent is obtained as effective as that of Example 6.

Exemple 7Example 7

Figure imgb0008
Figure imgb0008

Remplir le réacteur avec l'acide sulfamique, ajouter la bentonite, agiter à homogénéité ; ajouter le chlorure d'aluminium ; agiter à homogénéité.Fill the reactor with sulfamic acid, add the bentonite, stir to homogeneity; add aluminum chloride; shake well.

Exemple 8Example 8

Figure imgb0009
Figure imgb0009

Le réactif est préparé selon les modalités données à l'exemple 4 en ce qui concerne l'ordre d'introduction des ingrédients. Ce réactif est dilué avec de l'eau au moment de l'emploi, par exemple comme indiqué ci-dessus pour l'obtention de la suspension B.The reagent is prepared according to the methods given in Example 4 with regard to the order of introduction of the ingredients. This reagent is diluted with water at the time of use, for example as indicated above to obtain suspension B.

Les exemples 9 à 13 qui suivent ont trait à l'application selon l'invention des réactifs décrits ci-dessus :Examples 9 to 13 which follow relate to the application according to the invention of the reagents described above:

Exemple 9Example 9

Cet exemple concerne le passage d'une émulsion de coupe à base d'huiles minérales ayant un pH initial de 10.This example concerns the passage of a cutting emulsion based on mineral oils having an initial pH of 10.

Ajouter à l'émulsion à casser la quantité de réactif acide selon l'exemple 1 ou 3, nécessaire pour effectuer le cassage (1 partie en poids de réactif pour 4 parties en poids d'émulsion), agiter vivement ; le cassage se produit dans un laps de temps de 3 à 5 secondes ; réduire la vitesse d'agitation afin qu'un bloc puisse se former ;, ajouter si nécessaire 5 à 10 grammes par m3 de la masse réactionnelle d'un polyélectrolyte convenable pour assister la floculation ; séparer les phases par filtration et/ou décantation.Add to the emulsion to break the amount of acid reagent according to example 1 or 3, necessary to effect the breaking (1 part by weight of reagent for 4 parts by weight of emulsion), shake vigorously; breaking occurs within 3 to 5 seconds; reduce the stirring speed so that a block can form; add, if necessary, 5 to 10 grams per m 3 of the reaction mass of a suitable polyelectrolyte to assist flocculation; separate the phases by filtration and / or decantation.

Exemple 10Example 10

Cet exemple concerne le cassage d'une émulsion de rectification à base d'huiles synthétiques à dispersion ultra-fine dans la phase continue de pH initial 8,5.This example concerns the breaking of a rectification emulsion based on synthetic oils with ultra-fine dispersion in the continuous phase of initial pH 8.5.

Ajouter à l'émulsion à casser la quantité de réactif acide tamponné selon l'exemple 2 ou 4, nécessaire pour effectuer le cassage (1 partie en poids de réactif pour 4 parties en poids d'émulsion), le cassage se produit dans un laps de temps de 3 à 5 secondes ; réduire la vitesse d'agitation afin qu'un bloc puisse se former ; ajouter, si nécessaire, 5 à 10 grammes par m3 de la masse réactionnelle d'un polyélectrolyte convenable pour assister la floculation ; séparer les phases par filtration et/ou décantation.Add to the emulsion to break the amount of buffered acid reagent according to example 2 or 4, necessary to carry out the breaking (1 part by weight of reagent for 4 parts by weight of emulsion), the breaking occurs in a lapse from 3 to 5 seconds; reduce the stirring speed so that a block can form; add, if necessary, 5 to 10 grams per m 3 of the reaction mass of a suitable polyelectrolyte to assist the flocculation; separate the phases by filtration and / or decantation.

Exemple 11Example 11

Cet exemple concerne le cassage d'une émulsion de tréfilage à base d'huiles semi-synthétiques et de substances savonneuses de pH initial 9,5.This example concerns the breaking of a wire drawing emulsion based on semi-synthetic oils and soapy substances with an initial pH of 9.5.

Ajouter à l'émulsion la quantité de réactif tamponné selon l'exemple 2 ou 4 nécessaire pour un bon cassage et pour transformation des substances savonneuses solubles dans l'eau aux savons calcaires. Procéder ensuite comme indiqué à l'exemple 9 ou 10.Add to the emulsion the quantity of buffered reagent according to example 2 or 4 necessary for good breaking and for transformation of the soapy substances soluble in water to calcareous soaps. Then proceed as indicated in example 9 or 10.

Exemple 12Example 12

Cet exemple concerne le traitement d'une émulsion de rectification à base d'huiles synthétiques et de nitrites de pH 7,5 au moyen du réactif de l'exemple 7.This example relates to the treatment of a rectification emulsion based on synthetic oils and nitrites of pH 7.5 using the reagent of example 7.

Ajouter à l'émulsion à traiter la quantité de réactif réducteur de nitrite afin d'avoir un pH de 3,5 à 4 ; après 10 secondes, ajouter à la masse réactionnelle une base jusqu'à l'obtention d'un pH de 7 à 8 ; procéder ensuite comme indiqué aux exemples 9 ou 10.Add the quantity of nitrite reducing reagent to the emulsion to be treated in order to have a pH of 3.5 to 4; after 10 seconds, add a base to the reaction mass until a pH of 7 to 8 is obtained; then proceed as indicated in examples 9 or 10.

Exemple 13Example 13

Cet exemple concerne le traitement d'une eau résiduaire de décapage avec des sels métalliques de pH initial 3,5.This example concerns the treatment of pickling waste water with metal salts with an initial pH of 3.5.

Ajouter à l'eau à traiter la quantité de réactif alcalin selon l'exemple 5 nécessaire pour l'obtention d'un pH de 7,5 à 8 dans cette gamme de pH, il y a coprécipitation des hydroxydes d'aluminium et des autres métaux ; les terres actives exercent un effet sur les

Figure imgb0010
pour donner une floculation épaisse, dense et lourde qui donne rapidement au fond du décanteur. Les boues ainsi recueillies peuvent être séchées selon une méthode connue en soi, notamment au moyen d'un filtre-presse ou d'une centrifugeuse-décanteuse.Add to the water to be treated the amount of alkaline reagent according to Example 5 necessary to obtain a pH of 7.5 to 8 in this pH range, there is coprecipitation of aluminum hydroxides and others metals ; active lands have an effect on
Figure imgb0010
to give a thick, dense and heavy flocculation which quickly gives to the bottom of the decanter. The sludge thus collected can be dried according to a method known per se, in particular using a filter press or a centrifuge-decanter.

L'objet de l'invention, à savoir le cassage des émulsions et des suspensions, s'applique avantageusement dans le traitement des émulsions huileuses et des eaux résiduaires. En particulier, les réactifs selon l'invention se sont révélés très efficaces dans l'industrie des mégisseries, tanneries,abattoirs, de l'industrie alimentaire, de l'industrie cosmétolo- gique, dans le traitement des eaux résiduaires, des industries des peintures, papiers, textiles, teintureries et blanchisseries industrielles.The object of the invention, namely the breaking of emulsions and suspensions, advantageously applies in the treatment of oily emulsions and waste water. In particular, the reagents according to the invention have been found to be very effective in the tanning industry, tanneries, slaughterhouses, in the food industry, in the cosmetics industry, in the treatment of waste water, in the paint industries. , papers, textiles, industrial dyers and laundries.

Dans la figure unique donnée ci-après, on a donné le schéma d'une installation mobile permettant de traiter en continu 5 à 10 m/h d'eaux résiduaires industrielles. Une telle installation, qui peut être montée sur un camion ou une remorque pour traiter les eaux résiduaires des diverses industries à raison d'une à plusieurs heures par semaine ou par mois, comprend une pompe à amorçage automatique (1), une chambre (2) faisant office de réacteur primaire de cassage, une seconde chambre (3) faisant office de réacteur secondaire de cassage, un réacteur (4) de floculation, une pompe (5) pour le dosage du réactif selon l'invention, une pompe (6) pour le dosage du floculant, un récipient (7) servant de réservoir de floculant, un filtre (8) permettant la séparation automatique de l'eau épurée des boues, un réceptacle (9) pour recueillir les boues et un récipient (10) servant de réservoir pour le réactif de cassage selon l'invention.In the single figure given below, a diagram has been given of a mobile installation making it possible to continuously treat 5 to 10 m / h of industrial waste water. Such an installation, which can be mounted on a truck or a trailer to treat waste water from various industries at the rate of one to several hours per week or per month, includes an automatic priming pump (1), a chamber (2 ) acting as primary breaking reactor, a second chamber (3) acting as secondary breaking reactor, a flocculation reactor (4), a pump (5) for dosing the reagent according to the invention, a pump (6 ) for dosing the flocculant, a container (7) serving as a flocculant reservoir, a filter (8) allowing the automatic separation of the purified water from the sludge, a receptacle (9) for collecting the sludge and a container (10) serving as a reservoir for the breaking reagent according to the invention.

De façon avantageuse, le réacteur primaire de cassage (2) peut être un dispositif du type "cycl8ne".Advantageously, the primary breaking reactor (2) can be a device of the "cycl8ne" type.

Claims (9)

1. Procédé de cassage des émulsions et des suspensions, utile notamment dans l'épuration des eaux résiduaires industrielles, ledit procédé étant caractérisé en ce que l'on traite sous agitation les émulsions et les suspensions à traiter, au moyen d'un réactif liquide choisi parmi l'ensemble constitué par les solutions et dispersions aqueuses comprenant : a) une substance adsorbante, et b) de l'aluminium ou un dérivé d'aluminium notamment A1C13, Al2O3, Al(OH)3,
ledit réactif liquide étant obtenu à partir d'eau, des produits a) et b), et d'une substance choisie parmi les acides et les bases, de façon que des micro-cristaux de dérivés d'aluminium soient associés aux sites actifs de a).1. Method for breaking emulsions and suspensions, useful in particular in the purification of industrial waste water, said method being characterized in that the emulsions and suspensions to be treated are treated with stirring, using a liquid reagent chosen from the group consisting of aqueous solutions and dispersions comprising: a) an adsorbent substance, and b) aluminum or an aluminum derivative, in particular A1C1 3 , Al 2 O 3 , Al (OH) 3 ,
said liquid reagent being obtained from water, products a) and b), and a substance chosen from acids and bases, so that micro-crystals of aluminum derivatives are associated with the active sites of at). 2. Procédé selon la revendication 1, caractérisé en ce que la substance adsorbante est choisie parmi l'ensemble constitué par les bentonites (notamment la bentonite de sodium et la bentonite de calcium), les terres argileuses, les terres alcalino-terreuses et leurs mélanges.2. Method according to claim 1, characterized in that the adsorbent substance is chosen from the group consisting of bentonites (in particular sodium bentonite and calcium bentonite), clay soils, alkaline earths and their mixtures . 3. Procédé selon la revendication 1, caractérisé en ce que le réactif liquide est choisi parmi l'ensemble constitué par les solutions et dispersions aqueuses comprenant : a) une bentonite éventuellement en association avec une terre active, et b) au moins un produit choisi parmi l'ensemble constitué par Al, AlCl3, Al2O3 et Al(OH)3. 3. Method according to claim 1, characterized in that the liquid reagent is chosen from the group consisting of aqueous solutions and dispersions comprising: a) a bentonite optionally in association with an active earth, and b) at least one product chosen from the group consisting of Al, AlCl 3 , Al 2 O 3 and Al (OH) 3 . 4. Procédé selon la revendication 1, caractérisé en ce que le réactif liquide renferme au moins un acide et est, le cas échéant, tamponné.4. Method according to claim 1, characterized in that the liquid reagent contains at least one acid and is, if necessary, buffered. 5. Procédé selon la revendication 1, caractérisé en ce que le réactif liquide renferme au moins une base et est, le cas échéant, tamponné.5. Method according to claim 1, characterized in that the liquid reagent contains at least one base and is, if necessary, buffered. 6. Procédé selon la revendication 4, caractérisé en ce que l'acide est choisi parmi les acides chlorhydrique et sulfamique.6. Method according to claim 4, characterized in that the acid is chosen from hydrochloric and sulfamic acids. 7. Procédé selon la revendication 5, caractérisé en ce que la base est choisie parmi NaOH et KOH.7. Method according to claim 5, characterized in that the base is chosen from NaOH and KOH. 8. Procédé selon la revendication 3, caractérisé en ce que la bentonite est une bentonite de calcium ou de sodium.8. Method according to claim 3, characterized in that the bentonite is a calcium or sodium bentonite. 9. Procédé selon la revendication 1, caractérisé en ce que le réactif est utilisé à raison de 0,5 à 8 kg de réactif pour 1 m3 d'émulsion ou suspension à traiter.9. Method according to claim 1, characterized in that the reagent is used in an amount of 0.5 to 8 kg of reagent per 1 m 3 of emulsion or suspension to be treated.
EP78400055A 1977-07-21 1978-07-06 Method for breaking up emulsions and means for carrying out this method. Expired EP0000674B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7722426 1977-07-21
FR7722426A FR2397863A1 (en) 1977-07-21 1977-07-21 EMULSIONS BREAKING PROCESS AND MEANS FOR IMPLEMENTING THIS PROCESS

Publications (2)

Publication Number Publication Date
EP0000674A1 true EP0000674A1 (en) 1979-02-07
EP0000674B1 EP0000674B1 (en) 1982-03-24

Family

ID=9193622

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78400055A Expired EP0000674B1 (en) 1977-07-21 1978-07-06 Method for breaking up emulsions and means for carrying out this method.

Country Status (9)

Country Link
US (1) US4217210A (en)
EP (1) EP0000674B1 (en)
JP (1) JPS5460272A (en)
BR (1) BR7804616A (en)
CA (1) CA1114532A (en)
DE (1) DE2861687D1 (en)
ES (1) ES471917A1 (en)
FR (1) FR2397863A1 (en)
IT (1) IT1108770B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090027A4 (en) * 1981-09-30 1983-12-01 Radecca Inc Method of breaking emulsions.
GB2157278A (en) * 1984-04-11 1985-10-23 Hydro Int Ltd Water treatment
WO1992008533A1 (en) * 1990-11-15 1992-05-29 Multiserv International Limited Treatment of dispersions
WO1995024963A1 (en) * 1994-03-16 1995-09-21 Vodní Stavby Praha Method of treatment of water polluted predominantly by an oily component using bentonite
EP2168920A1 (en) * 2008-09-25 2010-03-31 Unilever N.V. Water purification composition and method

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS599203B2 (en) * 1979-12-10 1984-03-01 丸智工研株式会社 Oil/water separation method by coarse graining
DE10018603A1 (en) * 2000-04-14 2001-10-25 Fariwar Mohseni Mohammad Process for the pretreatment of organically contaminated water
US6805802B2 (en) * 2002-04-09 2004-10-19 General Chemical Corporation De-watering process
US7442293B2 (en) * 2005-01-14 2008-10-28 Jyonan Electric Industrial Corporation Limited Oil/water separation apparatus for oil-containing mixture
FR2883862A1 (en) * 2005-04-05 2006-10-06 Barba Willy Del Recovering oil and emulsified hydrocarbon in water comprises homogenizing mixture to high speed mode in mixer, mixing flocculating agent in bath to agglomerate agent with hydrocarbon and evacuating heterogeneous mixture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE625375A (en) * 1961-02-03
FR1539569A (en) * 1966-10-06 1968-09-13 Exxon Research Engineering Co Process for removing finely dispersed oil or petroleum droplets from water
FR2020564A1 (en) * 1968-10-12 1970-07-17 Krupp Gmbh Purification of polluted water by treatment with - bentonite
FR2236793A1 (en) * 1973-07-09 1975-02-07 Degussa
DE2507733A1 (en) * 1975-02-22 1976-09-09 Baerle & Co Kg Van Purifying waste waters contg oils and fats - esp as emulsions by adding mixt contg aluminium sulphate and kaolin
DE2527987A1 (en) * 1975-06-24 1977-01-13 Piepho Abwassertech Ralf F Compsns. for purifying waste water emulsions - contg. talcum, adipic acid, aluminium sulphate, Tixoton, flocculant, lime and bentonite

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE197806C (en) *
US1993761A (en) * 1932-09-12 1935-03-12 Activated Alum Corp Composition for water purification
US3342742A (en) * 1964-03-24 1967-09-19 Nalco Chemical Co Method of preparing aluminate coagulants
GB1420394A (en) * 1973-07-05 1976-01-07 Ciba Geigy Ag Composition for removal of organic materials from water

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE625375A (en) * 1961-02-03
FR1539569A (en) * 1966-10-06 1968-09-13 Exxon Research Engineering Co Process for removing finely dispersed oil or petroleum droplets from water
FR2020564A1 (en) * 1968-10-12 1970-07-17 Krupp Gmbh Purification of polluted water by treatment with - bentonite
FR2236793A1 (en) * 1973-07-09 1975-02-07 Degussa
DE2507733A1 (en) * 1975-02-22 1976-09-09 Baerle & Co Kg Van Purifying waste waters contg oils and fats - esp as emulsions by adding mixt contg aluminium sulphate and kaolin
DE2527987A1 (en) * 1975-06-24 1977-01-13 Piepho Abwassertech Ralf F Compsns. for purifying waste water emulsions - contg. talcum, adipic acid, aluminium sulphate, Tixoton, flocculant, lime and bentonite

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0090027A4 (en) * 1981-09-30 1983-12-01 Radecca Inc Method of breaking emulsions.
GB2157278A (en) * 1984-04-11 1985-10-23 Hydro Int Ltd Water treatment
WO1992008533A1 (en) * 1990-11-15 1992-05-29 Multiserv International Limited Treatment of dispersions
WO1995024963A1 (en) * 1994-03-16 1995-09-21 Vodní Stavby Praha Method of treatment of water polluted predominantly by an oily component using bentonite
EP2168920A1 (en) * 2008-09-25 2010-03-31 Unilever N.V. Water purification composition and method
WO2010034604A1 (en) * 2008-09-25 2010-04-01 Unilever Nv Water purification composition and method

Also Published As

Publication number Publication date
ES471917A1 (en) 1979-02-01
DE2861687D1 (en) 1982-04-29
CA1114532A (en) 1981-12-15
BR7804616A (en) 1979-04-10
IT1108770B (en) 1985-12-09
EP0000674B1 (en) 1982-03-24
FR2397863A1 (en) 1979-02-16
JPS5460272A (en) 1979-05-15
IT7868730A0 (en) 1978-07-20
US4217210A (en) 1980-08-12

Similar Documents

Publication Publication Date Title
CA2080959C (en) Water soluble polymers and/or copolymers having enhanced biodegradability and applications thereof
EP0000674B1 (en) Method for breaking up emulsions and means for carrying out this method.
EP0164286B1 (en) A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals
CA1162870A (en) Regeneration treatment of spent lubricating oils
CN107321316B (en) A kind of method of oil emulsion in removal ternary compound oil drive water exit
EP0416969B1 (en) New water-in-oil emulsions and their use for removing hydrogen sulfide
US4539117A (en) Method for improving the separating action in the ultrafiltration of aqueous solutions
GB1438427A (en) Process and an agent for treating waste water
FR2781477A1 (en) PROCESS FOR THE SYNTHESIS OF ALUMINS IN A BASIC MEDIUM
RU2092516C1 (en) Composition for well killing and well completion
EP0172073B1 (en) Process for obtaining a stable aqeous pumpable zeolithic suspension and the suspension thus obtained
FR3037580B1 (en) METHOD FOR STABILIZING METAL MERCURY
US3155617A (en) Dispersing calcium carbonate
RU2177984C1 (en) Method for regeneration of exhausted water-emulsion lubrication fluid
FR3004721A1 (en) IMPROVED METHOD FOR THE RECOVERY OF BITUMEN BITUMEN BITUMEN
EP1216207A1 (en) Composition useful for conditioning sludge derived from the treatment of an aqueous medium and uses thereof
FR2502509A1 (en) PROCESS FOR DEHYDRATING SUSPENSION OF MINERAL MATERIALS
EP0562914A1 (en) Washing method of solid particles using a solution containing sophorosides
FR2640613A1 (en) Product and process for treating a spent aqueous dispersion with the aid of a montmorillonite
CN116144390B (en) Phase transfer type sludge treating agent and its application
RU2752312C1 (en) Compound for cleaning the water surface from oil and petroleum product films
FR2766477A1 (en) PROCESS FOR TREATING ALKALINE WASTE WATER
FR2580620A1 (en) WASTEWATER TREATMENT AGENT AND PROCESS FOR PRODUCING THE SAME
FR2718656A1 (en) Reducing viscosity of mineral sludges
FR2817489A1 (en) Preparation of a new composition useful for wastewater treatment, comprises mixing an anionic surfactant solution with a water-in-oil emulsion or polyvalent inorganic cation solution and urea

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE GB NL SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE GB NL SE

REF Corresponds to:

Ref document number: 2861687

Country of ref document: DE

Date of ref document: 19820429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19820706

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19820707

KL Correction list

Free format text: 82/04 NEUDRUCK

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19830106

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19830201

26 Opposition filed

Opponent name: DEGUSSA AG, FRANKFURT - ZWEIGNIEDERLASSUNG WOLFGAN

Effective date: 19821217

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
26 Opposition filed

Opponent name: SUED-CHEMIE AG

Effective date: 19821223

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19830401

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19831013

GBPC Gb: european patent ceased through non-payment of renewal fee
EUG Se: european patent has lapsed

Ref document number: 78400055.6

Effective date: 19850611