EP1216207A1 - Composition useful for conditioning sludge derived from the treatment of an aqueous medium and uses thereof - Google Patents
Composition useful for conditioning sludge derived from the treatment of an aqueous medium and uses thereofInfo
- Publication number
- EP1216207A1 EP1216207A1 EP00964332A EP00964332A EP1216207A1 EP 1216207 A1 EP1216207 A1 EP 1216207A1 EP 00964332 A EP00964332 A EP 00964332A EP 00964332 A EP00964332 A EP 00964332A EP 1216207 A1 EP1216207 A1 EP 1216207A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- cationic
- emulsion
- mineral cation
- polyelectrolyte
- 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.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
- B01D21/262—Separation of sediment aided by centrifugal force or centripetal force by using a centrifuge
Definitions
- the present invention relates to a new composition which can be used in particular for the treatment of aqueous media such as waste or urban or industrial water and more particularly the conditioning of sludge prior to their dewatering operation.
- sludge The treatment of waste water, urban or industrial, in particular by biological means, in the purification stations, leads to the production of sludge.
- This sludge generally undergoes a mechanical dewatering operation (in particular filtration, centrifugation), before being transported to a landfill, agricultural spreading or incineration site.
- the sludge to be treated consists mainly of water in which biomass is dispersed at a rate of 12 to 40 g / l.
- the treatments therefore aim to concentrate the dry matter as much as possible and to remove the water.
- the object of the present invention is precisely to propose a new composition which can be used effectively in the conditioning of this type of sludge, making it possible in particular to increase their dryness, that is to say to increase the dry extracts obtained during the subsequent operation. dehydration.
- the drainability necessary for the evacuation of the water is generally obtained by adding to them in sequence a inorganic salt, a cationic polymer and then optionally a polymer anionic.
- the sludge treatment methods currently available are therefore different depending on the water / biomass separation technique used. On the other hand, they generally require the successive addition of several reagents. It is indeed difficult to formulate in a single composition and at significant concentrations, an organic salt of the aluminum polychloride type and a cationic polyelectrolyte.
- Aluminum is a complexing certain polyelectrolytes, their mixtures lead from a certain concentration in these compounds, to the formation of gels which are of course detrimental in terms of fluidity to the corresponding mixtures.
- the object of the present invention is precisely to propose a universal composition, that is to say which can be used indifferently for the treatment of sludge according to one or the other of the techniques mentioned above.
- the claimed composition has the advantage of combining, in the form of a mixture, an inorganic cation of charge greater than or equal to 2 and a cationic polyelectrolyte while not being subject to the gelling phenomenon discussed above.
- the main object of the present invention is a composition useful for conditioning sludge obtained by mixing at least one reverse emulsion containing at least one cationic polyelectrolyte with a reverse emulsion or an aqueous solution containing at least one inorganic filler cation. greater than or equal to two.
- composition useful for conditioning sludge characterized in that it is in the form of an emulsion comprising in aqueous phase (s) and separately at least one mineral cation of charge greater than or equal to 2 and a cationic polyelectrolyte.
- said composition is in the form of a reverse water-in-oil emulsion in which said mineral cation and said cationic polyelectrolyte are distributed in separate water droplets in the oily phase.
- This type of composition is generally obtained by mixing, with stirring, a reverse emulsion containing said mineral cation with a reverse emulsion containing said cationic polyelectrolyte.
- said composition is in the form of a double water / oil / water emulsion in which the mineral cation is present at the level of the aqueous continuous phase and the cationic polyelectrolyte is distributed at least in part in water droplets constituting the second aqueous phase dispersed in the oily phase.
- This second type of emulsion can be obtained by mixing an inverse emulsion of the cationic polyelectrolyte with an aqueous solution of the mineral cation.
- compositions are particularly advantageous insofar as they prove effective for all of the sludge treatment techniques, namely belt filtration and / or centrifugation or filtration on a press.
- composition obtained by mixing the two inverse emulsions, namely that of the mineral cation and that of the cationic polyelectrolyte. Indeed, these two compounds are then distributed at the level of the emulsion in separate water droplets and are therefore effectively isolated from one another.
- the mineral cation has a charge greater than or equal to 2. It is usually chosen from Mg 2+ , Al 3+ , Fe 3+ , La 3+ , Zr 4 * and their polymerized forms when they exist. Very preferably, the cation is Al 3+ or one of its polymerized forms.
- This mineral cation is present in the form of a water-soluble salt.
- soluble salts chlorides, nitrates, sulfates and acetates can be used.
- a soluble salt is used, free of the nitrogen element, which makes it possible to overcome any problems linked to its presence.
- a chloride is used.
- the cation is preferably an aluminum chloride or one of its polymerized forms and more preferably poly aluminum chloride.
- the amount of mineral cation used is preferably between 0.05 and 2 moles, in particular between 0.49 and 1.8 moles per kg of the composition.
- the pH of the solution or emulsion is adjusted so as to prevent precipitation of the mineral salt in the continuous aqueous phase. This adjustment falls within the competence of man and art.
- the cationic polyelectrolyte it is preferably of high molecular weight, that is to say of molecular weight greater than 1.10 6 .
- the polyelectrolytes preferably have a molecular weight from 1.10 e to approximately 20.10 e , more preferably from 1.10 e to approximately 10.10 6 .
- the cationic polyelectrolyte can be linear or branched and is preferably in a branched form. It was indeed noted that the ramifications had a beneficial effect on the kinetics of coagulation and flocculation.
- Polyacrylamides polyethylene oxides, polyvinylpyrrolidones, as well as polymers of natural origin such as starch and its derivatives or gum such as guar gum, are particularly suitable as cationic polyelectrolyte, insofar as they are cationic.
- the polyelectrolyte is a polyacrylamide.
- the polyacrylamide can be cationic up to 100% filler and is preferably cationic between about 0.1 and 15% filler.
- Cationic polyacrylamides include copolymers of polyacrylamide with cationic monomers or polyacrylamides modified according to the Mannich reaction.
- cationic polyacrylamide copolymers include acrylamide / halide copolymers, preferably diallyldialkylammonium chloride, diaminoalkylmethacrylate / acrylamide copolymers and dialkylaminoalkylmethacrylate / acrylamide copolymers, the C 6 to C 6 alkyl group.
- the cationic polyelectrolyte is a polyacrylamide copolymer, and preferably the polyacrylamide / diallyldimethylammonium chloride copolymer with a molecular weight of the order of 3.10 6 . It is more preferably combined with a polychloride of aluminum in the claimed composition.
- the amount of cationic polyelectrolyte present in the claimed composition is preferably at most 10% by weight, in particular between 0.3% and 8% by weight of said composition.
- the reverse emulsion of the cationic polyelectrolyte for example in the case of a high molecular weight polyacrylamide and the aqueous solution or the reverse emulsion of the mineral cation, for example in the case of polychloride of aluminum, are used. works in such a way that the molar ratio (mineral cation of charge greater than or equal to 2) / (cationic polyéectrolyte) is between 1.10 2 and 8.10 e in particular between 1.10 3 and 8.10 e .
- composition comprising polychloride of aluminum and a copolymer acrylamide / diallyldialkylammonium chloride of high molecular weight
- a weight ratio polychloride of aluminum / polyacrylamide ranging between 0,1 and 15 and more particularly between 0.1 and 10.
- compositions containing the mineral cation and the cationic polyelectrolyte distributed in separate water droplets in the oily continuous phase are particularly advantageous for the formulation of a composition concentrated in these two compounds. This is how this mode of formulation will be favored for compositions containing a polyacrylamide concentration of the order of 4 to 10% by weight relative to the composition.
- the claimed composition can be stabilized in the form of an emulsion using surfactant (s).
- surfactants are generally introduced at the level of the reverse emulsion (s) constituting said composition.
- the surfactant present in the oily phase of the emulsion is preferably a surfactant which naturally remains inert with respect to the mineral cation.
- the liposoluble surfactants which can be used in the emulsion according to the invention, can be chosen from liposoluble lecithins, esters of sorbitan and of fatty acids, of polyalkylenes dipolyhydroxystea spleens, fatty acids, monoglycerides, polygiycerol esters and lactic and tartaric acid esters.
- water-soluble lecithins may be cited, sucrose esters, fatty acid esters (including Tweens ®), polyoxyethylene alkylamides, triglyceride sulphates, alkyl sulphates (including dodecyl sodium sulfate SDS), alkyl ether sulfates, alkyl sulfonates, alkylamine salts, fatty amines, lipoamino acids, modified polyesters and polymeric silica-born surfactants.
- the amounts of surfactants are adjusted so as to stabilize the formulation (reverse or double emulsion) of the composition.
- the claimed composition can be prepared either by mixing the two reverse emulsions containing the mineral cation and the polyelectrolyte respectively or by adding the reverse emulsion containing the polyelectrolyte in an aqueous solution of the polyelectrolyte.
- the mixtures are generally carried out at room temperature and with sufficient mechanical stirring to lead to an emulsion stabilized over time.
- hydrophobic materials such as in particular rosin esters, lanolin, petrolatum, waxes, polybutadienes of low molecular weights natural animal, vegetable or mineral oils and their mixtures.
- compositions find a particularly advantageous application in the chemical conditioning of sludge, in particular of sludge from sewage treatment plants or waste or urban or industrial: its incorporation in sludge, which can be subjected before treatment anaerobic digestion, allows to structure them in such a way that the water contained in these sludges is better exuded during the dehydration operation which follows.
- the efficiency of the mechanical dehydration operation such as filtration or centrifugation can thus be improved, the volumes produced after this dehydration being reduced by obtaining a filtration cake of high dryness.
- the amount of composition used during the conditioning of a sludge is such that it generally corresponds between 0.05 to 3 times, preferably between 0.1 to 2 times, the amount of theoretical cationic charge necessary to neutralize the amount of anionic charge of the sludge to be treated; in other words, the quantity of composition claimed is such that it has, in absolute value, a cationicity generally equal to 0.05 to 3 times, preferably between 0.1 to 2 times, the anionicity of the mud treat.
- the claimed compositions are diluted before use.
- This dilution is more particularly necessary for the composition in the form of a reverse emulsion obtained by mixing the reverse emulsion of the mineral cation and that of the polyelectrolyte to transform it into a direct emulsion.
- This phase inversion can also be carried out by adding an adequate surfactant.
- this dilution operation is on the other hand optional.
- Figure 1 Representation for composition A as well as for its constituents added separately, of the evolution of the volume drained after 2 minutes depending on the conditioning dose.
- Figure 2 Representation for composition B as well as for its constituents added separately, of the evolution of the drained volume after 2 minutes depending on the conditioning dose.
- Figure 3 Representation of the t / v monitoring graph as a function of v for composition A and its constituents added separately.
- Figure 4 Representation of the t / v monitoring graph as a function of v for composition B and its constituents added separately.
- PAM cationic polyacrylamide
- PAC poly aluminum chloride
- PAM emulsion Reverse emulsion of acrylamide / diallyldimalkylammonium chloride copolymer with a molecular weight of approximately 3.10 6 in powder form.
- Alkamuls S80 ® sorbitan oleate from HLB 4.3 (Rhodia)
- Span 85 ® sorbitan trioleate from HLB 1, 7 (Sigma-AIdrich)
- Alkamuls T20 ® sorbitan monolaurate of 20OE HLB 16.6 (Rhodia)
- Alkamuls T85 ® sorbitan trioleate of 20OE HLB 11 (Rhodia)
- a reverse emulsion is produced in a water / vaseline mixture 1 g / 47.4 g using 1.6 g of a monolaurate / sorbitan oleate S20 mixture. / S80 88% / 12% (i.e. the required HLB of 8 for petroleum jelly).
- a fluid reverse emulsion comprising by weight: 16.1% in PAC, 3.8% in PAM, 42.8% in water, 35.7% in oil and at least 1.6% in surfactant.
- the two compounds are therefore effectively separated within the reverse emulsion, thus preserving the latter a satisfactory fluidity.
- This emulsion is prepared by mixing an aqueous solution of polychloride of aluminum (commercial solution Aquarhône 18 ® ) and an inverse emulsion of PAM.
- the reverse PAM emulsion is prepared according to the protocol described above in example 1. It is then added with stirring to the Aquarhône 18 ® . Two mixtures A and B are thus obtained at different PAC / PAM ratios.
- B mixture a 2% commercial PAM emulsion is mixed with an Aquarhône 18 ® solution , to obtain a 20% mixture in commercial Aquarhône 18 ® and 1.6% in PAM emulsion, i.e. weight ratio of active ingredients.
- PAC / PAM 8.75.
- mixtures A and B are evaluated in drainability tests and piston filter and compared with that obtained with sludges in which have been incorporated in a separate and sequenced manner, Aquarhône 18 ® and the PAM emulsion, in identical quantities to those present in the respective mixtures.
- This test is carried out on 200 g of biological sludge from an urban wastewater treatment plant having a dry matter of 6.35% including 37.2% of mineral matter.
- the latter is added to 200 g of mud with mechanical stirring with a pale lacerator at 700 rpm in a beaker, the mixture is then transferred to a filter and the quantity of d is evaluated. water that percolated over time.
- the whole is transferred twice from one beaker to another and then stirred for 15 seconds at 700 rpm. It is then deposited on a filter and the quantity of percolated water is measured.
- B is diluted to 1/3, which means that the Aquarhône 18 ® content goes from 20.0% to 6.67% and that in PAM emulsion from 1.6% to 0.53%.
- mixtures A and B prove to be much less viscous than the 0.56% PAM solution.
- the conditioning dose is determined by measuring the capillary suction time (CST) at different doses.
- Two doses for packaging are used: the dose at the minimum CST time and the dose with a slight overdose.
- the doses used are: - 3g of A at 1/6 for 50g of mud, and - 3.5g of A at 1/6 for 50g of mud.
- the doses at A are determined by measurements of CST at different doses. They are listed in Table II below.
- the doses used are 2 g of 1/3 B for 50 g of mud and 3 g of 1/3 B for 50 g of mud.
- FIGS. 3 and 4 The results obtained with emulsion A and its control mixture as well as emulsion B and its control mixture are respectively presented in FIGS. 3 and 4.
- the graphs for monitoring t / v as a function of v are represented. for the two mixtures and their constituents added separately. It appears that it is in terms of dryness or in terms of filtration behavior that the fact of adding the products constituting the mixtures separately reduces the effectiveness of the packaging. The specific resistances are indeed higher and the dryness lower.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention concerns a composition useful for conditioning sludge obtained by mixing an invert emulsion containing at least a cationic polyelectrolyte with an invert emulsion or an aqueous solution containing at least a mineral cation with a charge not less than two. The invention also concerns the corresponding applications.
Description
COMPOSITION UTILE POUR LE CONDITIONNEMENT DES BOUES ISSUES DU TRAITEMENT DECOMPOSITION USEFUL FOR THE CONDITIONING OF SLUDGE RESULTING FROM THE TREATMENT OF
MILIEUX AQUEUX ET SES APPLICATIONS.AQUEOUS MEDIA AND ITS APPLICATIONS.
La présente invention concerne une nouvelle composition utilisable notamment pour le traitement des milieux aqueux comme les eaux résiduaires ou urbaines ou industrielles et plus particulièrement le conditionnement de boues préalablement à leur opération de déshydratation.The present invention relates to a new composition which can be used in particular for the treatment of aqueous media such as waste or urban or industrial water and more particularly the conditioning of sludge prior to their dewatering operation.
Le traitement des eaux résiduaires, urbaines ou industrielles, en particulier par voie biologique, dans -les stations d'épuration, conduit à la production de boues. Ces boues subissent généralement une opération de déshydratation mécanique (en particulier filtration, centrifugation), avant d'être transportées vers un site de décharge, d'épandage agricole ou d'incinération.The treatment of waste water, urban or industrial, in particular by biological means, in the purification stations, leads to the production of sludge. This sludge generally undergoes a mechanical dewatering operation (in particular filtration, centrifugation), before being transported to a landfill, agricultural spreading or incineration site.
Les boues à traiter sont constituées majoritairement d'eau dans laquelle est dispersée de la biomasse à raison de 12 à 40 g/l. Les traitements visent donc à concentrer au maximum la matière sèche et à éliminer l'eau. La présente invention a précisément pour objet de proposer une nouvelle composition utilisable efficacement dans le conditionnement de ce type de boues permettant notamment d'augmenter leur siccité, c'est-à-dire d'accroître les extraits secs obtenus lors de l'opération subséquente de déshydratation.The sludge to be treated consists mainly of water in which biomass is dispersed at a rate of 12 to 40 g / l. The treatments therefore aim to concentrate the dry matter as much as possible and to remove the water. The object of the present invention is precisely to propose a new composition which can be used effectively in the conditioning of this type of sludge, making it possible in particular to increase their dryness, that is to say to increase the dry extracts obtained during the subsequent operation. dehydration.
Lorsque les boues sont destinées à un filtre presse, on ajoute classiquement aux boues à traiter un sel inorganique associé le cas échéant à un électrolyte, couramment la chaux.When the sludge is intended for a filter press, conventionally added to the sludge to be treated is an inorganic salt associated, where appropriate, with an electrolyte, commonly lime.
En revanche, lorsque les boues sont destinées à être traitées sur filtre à bande ou par centrifugeuse, la drainabilité nécessaire à l'évacuation de l'eau est obtenue généralement en leur ajoutant de manière séquencée un sel inorganique, un polymère cationique puis éventuellement un polymère anionique.On the other hand, when the sludge is intended to be treated on a band filter or by centrifuge, the drainability necessary for the evacuation of the water is generally obtained by adding to them in sequence a inorganic salt, a cationic polymer and then optionally a polymer anionic.
Les méthodes de traitement des boues actuellement disponibles sont donc distinctes selon la technique de séparation eau/biomasse retenue. D'autre part, elles nécessitent généralement l'ajout successif de plusieurs réactifs. Il s'avère en effet difficile de formuler dans une unique composition et à des concentrations significatives, un sel organique de type polychlorure d'aluminium et un polyelectrolyte cationique. L'aluminium étant un complexant de certains polyélectrolytes, leurs mélanges mènent à partir d'une certaine concentration en
ces composés, à la formation de gels qui sont bien entendu préjudiciables en terme de fluidité aux mélanges correspondants.The sludge treatment methods currently available are therefore different depending on the water / biomass separation technique used. On the other hand, they generally require the successive addition of several reagents. It is indeed difficult to formulate in a single composition and at significant concentrations, an organic salt of the aluminum polychloride type and a cationic polyelectrolyte. Aluminum is a complexing certain polyelectrolytes, their mixtures lead from a certain concentration in these compounds, to the formation of gels which are of course detrimental in terms of fluidity to the corresponding mixtures.
La présente invention a précisément pour objet de proposer une composition universelle c'est à dire pouvant être utilisée de manière indifférente pour le traitement des boues selon l'une ou l'autre des techniques évoquées ci- dessus.The object of the present invention is precisely to propose a universal composition, that is to say which can be used indifferently for the treatment of sludge according to one or the other of the techniques mentioned above.
Par ailleurs, la composition revendiquée présente l'avantage de réunir sous forme d'un mélange, -un cation minéral de charge supérieure ou égale à 2 et un polyelectrolyte cationique tout en n'étant pas sujette au phénomène de gélification discuté précédemment.Furthermore, the claimed composition has the advantage of combining, in the form of a mixture, an inorganic cation of charge greater than or equal to 2 and a cationic polyelectrolyte while not being subject to the gelling phenomenon discussed above.
Plus précisément, la présente invention a pour objet principal une composition utile pour le conditionnement des boues obtenue par mélange d'au moins une emulsion inverse contenant au moins un polyelectrolyte cationique avec une emulsion inverse ou une solution aqueuse contenant au moins un cation minéral de charge supérieure ou égale à deux.More specifically, the main object of the present invention is a composition useful for conditioning sludge obtained by mixing at least one reverse emulsion containing at least one cationic polyelectrolyte with a reverse emulsion or an aqueous solution containing at least one inorganic filler cation. greater than or equal to two.
Elle s'étend ainsi à une composition utile pour le conditionnement des boues, caractérisée en ce qu'elle se présente sous la forme d'une emulsion comprenant en phase(s) aqueuse(s) et de manière séparée au moins un cation minéral de charge supérieure ou égale à 2 et un polyelectrolyte cationique. Selon un premier mode de réalisation, ladite composition se présente sous la forme d'une emulsion inverse eau dans huile dans laquelle ledit cation minéral et ledit polyelectrolyte cationique sont répartis dans des gouttelettes d'eau distinctes dans la phase huileuse.It thus extends to a composition useful for conditioning sludge, characterized in that it is in the form of an emulsion comprising in aqueous phase (s) and separately at least one mineral cation of charge greater than or equal to 2 and a cationic polyelectrolyte. According to a first embodiment, said composition is in the form of a reverse water-in-oil emulsion in which said mineral cation and said cationic polyelectrolyte are distributed in separate water droplets in the oily phase.
Ce type de composition est généralement obtenu en mélangeant sous agitation une emulsion inverse contenant ledit cation minéral avec une emulsion inverse contenant ledit polyelectrolyte cationique.This type of composition is generally obtained by mixing, with stirring, a reverse emulsion containing said mineral cation with a reverse emulsion containing said cationic polyelectrolyte.
Selon un second mode de réalisation, ladite composition se présente sous la forme d'une emulsion double eau/huile/eau dans laquelle le cation minéral est présent au niveau de la phase continue aqueuse et le polyelectrolyte cationique est réparti au moins en partie dans des gouttelettes d'eau constituant la seconde phase aqueuse dispersée dans la phase huileuse.
Ce second type d'émulsion peut être obtenu par mélange d'une emulsion inverse du polyelectrolyte cationique avec une solution aqueuse du cation minéral.According to a second embodiment, said composition is in the form of a double water / oil / water emulsion in which the mineral cation is present at the level of the aqueous continuous phase and the cationic polyelectrolyte is distributed at least in part in water droplets constituting the second aqueous phase dispersed in the oily phase. This second type of emulsion can be obtained by mixing an inverse emulsion of the cationic polyelectrolyte with an aqueous solution of the mineral cation.
Les compositions revendiquées sont particulièrement avantageuses dans la mesure où elles s'avèrent efficaces pour l'ensemble des techniques de traitement des boues à savoir filtration à bande et/ou centrifugation ou filtration sur presse.The claimed compositions are particularly advantageous insofar as they prove effective for all of the sludge treatment techniques, namely belt filtration and / or centrifugation or filtration on a press.
Par ailleurs, en permettant l'isolement du cation minéral du polyelectrolyte cationique, elles rendent possible la formulation de ces réactifs en concentrations plus importantes. Grâce à cette formulation en emulsion, le risque de gélification se trouve significativement réduit.Furthermore, by allowing the mineral cation to be isolated from the cationic polyelectrolyte, they make it possible to formulate these reagents in higher concentrations. Thanks to this emulsion formulation, the risk of gelation is significantly reduced.
Convient tout particulièrement à la formulation d'une composition concentrée, la composition obtenue par mélange des deux émuisions inverses à savoir celle du cation minéral et celle du polyelectrolyte cationique. En effet, ces deux composés se trouvent alors répartis au niveau de l'émulsion dans des gouttelettes d'eau distinctes et sont donc efficacement isolés l'un de l'autre.Particularly suitable for the formulation of a concentrated composition, the composition obtained by mixing the two inverse emulsions, namely that of the mineral cation and that of the cationic polyelectrolyte. Indeed, these two compounds are then distributed at the level of the emulsion in separate water droplets and are therefore effectively isolated from one another.
Le cation minéral présente une charge supérieure ou égale à 2. Il est habituellement choisi parmi Mg2+, Al3+, Fe3+, La3+, Zr4* et leurs formes polymérisées lorsqu'elles existent. De manière très préférée, le cation est Al3+ ou une de ses formes polymérisées.The mineral cation has a charge greater than or equal to 2. It is usually chosen from Mg 2+ , Al 3+ , Fe 3+ , La 3+ , Zr 4 * and their polymerized forms when they exist. Very preferably, the cation is Al 3+ or one of its polymerized forms.
Ce cation minéral est présent sous forme d'un sel hydrosoluble. A titre de sels solubles, on peut utiliser les chlorures, les nitrates, les sulfates et les acétates.This mineral cation is present in the form of a water-soluble salt. As soluble salts, chlorides, nitrates, sulfates and acetates can be used.
En général, on utilise un sel soluble, exempt de l'élément azote, ce qui permet de s'affranchir des problèmes éventuels liés à sa présence. De manière très préférée, on emploie un chlorure. Le cation est de préférence un chlorure d'aluminium ou une de ses formes polymérisées et plus préférentiellement du polychlorure d'aluminium.In general, a soluble salt is used, free of the nitrogen element, which makes it possible to overcome any problems linked to its presence. Very preferably, a chloride is used. The cation is preferably an aluminum chloride or one of its polymerized forms and more preferably poly aluminum chloride.
La quantité de cation minéral mise en œuvre est de préférence comprise entre 0,05 et 2 moles, en particulier entre 0,49 et 1 ,8 moles par kg de la composition.
Le pH de la solution ou emulsion est ajusté de manière à prévenir la précipitation du sel minéral dans la phase aqueuse continue. Cet ajustement relève des compétences de l'homme et de l'art.The amount of mineral cation used is preferably between 0.05 and 2 moles, in particular between 0.49 and 1.8 moles per kg of the composition. The pH of the solution or emulsion is adjusted so as to prevent precipitation of the mineral salt in the continuous aqueous phase. This adjustment falls within the competence of man and art.
En ce qui concerne le polyelectrolyte cationique, il est de préférence de haut poids moléculaire, c'est à dire de poids moléculaire supérieur à 1.106.As regards the cationic polyelectrolyte, it is preferably of high molecular weight, that is to say of molecular weight greater than 1.10 6 .
Les polyélectrolytes ont de préférence un poids moléculaire de 1.10e à environ 20.10e, plus préférentiellement de 1.10e à environ 10.106.The polyelectrolytes preferably have a molecular weight from 1.10 e to approximately 20.10 e , more preferably from 1.10 e to approximately 10.10 6 .
Le polyelectrolyte cationique peut être linéaire ou ramifié et est de préférence sous une forme ramifiée. Il a en effet été noté que les ramifications avaient un effet bénéfique sur les cinétiques de coagulation et de floculation.The cationic polyelectrolyte can be linear or branched and is preferably in a branched form. It was indeed noted that the ramifications had a beneficial effect on the kinetics of coagulation and flocculation.
Conviennent tout particulièrement comme polyelectrolyte cationique les polyacrylamides, oxydes de polyethylènes, polyvinylpyrrolidones, ainsi que les polymères d'origine naturelle tel l'amidon et ses dérivés ou gomme telle la gomme guar, dans la mesure où ils sont cationiques. De manière préférée, le polyelectrolyte est un polyacrylamide.Polyacrylamides, polyethylene oxides, polyvinylpyrrolidones, as well as polymers of natural origin such as starch and its derivatives or gum such as guar gum, are particularly suitable as cationic polyelectrolyte, insofar as they are cationic. Preferably, the polyelectrolyte is a polyacrylamide.
Le polyacrylamide peut être cationique jusqu'à 100 % en charge et est de préférence cationique entre environ 0,1 et 15 % en charge.The polyacrylamide can be cationic up to 100% filler and is preferably cationic between about 0.1 and 15% filler.
Les polyacrylamides cationiques comprennent les copolymères de polyacrylamide avec des monomères cationiques ou les polyacrylamides modifiés selon la réaction de Mannich.Cationic polyacrylamides include copolymers of polyacrylamide with cationic monomers or polyacrylamides modified according to the Mannich reaction.
Les exemples de copolymères polyacrylamides cationiques incluent les copolymères acrylamide/ halogénure de préférence chlorure de diallyldialkylammonium, les copolymères diaminoalkylméthacrylate/acrylamide et les copolymères dialkylaminoalkylméthacrylates/acrylamides, le groupement alkyle étant en C, à C6.Examples of cationic polyacrylamide copolymers include acrylamide / halide copolymers, preferably diallyldialkylammonium chloride, diaminoalkylmethacrylate / acrylamide copolymers and dialkylaminoalkylmethacrylate / acrylamide copolymers, the C 6 to C 6 alkyl group.
De manière avantageuse, le polyelectrolyte cationique est un copolymère polyacrylamide, et de préférence, le copolymère polyacrylamide/chlorure de diallyldiméthylammonium de poids moléculaire de l'ordre de 3.106. Il est plus préférentiellement associé à un polychlorure d'aluminium dans la composition revendiquée.Advantageously, the cationic polyelectrolyte is a polyacrylamide copolymer, and preferably the polyacrylamide / diallyldimethylammonium chloride copolymer with a molecular weight of the order of 3.10 6 . It is more preferably combined with a polychloride of aluminum in the claimed composition.
La quantité en polyelectrolyte cationique présente dans la composition revendiquée est de préférence d'au plus 10% en poids, en particulier comprise entre 0,3% et 8% en poids de ladite composition.
Généralement, l'émulsion inverse du polyelectrolyte cationique, par exemple dans le cas d'un polyacrylamide de haut poids moléculaire et la solution aqueuse ou l'émulsion inverse du cation minéral, par exemple dans le cas du polychlorure d'aluminium, sont mises en œuvre de telle manière que le rapport molaire (cation minéral de charge supérieure ou égale à 2)/(polyéiectrolyte cationique) soit compris entre 1.102 et 8.10e en particulier entre 1.103 et 8.10e. Dans le cas particulier d'une composition comprenant du polychlorure d'aluminium et un copolymère acrylamide/chlorure de diallyldialkylammonium de haut poids moléculaire, on utilise de préférence un rapport pondéral polychlorure d'aluminium/polyacrylamide compris entre 0,1 et 15 et plus particulièrement entre 0,1 et 10.The amount of cationic polyelectrolyte present in the claimed composition is preferably at most 10% by weight, in particular between 0.3% and 8% by weight of said composition. Generally, the reverse emulsion of the cationic polyelectrolyte, for example in the case of a high molecular weight polyacrylamide and the aqueous solution or the reverse emulsion of the mineral cation, for example in the case of polychloride of aluminum, are used. works in such a way that the molar ratio (mineral cation of charge greater than or equal to 2) / (cationic polyéectrolyte) is between 1.10 2 and 8.10 e in particular between 1.10 3 and 8.10 e . In the particular case of a composition comprising polychloride of aluminum and a copolymer acrylamide / diallyldialkylammonium chloride of high molecular weight, one preferably uses a weight ratio polychloride of aluminum / polyacrylamide ranging between 0,1 and 15 and more particularly between 0.1 and 10.
Comme évoqué précédemment les compositions revendiquées contenant le cation minéral et le polyelectrolyte cationique répartis dans des gouttelettes d'eau distinctes dans la phase continue huileuse sont particulièrement intéressantes pour la formulation d'une composition concentrée en ces deux composés. C'est ainsi que l'on privilégiera ce mode de formulation pour des compositions contenant une concentration en polyacrylamide de l'ordre de 4 à 10% en poids par rapport à la composition.As mentioned above, the claimed compositions containing the mineral cation and the cationic polyelectrolyte distributed in separate water droplets in the oily continuous phase are particularly advantageous for the formulation of a composition concentrated in these two compounds. This is how this mode of formulation will be favored for compositions containing a polyacrylamide concentration of the order of 4 to 10% by weight relative to the composition.
Si nécessaire la composition revendiquée peut être stabilisée sous la forme d'une emulsion à l'aide de tensio-actif(s). Les tensio-actifs sont généralement introduits au niveau de la ou des émulsion(s) inverse(s) constituant ladite composition.If necessary, the claimed composition can be stabilized in the form of an emulsion using surfactant (s). The surfactants are generally introduced at the level of the reverse emulsion (s) constituting said composition.
En ce qui concerne le tensio-actif présent dans la phase huileuse de l'émulsion, il s'agit de préférence d'un agent de surface qui demeure bien entendu inerte vis à vis du cation minéral.As regards the surfactant present in the oily phase of the emulsion, it is preferably a surfactant which naturally remains inert with respect to the mineral cation.
Les agents de surface liposolubles, susceptibles d'être mis en œuvre dans l'émulsion selon l'invention, peuvent être choisis parmi les lécithines liposolubles, les esters de sorbitanne et d'acides gras, de polyalkylènes dipolyhydroxystéa rates, les acides gras, les monoglycérides, les esters de polygiycérol et les esters d'acide lactique et tartrique.The liposoluble surfactants, which can be used in the emulsion according to the invention, can be chosen from liposoluble lecithins, esters of sorbitan and of fatty acids, of polyalkylenes dipolyhydroxystea spleens, fatty acids, monoglycerides, polygiycerol esters and lactic and tartaric acid esters.
A titre illustratif des agents de surface hydrosolubles, on peut notamment citer les lécithines hydrosolubles, esters de sucrose, esters d'acide gras (dont les Tweens®), alkylamides polyoxyéthylénés, triglycérides sulfates, alkyles sulfates
(dont le dodécyle sulfate de sodium SDS), alkyles éther sulfates, alkyles sulfonates, sels d'alkylamines, aminés grasses, lipoamino-acides, polyesters modifiés et tensioactifs polymériques silice-nés.Illustratively water-soluble surfactants, water-soluble lecithins may be cited, sucrose esters, fatty acid esters (including Tweens ®), polyoxyethylene alkylamides, triglyceride sulphates, alkyl sulphates (including dodecyl sodium sulfate SDS), alkyl ether sulfates, alkyl sulfonates, alkylamine salts, fatty amines, lipoamino acids, modified polyesters and polymeric silica-born surfactants.
Les quantités en tensio-actifs sont ajustées de manière à stabiliser la formulation (emulsion inverse ou double) de la composition.The amounts of surfactants are adjusted so as to stabilize the formulation (reverse or double emulsion) of the composition.
La composition revendiquée peut être préparée soit par mélange des deux émulsions inverses contenant respectivement le cation minéral et le polyelectrolyte soit par ajout de l'émulsion inverse contenant le polyelectrolyte dans une solution aqueuse du polyelectrolyte. Les mélanges sont effectués généralement à température ambiante et sous une agitation mécanique suffisante pour conduire à une emulsion stabilisée dans le temps.The claimed composition can be prepared either by mixing the two reverse emulsions containing the mineral cation and the polyelectrolyte respectively or by adding the reverse emulsion containing the polyelectrolyte in an aqueous solution of the polyelectrolyte. The mixtures are generally carried out at room temperature and with sufficient mechanical stirring to lead to an emulsion stabilized over time.
A titre illustratif des composés susceptibles d'être utilisés à titre de phase huileuse selon l'invention, on peut tout particulièrement citer des matériaux hydrophobes comme notamment les esters de colophane, la lanoline, la vaseline, les cires, les polybutadiènes de faibles masses moléculaires les huiles naturelles animales, végétales ou minérales et leurs mélanges.By way of illustration of the compounds capable of being used as oily phase according to the invention, mention may be made most particularly of hydrophobic materials such as in particular rosin esters, lanolin, petrolatum, waxes, polybutadienes of low molecular weights natural animal, vegetable or mineral oils and their mixtures.
Les compositions revendiquées trouvent une application particulièrement intéressante dans le conditionnement chimique des boues, notamment de boues issues des stations d'épuration des eaux usées ou résiduaires ou urbaines ou industrielles : son incorporation dans les boues, que l'on peut soumettre préalablement à un traitement de digestion anaérobie, permet de les structurer de telle manière que l'eau contenue dans ces boues est mieux exsudée iors de l'opération de déshydratation qui suit. L'efficacité de l'opération de déshydratation mécanique comme la filtration ou la centrifugation peut ainsi être améliorée, les volumes produits après cette déshydratation étant réduits par l'obtention d'un gâteau de filtration de siccité élevée.The claimed compositions find a particularly advantageous application in the chemical conditioning of sludge, in particular of sludge from sewage treatment plants or waste or urban or industrial: its incorporation in sludge, which can be subjected before treatment anaerobic digestion, allows to structure them in such a way that the water contained in these sludges is better exuded during the dehydration operation which follows. The efficiency of the mechanical dehydration operation such as filtration or centrifugation can thus be improved, the volumes produced after this dehydration being reduced by obtaining a filtration cake of high dryness.
La quantité en composition utilisée lors du conditionnement d'une boue est telle qu'elle correspond en général entre 0,05 à 3 fois, de préférence entre 0,1 à 2 fois, la quantité de charge cationique théorique nécessaire pour neutraliser la quantité de charge anionique de la boue à traiter ; en d'autres termes, la quantité en composition revendiquée est telle qu'elle présente en valeur absolue une cationicité égale en général à 0,05 à 3 fois, de préférence comprise entre 0,1 à 2 fois, l'anionicité de la boue à traiter.
Généralement, les compositions revendiquées sont diluées avant utilisation. Cette dilution est plus particulièrement nécessaire pour la composition se présentant sous la forme d'une emulsion inverse obtenue par mélange de l'émulsion inverse du cation minéral et celle du polyelectrolyte pour la transformer en emulsion directe. Cette inversion de phase peut également être réalisée par ajout d'un tensio-actif adéquat. Dans le cas où les compositions se présentent sous la forme d'émulsions doubles, cette opération de dilution est en revanche facultative.The amount of composition used during the conditioning of a sludge is such that it generally corresponds between 0.05 to 3 times, preferably between 0.1 to 2 times, the amount of theoretical cationic charge necessary to neutralize the amount of anionic charge of the sludge to be treated; in other words, the quantity of composition claimed is such that it has, in absolute value, a cationicity generally equal to 0.05 to 3 times, preferably between 0.1 to 2 times, the anionicity of the mud treat. Generally, the claimed compositions are diluted before use. This dilution is more particularly necessary for the composition in the form of a reverse emulsion obtained by mixing the reverse emulsion of the mineral cation and that of the polyelectrolyte to transform it into a direct emulsion. This phase inversion can also be carried out by adding an adequate surfactant. In the case where the compositions are in the form of double emulsions, this dilution operation is on the other hand optional.
Les exemples et figures qui suivent sont présentés à titre illustratif et non limitatif de l'invention.The examples and figures which follow are presented by way of nonlimiting illustration of the invention.
FIGURESFIGURES
Figure 1 : Représentation pour la composition A ainsi que pour ses constituants ajoutés séparément, de l'évolution du volume drainé au bout de 2 minutes en fonction de la dose de conditionnement.Figure 1: Representation for composition A as well as for its constituents added separately, of the evolution of the volume drained after 2 minutes depending on the conditioning dose.
Figure 2 : Représentation pour la composition B ainsi que pour ses constituants ajoutés séparément, de l'évolution du volume drainé au bout de 2 minutes en fonction de la dose de conditionnement.Figure 2: Representation for composition B as well as for its constituents added separately, of the evolution of the drained volume after 2 minutes depending on the conditioning dose.
Figure 3 : Représentation du graphe de suivi de t/v en fonction de v pour la composition A et ses constituants ajoutés séparément.Figure 3: Representation of the t / v monitoring graph as a function of v for composition A and its constituents added separately.
Figure 4 : Représentation du graphe de suivi de t/v en fonction de v pour la composition B et ses constituants ajoutés séparément.Figure 4: Representation of the t / v monitoring graph as a function of v for composition B and its constituents added separately.
Abréviations : PAM = polyacrylamide cationique PAC = polychlorure d'aluminiumAbbreviations: PAM = cationic polyacrylamide PAC = poly aluminum chloride
MatérielEquipment
Emulsion inverse de copolymère acrylamide/chlorure de diallyldimalkylammonium de poids moléculaire d'environ 3.10e, à 50% en poids dites ci-après « emulsion de PAM ».
Copolymère acrylamide/chlorure de diallyidimethylammonium de poids moléculaire d'environ 3.106 sous forme de poudre.Reverse emulsion of acrylamide / diallyldimalkylammonium chloride copolymer with a molecular weight of approximately 3.10 e , at 50% by weight, referred to below as "PAM emulsion". Acrylamide / diallyidimethylammonium chloride copolymer with a molecular weight of approximately 3.10 6 in powder form.
Aquarhône 18® (solution de polychlorure d'aluminium commercialisé par Rhodia contenant 4,56 moles d'aluminium par kg - E.S = 38,2%) Vaseline (Sté Prolabo)Aquarhône 18 ® (poly aluminum chloride solution marketed by Rhodia containing 4.56 moles of aluminum per kg - ES = 38.2%) Vaseline (Prolabo company)
Alkamuls S80® : oléate de sorbitan de HLB 4,3 (Rhodia)Alkamuls S80 ® : sorbitan oleate from HLB 4.3 (Rhodia)
Alkamuls S20® : monolaurate de sorbitan de HLB 8,6 (Rhodia)Alkamuls S20 ® : HLB 8.6 sorbitan monolaurate (Rhodia)
Span 85® : trioléate de sorbitan de HLB 1 ,7 (Sigma-AIdrich)Span 85 ® : sorbitan trioleate from HLB 1, 7 (Sigma-AIdrich)
Alkamuls T20® : monolaurate de sorbitan de 20OE HLB 16,6 (Rhodia) Alkamuls T85® : trioléate de sorbitan 20OE HLB 11 (Rhodia)Alkamuls T20 ® : sorbitan monolaurate of 20OE HLB 16.6 (Rhodia) Alkamuls T85 ® : sorbitan trioleate of 20OE HLB 11 (Rhodia)
Esters phosphate éthoxylés PA35 (Rhodia)PA35 ethoxylated phosphate esters (Rhodia)
EXEMPLE 1 :EXAMPLE 1:
Obtention d'une emulsion inverse de PAM. Chlorure de diallyidimethylammonium de poids moléculaire d'environObtaining a reverse PAM emulsion. Diallyidimethylammonium chloride of molecular weight approximately
3.106.3.10 6 .
A partir de 50 g de copolymère polyacrylamide cationique sous forme d'une poudre, on réalise une emulsion inverse dans un mélange eau/vaseline 1 g/47,4 g en utilisant 1 ,6 g d'un mélange monolaurate / oléate de sorbitan S20/S80 88%/12% (soit la HLB requise de 8 pour la vaseline).From 50 g of cationic polyacrylamide copolymer in the form of a powder, a reverse emulsion is produced in a water / vaseline mixture 1 g / 47.4 g using 1.6 g of a monolaurate / sorbitan oleate S20 mixture. / S80 88% / 12% (i.e. the required HLB of 8 for petroleum jelly).
EXEMPLE 2 :EXAMPLE 2:
Obtention d'une emulsion inverse de PAC. a) on dilue une solution, Aquarhône 18®, avec de l'eau (20g d'eau pour 50g d'Aqua 18). b) on additionne de 5% en tensioactif S80® l'huile de vaseline (soit 2g de S80 pour 38g de vaseline).Obtaining a reverse PAC emulsion. a) dilute a solution, Aquarhône 18 ® , with water (20g of water for 50g of Aqua 18). b) adding 5% surfactant S80 ® vaseline oil (either 2g to 38g Vaseline S80).
Après un passage de b) pendant 30s à l'utraturax 8000tr/min, on verse progressivement a) dans b) pendant environ 5 minutes toujours à la même vitesse. On ajoute une minute à la vitesse 9500tr/min.After passing b) for 30s at the 8000 rpm utraturax, gradually pour a) into b) for approximately 5 minutes, always at the same speed. One minute is added at the speed 9500 rpm.
Après une semaine de stockage à 45°C, ces émulsions, dont la taille est inférieure à 5μm, sédimentent légèrement (apparition d'un petit surnageant
huile). Le tout se remet toutefois assez aisément en solution par simple agitation manuelle.After a week of storage at 45 ° C., these emulsions, the size of which is less than 5 μm, sediment slightly (appearance of a small supernatant oil). However, everything is fairly easily restored by simple manual stirring.
EXEMPLE 3 : Obtention d'une emulsion inverse PAC-PAM.EXAMPLE 3 Obtaining a PAC-PAM reverse emulsion.
On mélange à l'uitraturax, 92,35g de l'émulsion de PAC préparée selon l'exemple 2 et 7,6g de l'émulsion de PAM préparée selon l'exemple 1.92.35 g of the PAC emulsion prepared according to Example 2 and 7.6 g of the PAM emulsion prepared according to Example 1 are mixed with the uratratax.
On obtient alors une emulsion inverse fluide comprenant en poids : 16,1 % en PAC, 3,8% en PAM, 42,8% en eau, 35,7% en huile et au moins 1 ,6% en tensioactif.A fluid reverse emulsion is then obtained comprising by weight: 16.1% in PAC, 3.8% in PAM, 42.8% in water, 35.7% in oil and at least 1.6% in surfactant.
Les différents essais réalisés montrent que le mélange à l'uitraturax des deux émulsions inverses obtenues selon les exemples précédents, permet d'obtenir une emulsion inverse PAC-PAM dont le comportement en stabilité est similaire aux émulsions inverses de PAC seul. L'inversion d'une emulsion PAC-PAM conservée 13 jours puis réhomogénéisée est obtenue après l'ajout d'un tensioactif tel que le monolaurate de sorbitan 20OE Alkamuls (T20®) dans l'eau. Dès que cette emulsion se retrouve directe, la viscosité du système augmente fortement et témoigne de la formation du gel polyacrylamide Al3+. Cette observation va dans le sens d'une diffusion limitée de PAM ou de PAC entre les gouttes d'eau pendant la durée de stockage.The various tests carried out show that the mixing with the uretraturax of the two reverse emulsions obtained according to the preceding examples, makes it possible to obtain a PAC-PAM reverse emulsion whose behavior in stability is similar to the PAC emulsions alone. The inversion of a PAC-PAM emulsion kept for 13 days and then rehomogenized is obtained after the addition of a surfactant such as sorbitan monolaurate 20OE Alkamuls (T20 ® ) in water. As soon as this emulsion is found direct, the viscosity of the system increases sharply and testifies to the formation of the polyacrylamide gel Al 3+ . This observation points towards a limited diffusion of PAM or PAC between the drops of water during the storage period.
Les deux composés sont donc efficacement séparés au sein de l'émulsion inverse, préservant ainsi à celle-ci une fluidité satisfaisante.The two compounds are therefore effectively separated within the reverse emulsion, thus preserving the latter a satisfactory fluidity.
EXEMPLE 4EXAMPLE 4
Préparation d'une emulsion double à base de PAC et PAM.Preparation of a double emulsion based on PAC and PAM.
Cette emulsion est préparée en mélangeant une solution aqueuse de polychlorure d'aluminium (solution commerciale Aquarhône 18®) et une emulsion inverse de PAM. L'émulsion inverse de PAM est préparée selon le protocole décrit précédemment en exemple 1. Elle est ensuite ajoutée sous agitation à
l' Aquarhône 18®. Deux mélanges A et B sont ainsi obtenus à des rapports PAC/PAM différents.This emulsion is prepared by mixing an aqueous solution of polychloride of aluminum (commercial solution Aquarhône 18 ® ) and an inverse emulsion of PAM. The reverse PAM emulsion is prepared according to the protocol described above in example 1. It is then added with stirring to the Aquarhône 18 ® . Two mixtures A and B are thus obtained at different PAC / PAM ratios.
- pour un mélange dit A : on mélange une emulsion de PAM à 4% commerciale et une solution Aquarhône 18®, de manière à obtenir un mélange à 18,2 % en Aquarhône 18® commercial et 3,27 % en emulsion PAM soit un rapport pondéral en matières actives PAC/PAM de 3,9.- For a mixture called A: a 4% commercial PAM emulsion and an Aquarhône 18 ® solution are mixed, so as to obtain a mixture of 18.2% in commercial Aquarhône 18 ® and 3.27% in PAM emulsion, i.e. weight ratio of active ingredients PAC / MAP of 3.9.
- pour un mélange dit B : on mélange une emulsion de PAM à 2% commerciale avec d'une solution d'Aquarhône 18®, pour obtenir un mélange à 20 % en Aquarhône 18® commercial et 1 ,6 % en emulsion PAM soit un rapport pondéral en matières actives. PAC/PAM de 8,75.- For a so-called B mixture: a 2% commercial PAM emulsion is mixed with an Aquarhône 18 ® solution , to obtain a 20% mixture in commercial Aquarhône 18 ® and 1.6% in PAM emulsion, i.e. weight ratio of active ingredients. PAC / PAM of 8.75.
L'efficacité des mélanges A et B est évaluée en tests de drainabilité et filtre piston et comparée à celle obtenue avec des boues dans lesquelles ont été incorporées de manière séparée et séquencée, de l' Aquarhône 18® et l'émulsion de PAM, en quantités identiques à celles présentes dans les mélanges respectifs.The effectiveness of mixtures A and B is evaluated in drainability tests and piston filter and compared with that obtained with sludges in which have been incorporated in a separate and sequenced manner, Aquarhône 18 ® and the PAM emulsion, in identical quantities to those present in the respective mixtures.
EXEMPLE 5.EXAMPLE 5.
Test de drainabilité.Drainability test.
Il s'agit d'un test qui permet d'identifier la composition convenant tout particulièrement à la déshydratation des boues sur filtre à bande et/ou centrifugeuse.This is a test which makes it possible to identify the composition which is particularly suitable for dewatering the sludge on a band filter and / or centrifuge.
Ce test est réalisé sur 200 g de boue biologique de station d'épuration urbaine possédant une matière sèche de 6,35 % dont 37,2 % de matières minérales.This test is carried out on 200 g of biological sludge from an urban wastewater treatment plant having a dry matter of 6.35% including 37.2% of mineral matter.
a) Avec le mélange A et son témoin (ajout séparé et séquence des deux constituants).a) With mixture A and its control (separate addition and sequence of the two constituents).
Lors des essais, A est dilué au 1/6, ce qui fait que la teneur en Aquarhône 18® passe de 18,2 à 3,03 % et en emulsion de PAM de 3,27 à 0,545%. En conséquence, les quantités respectives des constituants témoins, c'est-à-dire ajoutés séparément, sont appréciées comme suit :
à 10g de A au 1 /6 (soit 1 ,67g de A pur) correspond 0,303g d'Aquarhône 18® commercial et 9,7g d'émulsion PAM.During the tests, A is diluted to 1/6, so that the Aquarhône 18 ® content goes from 18.2 to 3.03% and in PAM emulsion from 3.27 to 0.545%. Consequently, the respective amounts of the control constituents, that is to say added separately, are assessed as follows: to 10g of A at 1/6 (i.e. 1.67g of pure A) corresponds to 0.303g of commercial Aquarhône 18 ® and 9.7g of PAM emulsion.
Dans le cas du test de drainabilité avec l'émulsion A, cette dernière est ajoutée à 200 g de boue sous agitation mécanique avec une pâle lacératrice à 700 rpm dans un bêcher, le mélange est ensuite transvasé dans un filtre et on évalue la quantité d'eau qui a percolé en fonction du temps.In the case of the drainability test with emulsion A, the latter is added to 200 g of mud with mechanical stirring with a pale lacerator at 700 rpm in a beaker, the mixture is then transferred to a filter and the quantity of d is evaluated. water that percolated over time.
Dans le cas du test de drainabilité témoin, on procède à l'ajout séquence des deux produits selon le protocole suivant :In the case of the control drainability test, the sequence of the two products is added according to the following protocol:
200 g de boue sont agités à 700 rpm. On y ajoute I' Aquarhône E 18® et on laisse l' agitation se poursuivre 1 0 secondes. La boue pré-conditionnée est ensuite versée dans un bêcher où l'on a pesé au préalable l'émulsion de PAM.200 g of mud are stirred at 700 rpm. The Aquarhône E 18 ® is added thereto and the stirring is allowed to continue for 10 seconds. The pre-conditioned mud is then poured into a beaker where the PAM emulsion has been weighed beforehand.
L'ensemble est transvasé deux fois d' un bêcher à un autre puis porté sous agitation 15 secondes à 700 rpm. Il est ensuite déposé sur un filtre et la quantité d'eau percolée est mesurée.The whole is transferred twice from one beaker to another and then stirred for 15 seconds at 700 rpm. It is then deposited on a filter and the quantity of percolated water is measured.
Les résultats obtenus avec A et le témoin sont présentés sous forme de graphes en figure 1 .The results obtained with A and the control are presented in the form of graphs in FIG. 1.
b Mélange B et mélange témoin.b Mixture B and control mixture.
Lors des essais, B est dilué au 1/3, ce qui fait que la teneur en Aquarhône 18® passe de 20,0% à 6,67% et celle en emulsion de PAM de 1 ,6% à 0,53%.During the tests, B is diluted to 1/3, which means that the Aquarhône 18 ® content goes from 20.0% to 6.67% and that in PAM emulsion from 1.6% to 0.53%.
C'est ainsi que 10g de B au 1 /6 (soit 3,33g de B pur) correspond à 0,667g d' Aquarhône 18® commercial et 9,33g d'émulsion de PAM à 0,57%. L'addition de l'émulsion B et celle de ses deux constituants, de manière séparée dans l'essai témoin, est réalisée selon les protocoles décrits pour l' essai précédent.Thus 10g of B at 1/6 (or 3.33g of pure B) corresponds to 0.667g of Aquarhône 18 ® commercial and 9.33g of PAM emulsion at 0.57%. The addition of emulsion B and that of its two constituents, separately in the control test, is carried out according to the protocols described for the previous test.
Les résultats obtenus avec B et son témoin sont présentés sous forme de graphe en figure 2.The results obtained with B and its control are presented in the form of a graph in FIG. 2.
L'ensemble des graphes en figures 1 et 2 donne pour les mélanges A et B ainsi que pour leurs constituants ajoutés séparément, le volume drainé au bout de 2 minutes en fonction de la dose de conditionnement. On note que les
conditionnements réalisés par ajout de l'Aquarhône 18® puis de l'émulsion de PAM donnent des volumes drainés plus faibles que dans le cas des conditionnements réalisés à partir des mélanges A et B. En conséquence, l'utilisation des mélanges permet une économie en produit de 20 à 40 % par rapport aux constituants ajoutés séparément, tout en préservant une efficacité optimale.The set of graphs in Figures 1 and 2 gives for the mixtures A and B as well as for their constituents added separately, the volume drained after 2 minutes depending on the conditioning dose. We note that the packaging made by adding Aquarhône 18 ® and then PAM emulsion gives lower drained volumes than in the case of packaging made from mixtures A and B. Consequently, the use of mixtures allows savings in product of 20 to 40% compared to the constituents added separately, while preserving an optimal efficiency.
Par ailleurs, les mélanges A et B s'avèrent nettement moins visqueux que la solution de PAM à 0,56%.Furthermore, mixtures A and B prove to be much less viscous than the 0.56% PAM solution.
EXEMPLE 6EXAMPLE 6
Evaluation sur filtre piston.Evaluation on piston filter.
Il s'agit d'un test permettant d'identifier les compositions convenant plus particulièrement à la déshydratation des boues sur filtre presse. Ce test est réalisé avec les conditions de filtration suivantes :This is a test to identify the compositions more particularly suitable for dewatering sludge on a filter press. This test is carried out with the following filtration conditions:
On filtre 100g de boue conditionnée sur un filtre piston à 2.105 Pascal pendant 10 minutes afin de tracer le graphe temps/volume (T/V) en fonction du volume qui permet de mettre en évidence le comportement à la filtration. Il est ensuite opéré une filtration à 1.10e Pascal pendant 5 minutes afin d'estimer l'influence des différents conditionnement sur la siccité limite obtenue.100 g of conditioned sludge are filtered on a piston filter at 2.10 5 Pascal for 10 minutes in order to draw the time / volume graph (T / V) as a function of the volume which makes it possible to highlight the behavior on filtration. Filtration is then carried out at 1.10 e Pascal for 5 minutes in order to estimate the influence of the different conditioning on the limit dryness obtained.
La dose de conditionnement est déterminée par mesure du temps de succion capillaire (CST) à différentes doses.The conditioning dose is determined by measuring the capillary suction time (CST) at different doses.
Deux doses pour les conditionnements sont retenues : la dose au temps de CST minimum et la dose avec un léger surdosage.Two doses for packaging are used: the dose at the minimum CST time and the dose with a slight overdose.
a) Mélange A et son témoin Résultats avec A dilué au 1/6.a) Mixture A and its results control with A diluted 1/6.
On détermine les doses de conditionnement par mesure du CST. En tableau I ci-après sont présentées les données obtenues.
TABLEAUThe conditioning doses are determined by measuring the CST. In Table I below are presented the data obtained. BOARD
Les doses retenues sont : - 3g de A au 1/6 pour 50g de boue, et - 3,5g de A au 1/6 pour 50g de boue.The doses used are: - 3g of A at 1/6 for 50g of mud, and - 3.5g of A at 1/6 for 50g of mud.
Le test de filtration est ensuite réalisé sur filtre piston selon le protocole décrit précédemment. Les résultats obtenus sont présentés sous forme de graphe en figure 3.The filtration test is then carried out on a piston filter according to the protocol described above. The results obtained are presented in the form of a graph in FIG. 3.
Sur cette figure 3, sont également présentés sous forme de graphe, les résultats obtenus pour une boue traitée successivement avec les deux constituants de A ajoutés séparément.In this figure 3, are also presented in the form of a graph, the results obtained for a sludge treated successively with the two constituents of A added separately.
Les doses en ces constituants sont calculées de la même façon que pour le test de drainabilité présenté en exemple V.The doses of these constituents are calculated in the same way as for the drainability test presented in example V.
b) Mélange B et son témoinb) Mixture B and its control
De la même façon que pour le mélange B, les doses en A sont déterminées par mesures de CST à différentes doses. Elles figurent dans le tableau II ci-après.In the same way as for mixture B, the doses at A are determined by measurements of CST at different doses. They are listed in Table II below.
TABLEAU 11TABLE 11
Les doses retenues sont 2 g de B au 1/3 pour 50g de boue et 3 g de B au 1/3 pour 50 g de boue. The doses used are 2 g of 1/3 B for 50 g of mud and 3 g of 1/3 B for 50 g of mud.
On procède ensuite à des essais de filtration sur le filtre piston selon le protocole décrit précédemment.Filtration tests are then carried out on the piston filter according to the protocol described above.
Les résultats obtenus avec l'émulsion A et son mélange témoin de même que l'émulsion B et son mélange témoin sont respectivement présentés en figures 3 et 4. Sur ces figures, sont représentés les graphes de suivi de t/v en fonction de v pour les deux mélanges et leurs constituants ajoutés séparément. Il apparaît que ce soit en terme de siccité ou en terme de comportement à la filtration que le fait d'ajouter les produits constituant les mélanges séparément diminue l'efficacité du conditionnement. Les résistances spécifiques sont en effet plus élevées et les siccités plus faibles.
The results obtained with emulsion A and its control mixture as well as emulsion B and its control mixture are respectively presented in FIGS. 3 and 4. In these figures, the graphs for monitoring t / v as a function of v are represented. for the two mixtures and their constituents added separately. It appears that it is in terms of dryness or in terms of filtration behavior that the fact of adding the products constituting the mixtures separately reduces the effectiveness of the packaging. The specific resistances are indeed higher and the dryness lower.
Claims
1. Composition utile pour le conditionnement des boues obtenue par mélange d'au moins une emulsion inverse contenant au moins un polyelectrolyte cationique avec une emulsion inverse ou une solution aqueuse contenant au moins un cation minéral de charge supérieure ou égale à deux.1. Composition useful for the conditioning of sludge obtained by mixing at least one reverse emulsion containing at least one cationic polyelectrolyte with a reverse emulsion or an aqueous solution containing at least one mineral cation of charge greater than or equal to two.
2. Composition utile pour le conditionnement des boues, caractérisée en ce qu'elle se présente sous la forme d'une emulsion comprenant en phase(s) aqueuse(s) et de manière séparée au moins un cation minéral de charge supérieure ou égale à 2 et un polyelectrolyte cationique.2. Composition useful for conditioning sludge, characterized in that it is in the form of an emulsion comprising in aqueous phase (s) and separately at least one mineral cation with a charge greater than or equal to 2 and a cationic polyelectrolyte.
3. Composition selon la revendication 1 ou 2 caractérisée en ce qu'elle se présente sous la forme d'une emulsion inverse eau dans huile dans laquelle ledit cation minéral et ledit polyelectrolyte cationique sont répartis dans des gouttelettes d'eau distinctes, dans la phase huileuse.3. Composition according to claim 1 or 2 characterized in that it is in the form of a reverse water-in-oil emulsion in which said mineral cation and said cationic polyelectrolyte are distributed in separate water droplets, in the phase oily.
4. Composition selon la revendication 1 ou 2, caractérisée en ce qu'elle se présente sous la forme d'une emulsion double eau/huile/eau dans laquelle le cation minéral est présent au niveau de la phase continue aqueuse et le polyelectrolyte cationique est réparti au moins en partie dans des gouttelettes d'eau constituant la seconde phase aqueuse dispersée dans la phase huileuse.4. Composition according to claim 1 or 2, characterized in that it is in the form of a double water / oil / water emulsion in which the mineral cation is present in the aqueous continuous phase and the cationic polyelectrolyte is distributed at least in part in water droplets constituting the second aqueous phase dispersed in the oily phase.
5. Composition selon l'une des revendications précédentes, caractérisée en ce que le cation minéral est choisi parmi Mg2\ La3+, Fe3+, Al3+, Zr4+ et leurs formes polymérisées lorsqu'elles existent.5. Composition according to one of the preceding claims, characterized in that the mineral cation is chosen from Mg 2 \ La 3+ , Fe 3+ , Al 3+ , Zr 4+ and their polymerized forms when they exist.
6. Composition selon la revendication 5, caractérisée en ce que ledit cation minéral est Al3+ ou une de ses formes polymérisées.6. Composition according to claim 5, characterized in that said mineral cation is Al 3+ or one of its polymerized forms.
7. Composition selon l'une des revendications précédentes caractérisée en ce que le cation minéral se présente sous la forme d'un sel hydrosoluble de préférence choisi parmi les chlorures, les nitrates, les sulfates et les acétates. 7. Composition according to one of the preceding claims, characterized in that the mineral cation is in the form of a water-soluble salt preferably chosen from chlorides, nitrates, sulfates and acetates.
8. Composition selon l'une des revendications précédentes, caractérisée en ce que le cation minéral est un chlorure d'aluminium ou une de ses formes polymérisées. 8. Composition according to one of the preceding claims, characterized in that the mineral cation is an aluminum chloride or one of its polymerized forms.
9. Composition selon l'une des revendications précédentes, caractérisée en ce que le cation minéral est mis en œuvre à raison de 0,05 à 2 moles, en particulier entre 0,49 et 1,8 moles par kg de ladite composition.9. Composition according to one of the preceding claims, characterized in that the mineral cation is used in an amount of 0.05 to 2 moles, in particular between 0.49 and 1.8 moles per kg of said composition.
10. Composition selon l'une des revendications précédentes, caractérisée en ce que le polyelectrolyte cationique est de poids moléculaire supérieur e 1.10e.10. Composition according to one of the preceding claims, characterized in that the cationic polyelectrolyte is of molecular weight greater than 1.10 e .
11. Composition selon l'une des revendications précédentes, caractérisée en ce que -le polyelectrolyte cationique est choisi parmi les polyacrylamides, oxydes de polyethylènes, polyvinylpyrrolidones, ainsi que les polymères d'origine naturelle cationiques.11. Composition according to one of the preceding claims, characterized in that -the cationic polyelectrolyte is chosen from polyacrylamides, polyethylene oxides, polyvinylpyrrolidones, as well as polymers of cationic natural origin.
12. Composition selon l'une des revendications précédentes, caractérisée en ce que ledit polyelectrolyte cationique est un polyacrylamide possédant entre 0,1 % et 15% en charge cationique.12. Composition according to one of the preceding claims, characterized in that said cationic polyelectrolyte is a polyacrylamide having between 0.1% and 15% in cationic charge.
13. Composition selon l'une des revendications précédentes, caractérisée en ce que le polyelectrolyte cationique est choisi parmi les copolymères de polyacrylamide avec des monomères cationiques ou les polyacrylamides modifiés selon la réaction de Mannich.13. Composition according to one of the preceding claims, characterized in that the cationic polyelectrolyte is chosen from copolymers of polyacrylamide with cationic monomers or polyacrylamides modified according to the Mannich reaction.
14. Composition selon l'une des revendications précédentes, caractérisée en ce que ledit polyelectrolyte est un copolymère polyacrylamide cationique choisi parmi les copolymères acrylamides/ halogénure de préférence chlorure de diallyldialkylammonium, les copolymères diaminoalkylméthacrylate/acrylamides et les copolymères diaikylaminoalkylméthacrylates/acrylamides.14. Composition according to one of the preceding claims, characterized in that the said polyelectrolyte is a cationic polyacrylamide copolymer chosen from acrylamide / halide copolymers preferably diallyldialkylammonium chloride, diaminoalkylmethacrylate / acrylamide copolymers and diaikylaminoalkylmethacrylate / acrylamide copolymers.
15. Composition selon l'une des revendications précédentes, caractérisée en ce que le polyelectrolyte cationique est mis en œuvre à raison d'au plus 10% et de préférence entre 0,3% et 8% en poids de ladite composition.15. Composition according to one of the preceding claims, characterized in that the cationic polyelectrolyte is used in an amount of at most 10% and preferably between 0.3% and 8% by weight of said composition.
16. Composition selon l'une des revendications précédentes, caractérisée en ce que le cation minéral est un polychlorure d'aluminium et le polyelectrolyte cationique est un copolymère acrylamide/chlorure de diallyldiméthyllammonium de PM de l'ordre de 3.10e.16. Composition according to one of the preceding claims, characterized in that the mineral cation is an aluminum polychloride and the cationic polyelectrolyte is an acrylamide / diallyldimethyllammonium chloride copolymer of PM of the order of 3.10 e .
17. Composition selon l'une des revendications précédentes, caractérisée en ce que le cation minéral et le polyelectrolyte sont mis en œuvre de telle manière que le rapport molaire cation minéral/polyélectrolyte cationique soit compris entre 1.102 et 8.10e, en particulier entre 1.103 et 8.10e.17. Composition according to one of the preceding claims, characterized in that the mineral cation and the polyelectrolyte are used in such a way that the mineral cation / cationic polyelectrolyte molar ratio is between 1.10 2 and 8.10 e , in particular between 1.10 3 and 8.10 e .
18. Composition selon la revendication 17, caractérisée en ce que lorsque le cation minéral est le polychlorure d'aluminium et le polyelectrolyte, un copolymère acrylamide/chlorure de diallyldiméthyllammonium, le rapport pondéral cation minéral/polyélectrolyte cationique est compris entre 0,1 et 15 et plus particulièrement entre 0,1 et 10.18. Composition according to Claim 17, characterized in that when the inorganic cation is poly aluminum chloride and the polyelectrolyte, an acrylamide / diallyldimethyllammonium chloride copolymer, the mineral cation / cationic polyelectrolyte weight ratio is between 0.1 and 15 and more particularly between 0.1 and 10.
19. Application d'une composition selon l'une des revendications 1 à 18 pour le traitement des milieux aqueux, en particulier des eaux résiduaires, urbaines ou industrielles.19. Application of a composition according to one of claims 1 to 18 for the treatment of aqueous media, in particular waste water, urban or industrial.
20. Application d'une composition selon l'une des revendications 1 à 18 pour le traitement des boues biologiques issues de l'épuration d'eaux usées ou résiduaires, en vue de leur déshydratation. 20. Application of a composition according to one of claims 1 to 18 for the treatment of biological sludges from the purification of waste or waste water, with a view to their dehydration.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9911747 | 1999-09-20 | ||
FR9911747A FR2798652B1 (en) | 1999-09-20 | 1999-09-20 | COMPOSITION USEFUL FOR THE CONDITIONING OF SLUDGES FROM THE TREATMENT OF AQUEOUS MEDIA AND ITS APPLICATIONS |
PCT/FR2000/002610 WO2001021532A1 (en) | 1999-09-20 | 2000-09-20 | Composition useful for conditioning sludge derived from the treatment of an aqueous medium and uses thereof |
Publications (1)
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EP1216207A1 true EP1216207A1 (en) | 2002-06-26 |
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EP00964332A Withdrawn EP1216207A1 (en) | 1999-09-20 | 2000-09-20 | Composition useful for conditioning sludge derived from the treatment of an aqueous medium and uses thereof |
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US (1) | US6855268B1 (en) |
EP (1) | EP1216207A1 (en) |
AU (1) | AU7529200A (en) |
FR (1) | FR2798652B1 (en) |
WO (1) | WO2001021532A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20030209499A1 (en) * | 2000-09-29 | 2003-11-13 | Haase Richard A. | Clarification of water and wastewater |
FR2824551B1 (en) * | 2001-03-22 | 2004-04-09 | Rhodia Chimie Sa | PROCESS FOR THE CONDITIONING OR DEHYDRATION OF SLUDGE FROM THE PAPER OR AGRI-FOOD INDUSTRY |
US7378023B2 (en) * | 2006-09-13 | 2008-05-27 | Nalco Company | Method of improving membrane bioreactor performance |
EP2611742A1 (en) * | 2010-09-02 | 2013-07-10 | Akzo Nobel Chemicals International B.V. | Composition, use thereof and process for reducing bulking sludge and/or foaming and preparation of the composition |
CN103011548A (en) * | 2012-12-27 | 2013-04-03 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Conditioner for combinedly conditioning sludge and method for dehydrating sludge through utilizing conditioner |
CN106186606B (en) * | 2016-08-03 | 2017-04-12 | 联盛纸业(龙海)有限公司 | Modification and reuse production method for floatation filter-pressed sludge of white manila board |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US4606913A (en) * | 1978-09-25 | 1986-08-19 | Lever Brothers Company | High internal phase emulsions |
US4617362A (en) * | 1984-12-31 | 1986-10-14 | Allied Corporation | Inverse emulsion polymers with improved incorporation of diallyldimethylammonium chloride |
US5200086A (en) * | 1991-08-20 | 1993-04-06 | Nalco Chemical Company | Emulsion destabilization and treatment |
US5763530A (en) * | 1993-11-24 | 1998-06-09 | Cytec Technology Corp. | Stable emulsion blends and methods for their use |
JPH0859770A (en) * | 1994-08-15 | 1996-03-05 | Dainippon Ink & Chem Inc | Polyurethane-polyurea crosslinked fine particle dispersion body and its production |
US5830388A (en) * | 1995-08-11 | 1998-11-03 | American Envirocare, Inc. | Coagulating and flocculating agent and method for making it |
US5906750A (en) * | 1996-09-26 | 1999-05-25 | Haase; Richard Alan | Method for dewatering of sludge |
US6120690A (en) * | 1997-09-16 | 2000-09-19 | Haase; Richard Alan | Clarification of water and wastewater |
US6168686B1 (en) * | 1998-08-19 | 2001-01-02 | Betzdearborn, Inc. | Papermaking aid |
-
1999
- 1999-09-20 FR FR9911747A patent/FR2798652B1/en not_active Expired - Fee Related
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2000
- 2000-09-20 US US10/088,234 patent/US6855268B1/en not_active Expired - Fee Related
- 2000-09-20 AU AU75292/00A patent/AU7529200A/en not_active Abandoned
- 2000-09-20 WO PCT/FR2000/002610 patent/WO2001021532A1/en not_active Application Discontinuation
- 2000-09-20 EP EP00964332A patent/EP1216207A1/en not_active Withdrawn
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See references of WO0121532A1 * |
Also Published As
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FR2798652B1 (en) | 2001-11-23 |
AU7529200A (en) | 2001-04-24 |
FR2798652A1 (en) | 2001-03-23 |
WO2001021532A1 (en) | 2001-03-29 |
US6855268B1 (en) | 2005-02-15 |
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