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WO1993009064A1 - Procede de floculation - Google Patents

Procede de floculation Download PDF

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Publication number
WO1993009064A1
WO1993009064A1 PCT/EP1992/002476 EP9202476W WO9309064A1 WO 1993009064 A1 WO1993009064 A1 WO 1993009064A1 EP 9202476 W EP9202476 W EP 9202476W WO 9309064 A1 WO9309064 A1 WO 9309064A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium
compound
wastewater
carbon dioxide
flocculation
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.)
Ceased
Application number
PCT/EP1992/002476
Other languages
German (de)
English (en)
Inventor
Wolfgang Berke
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993009064A1 publication Critical patent/WO1993009064A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • the invention relates to a process for flocculating a finely divided inorganic or organic synthetic substance from the aqueous phase, in particular in wastewater treatment.
  • wastewater with inorganic and organic components is generally cleaned as follows: a) A computing unit removes coarse solids. b) Light liquids are separated in a separator. c) The pH is adjusted to approx. 7 with NaOH or H2SO4 in order to precipitate heavy metal ions and phosphates. d) The precipitation is further completed by the addition of precipitants and flocculants. The solids are removed after their sedimentation and, depending on their nature, further treated, e.g. deposited as hazardous waste or used as a valuable material. e) The treated wastewater is still biologically cleaned, e.g. in that the remaining organic compounds are broken down aerobically and / or anaerobically.
  • one or more stages can be omitted without missing the main objectives of cleaning, namely a) to improve the quality of the wastewater in such a way that it can either be recycled or discharged into the public sewerage system without damage, and b) to recover valuable materials.
  • Waste water with finely divided organic and inorganic substances is very common in industry, e.g. in the manufacture and processing of lacquers, emulsion paints, wallpapers, adhesives, fibers, carpets, textiles, dyes, pigments, rubber, oil, lubricants, greases, waxes etc.
  • the waste water can contain very little solids, e.g. Waste water from rinsing and cleaning processes, as well as very much, e.g. a mud-like soil.
  • such wastewater typically contains:
  • Base polymer e.g. polystyrene-butadiene, polyvinyl acetate, polyvinyl alcohol, polyolefin, polyvinyl chloride, polyacrylates, polymethacrylates and epoxy resins with additives such as plasticizers (e.g. dibutyl phthalate), protective colloids: PVA, HEC r dextrins, hydroxyethyl starch, emulsifiers: nonylphenol ethoxylates, fatty alcohol fillers, colorants, fillers, colorants, coloring agents, colorants, fillers, colorants, colorants, fillers, colorants, colorants, fillers, colorants, colorants, coloring agents, fillers, colorants, colorants, fillers: .
  • plasticizers e.g. dibutyl phthalate
  • protective colloids PVA, HEC r dextrins, hydroxyethyl starch
  • emulsifiers nonylphenol ethoxylates
  • the components in solid or liquid form (suspensions or emulsions) which are finely divided, ie molecularly, colloidally or coarsely dispersed, can be removed by filtration, sedimentation, centrifugation or else by flocculation from the aqueous phase.
  • Flocculation or flocculation is understood to mean the removal of undesired constituents by the formation of sparingly soluble substances in the form of flakes, whether by coalescence, occultation or Adsorption.
  • a liquid clouded by dispersed particles is clear again. This is achieved primarily with the aid of suitable additives (flocculants or clarifiers) on inorganic electrolytes with polyvalent cations, for example iron and aluminum chloride or sulfate and calcium hydroxide, or by adding macromolecular organic polyelectrolytes based on polyacrylic acid, polyacrylamide, Polyethylene oxide, polyethylene imine, etc.
  • adsorption processes in the particle surfaces break down the potential barriers that hinder flocculation.
  • the particles are additionally crosslinked by the filiform molecules of the flocculant, the binding-active groups of which interact with the particle surfaces.
  • hydroxide precipitates An essential factor for a successful clarification effect in conventional processes is the formation of hydroxide precipitates.
  • the metering of increasing amounts of aluminum or iron salt at approximately neutral pH values leads to hydroxide flakes which occur when they are formed or subsequently Can bind the remaining turbidity through adsorption and inclusion (precipitation flocculation).
  • the resulting products are highly water-containing, amorphous hydroxides, which have only low flake strength and are difficult to separate and dewater by sedimentation or filtration.
  • the pH value is corrected by adding lime.
  • Calcium also leads to precipitation such as CaSOj, which improves separation as a filler.
  • the object of the invention consists in particular in reducing or even eliminating these disadvantages, and in general in improving the effectiveness and economy of the flocculation.
  • the solution according to the invention can be found in the patent claims. It essentially consists of flocculation with poorly soluble calcium compounds in situ.
  • the flocculation according to the invention is characterized by the addition of a polyvalent electrolyte, a calcium compound and a carbon compound, which gives a poorly soluble reaction product with calcium, to an aqueous liquid with finely divided inorganic or organic substances.
  • polyvalent electrolytes are known flocculants, that is to say inorganic electrolytes with 2- and in particular trivalent cations such as calcium, magnesium, iron, aluminum or organic polyelectrolytes, in particular cationic polyelectrolytes.
  • inorganic electrolytes with 2- and in particular trivalent cations such as calcium, magnesium, iron, aluminum or organic polyelectrolytes, in particular cationic polyelectrolytes.
  • Such substances are commercially available, for example under the name Sachtopur-S, Sachtoklar (Sachtleben Chemie, Duisburg), Quickfloc, Ferrifloc (Kronos, Langenfeld), P3-Ferrocryl, P3-Ferrolin (Henkel, Düsseldorf) , Rohafloc (Röhm, Darmstadt).
  • the electrolytes are added in the concentrations specified by the manufacturer, for example 5 to 500 g / ⁇ solids in the waste water. Coagulation can also be achieved by lowering the pH, especially by gassing with carbon dioxide.
  • the dispersion or the emulsion can be cleaved at a higher temperature.
  • the calcium compounds are water-soluble or colloidally dispersed calcium compounds such as calcium chloride, calcium hydroxide, calcium oxide.
  • Lime milk and lime water are preferred, in particular calcium oxide or calcium hydroxide (ie dry substances). Burnt or slaked lime is the cheapest source of calcium and is available everywhere in large quantities.
  • the calcium compound can be added to the aqueous liquid before and / or after coagulation with the polyvalent electrolyte; it can also serve to set an optimal pH.
  • the calcium compound is precipitated in situ by the addition of a carbon compound.
  • the carbon compound is said to produce a poorly soluble reaction product with the calcium.
  • carboxylic acids in particular monocarboxylic acids, and polyols, in particular amino acids or proteins.
  • an addition of carbon dioxide is preferred.
  • the acids, in particular the CO2 are added until the pH is in the weakly alkaline range, in particular until it is approximately 8.7 to 9.
  • the Calcium compound and the carbon dioxide can be metered in successively, alternately in several stages or simultaneously (continuously).
  • the precipitation flocculation with the sparingly soluble calcium salt or complex can be repeated or carried out until the aqueous liquid is no longer cloudy or has the desired purity.
  • the course of the titratation with the carbonic acid allows the pH of the liquid to be set precisely.
  • the process according to the invention can be carried out both at room temperature and at elevated temperature. It is therefore possible to clarify with liquids at the temperature of 10 to 80 ° C. which is produced.
  • the process components according to the invention are added and distributed using conventional devices, for example the electrolytes are added by freshly preparing a working solution according to the manufacturer's instructions, for example from a stock solution or the undiluted electrolyte, and mixing it intensively into the water to be treated.
  • the calcium compound is added by preparing a working solution and mixing it intensively into the water to be treated, for example by producing lime milk from burnt or extinguished lime.
  • the use of solid substances, for example by sprinkling salts into the water to be treated, is possible, but usually requires additional consumption.
  • the carbon dioxide is added by Introduces carbon dioxide gas into the preferably alkaline solution. Simple gassing devices for containers or pipes are sufficient.
  • a soluble hydrogen carbonate or carbonate preferably sodium hydrogen carbonate, can be dissolved or added to the water as a solid.
  • the control of the pH value is the decisive factor in all steps.
  • the optimal pH is between 10.8 and 11.2.
  • the pH should not fall below 8.7. This also applies to a gradual, changing dosage of the reagents.
  • the process according to the invention can be used to clarify aqueous liquids with finely divided inorganic or organic synthetic substances, in particular fully synthetic substances.
  • Aqueous dispersions with such substances are stabilized with dispersants.
  • dispersants These are water-soluble polymers as protective colloids and emulsifiers.
  • Polymers are natural products such as alginates, tragacanth, agar-agar, dextrins and starch, modified natural polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, hydroxyethyl starch and synthetic polymers such as copolymers styrene / maleic anhydride, polymethacrylate, polyvinyl pyrrolidone, polyvinyl alcohol, partially saponified polyvinyl acetate, etc.
  • Emulsifiers are, in particular, anionic surfactants such as alkanesulfonates and fatty alcohol ether sulfates or nonionic surfactants such as nonylphenol oxethylates.
  • the flocculation process according to the invention is particularly suitable for cleaning industrial wastewater.
  • These industrial wastewater are generally characterized by the presence of a stabilized emulsion or dispersion of inorganic or organic synthetic substances, which cannot be purified solely by using polyvalent electrolytes.
  • the solubility of the precipitate is extremely low.
  • the solid has a high density and can be sedated or filtered quickly. Since the separation of the solid determines the grain size, it can easily be influenced by the type and duration of the addition of carbon dioxide.
  • Waste water from a plant producing and processing PVAc dispersions (washing and rinsing water) with a dry matter content of 28 g / 1 (s 28 kg / m 3 ).
  • the filtrate was clear.
  • the filtration of the solid from the liquid took only half as long as in a conventional cleaning process using only an electrolyte and a lime compound.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

On décrit un procédé de floculation d'une substance synthétique organique ou inorganique finement divisée et contenue dans un liquide aqueux, procédé selon lequel on ajoute au liquide un électrolyte polyvalent, un composé du calcium et un composé du carbone qui donne avec le calcium un produit de réaction peu soluble. On utilise de préférence des sels ferriques, de la chaux vive et du CO2. On peut ainsi purifier principalement des effluents de dispersions stabilisées de polymères entièrement synthétiques.
PCT/EP1992/002476 1991-11-07 1992-10-29 Procede de floculation Ceased WO1993009064A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914136616 DE4136616A1 (de) 1991-11-07 1991-11-07 Ausflockung
DEP4136616.6 1991-11-07

Publications (1)

Publication Number Publication Date
WO1993009064A1 true WO1993009064A1 (fr) 1993-05-13

Family

ID=6444253

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002476 Ceased WO1993009064A1 (fr) 1991-11-07 1992-10-29 Procede de floculation

Country Status (3)

Country Link
DE (1) DE4136616A1 (fr)
MX (1) MX9206397A (fr)
WO (1) WO1993009064A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672624A1 (fr) * 1994-02-21 1995-09-20 Ecc International Limited Traitement d'eau usée
US5618439A (en) * 1993-04-20 1997-04-08 Boliden Contech Ab Method for purifying industrial sewage water
FR3040387A1 (fr) * 2015-08-25 2017-03-03 Sarp Ind Procede de regeneration de liquides de rincage

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2775682B1 (fr) * 1998-03-09 2000-04-14 Carboxyque Francaise Traitement d'effluents aqueux par injection d'anhydride carbonique
RU2151745C1 (ru) * 1998-05-25 2000-06-27 Государственное предприятие "Научно-исследовательский институт синтетического каучука им. акад. С.В.Лебедева" Способ очистки сточных вод
AU2013207170A1 (en) 2012-01-06 2014-06-26 Pureteq A/S Method and system for purification of produced water

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1459497A1 (de) * 1963-07-10 1969-04-17 Metallgesellschaft Ag Verfahren zur Schlammbehandlung mit kohlensaeurehaltigen Gasen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1459497A1 (de) * 1963-07-10 1969-04-17 Metallgesellschaft Ag Verfahren zur Schlammbehandlung mit kohlensaeurehaltigen Gasen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7729, Derwent Publications Ltd., London, GB; AN 77-51001Y *
DATABASE WPI Week 7850, Derwent Publications Ltd., London, GB; AN 78-90138A *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5618439A (en) * 1993-04-20 1997-04-08 Boliden Contech Ab Method for purifying industrial sewage water
EP0622338B1 (fr) * 1993-04-20 1997-08-27 Boliden Contech Ab Procédé d'épuration des eaux industrielles
EP0672624A1 (fr) * 1994-02-21 1995-09-20 Ecc International Limited Traitement d'eau usée
FR3040387A1 (fr) * 2015-08-25 2017-03-03 Sarp Ind Procede de regeneration de liquides de rincage

Also Published As

Publication number Publication date
MX9206397A (es) 1993-03-01
DE4136616A1 (de) 1993-05-13

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