WO1988007026A1 - Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques - Google Patents

Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques Download PDF

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Publication number
WO1988007026A1
WO1988007026A1 PCT/HU1987/000015 HU8700015W WO8807026A1 WO 1988007026 A1 WO1988007026 A1 WO 1988007026A1 HU 8700015 W HU8700015 W HU 8700015W WO 8807026 A1 WO8807026 A1 WO 8807026A1
Authority
WO
WIPO (PCT)
Prior art keywords
emulsions
iron chloride
polyelectrolyte
carried out
chloride sulfate
Prior art date
Application number
PCT/HU1987/000015
Other languages
German (de)
English (en)
Inventor
István GYO^"RFFY
Miklós DOBOS
András ZSO^´RI
László BA^´LINT
Attila SZILA^´GYI
István APRO^´
Ferenc TÖRÖCSIK
Béla KONKOLY
Gyula Czepek
Zoltán CSIPAI
András LOVAS
László BA^´NDI
Sándor KEREKES
Pál SZALA
Gyula Szepsi
Original Assignee
Kelet-Magyarorsza^´Gi Vizügyi Tervezo^" Va^´Llalat
E^´Szak-Magyarorsza^´Gi Regiona^´Lis Vizmüvek
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
Priority claimed from HU21586A external-priority patent/HU200576B/hu
Application filed by Kelet-Magyarorsza^´Gi Vizügyi Tervezo^" Va^´Llalat, E^´Szak-Magyarorsza^´Gi Regiona^´Lis Vizmüvek filed Critical Kelet-Magyarorsza^´Gi Vizügyi Tervezo^" Va^´Llalat
Priority to PCT/HU1987/000015 priority Critical patent/WO1988007026A1/fr
Publication of WO1988007026A1 publication Critical patent/WO1988007026A1/fr

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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
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

Definitions

  • the invention relates to a process for the treatment of highly disperse emulsions and liquids containing organic contaminants, in particular for the purification of waste water.
  • waste water and waste water sludge containing emulsions and organic contaminants are dangerous for the following reasons, among others:
  • oils and fats get into the soil, they endanger the groundwater, water contaminated with oil and organic contaminants can only be used as drinking water after very complex cleaning processes (membrane process, adsorption on activated carbon).
  • Aim of treatment of herbal emulsions, Wastewater and sewage sludge containing animal or mineral origin is to discharge the thin phase into open water or to remove pollutants in municipal wastewater treatment and to use the sludge phase or to deposit it in an environmentally friendly manner.
  • coarse emulsions For the purification of wastewater containing oil emulsions with a low degree of dispersion (so-called coarse emulsions), several systems are known. For example, the so-called M-AERMIX process is used for this purpose, electroflotation methods are known, etc. However, these methods are only suitable for removing the oil present in drops in water, which is present as a colloid, in micelles or in the form of real solutions are practically not touched by it.
  • the content of emulsified oil can be reduced from 1000 mg / l to 12-16 mg / l, ie the efficiency ⁇ OL (organic solvent extract) is 98.6%.
  • the oil-containing sole lamb is diluted with water in a ratio of 1x3 to 1: 6, adjusted to a pH of 8-8.5 and then mixed with surfactants and organic reagents. The sludge made safe in this way is used in agriculture.
  • the reason for this relative ineffectiveness of the processes is that the extremely different chemical-physical properties (acidic or alkaline reaction, salt content, electrokinetic zeta potential, interfacial activity) of the fat, oil and other organic emulsions of different origins and extraordinary different compositions (e.g. cooling and lubricating emulsions for machining, emulsions from alkaline soda ash, from car wash, protein, oils and fat-containing emulsions from meat, milk and vegetable oil processing) are not sufficiently taken into account, and all these emulsions treated in the same way, under identical conditions. In the case of these processes, it is therefore not possible to speak of an optimal technology adapted to the different composition and the changing character of the emulsions.
  • the object of the invention was to provide an economical method which has a high degree of efficiency and which also guarantees the respective optimal parameters in the case of emulsions of different origins and different properties.
  • the role of the hydrogen carbonates which crucially determine the alkalinity, is that in the course of the hydrolysis of the clarifying agents, the hydrogen ion concentration in the system increases and the shifted pH value counteracts the further hydrolysis.
  • the hydrogen carbonate ions bind the hydrogen ions released during the hydrolysis of the clarifying agents and in this way prevent the pH value from dropping too much.
  • the salt content of the emulsions (in particular the content of hydrogen carbonates and chlorides) has an advantageous effect on the structure of the flakes, resulting in flakes with a spongy structure which have a greater adsorption capacity.
  • the invention is based on the knowledge that it was partly possible for highly disperse emulsions and organi see liquids containing impurities to find the optimal coagulation range, which is identical for the most diverse emulsions, and that it was also recognized that the pH of the liquid had to be corrected for some of the emulsions before the coagulation was carried out in this range depending on the original pH either with acid or with alkali.
  • the process according to the invention for cleaning highly disperse emulsions and liquids containing organic impurities, in particular waste water is suitable for every starting pH value, for every starting salt concentration.
  • the process begins with a removal of the coarse emulsions by flotation, if necessary, followed by treatment with chemicals, and this is followed by phase separation.
  • the essence of the process is that after the floatation, if necessary, the pH is corrected and then iron chloride sulfate (feSO 4 Cl) is added to decompose the emulsion until a pH of 5.4-5.7 is reached. Thereafter, the flake polyelectrolytes are added to promote coagulation, and finally the phases are separated.
  • “highly disperse emulsions and liquids containing organic contaminants” are understood primarily to mean the following: vegetable emulsions, for example the waste water from vegetable oil production,
  • feSO 4 Cl 200 g / l Fe III
  • This range - 5.4-5.7 - is a fairly narrow range.
  • Coagulation in this area proceeds in the manner known for iron (III) salts.
  • the pH or the HCO content must be corrected if necessary 3 , -CO 3 can be taken care of.
  • the amount of -HCO 3 and -CO 3 must be supplemented before the iron chloride sulfate is added.
  • a solution containing the corresponding ions for example lime milk
  • the coagulator iron chloride sulfate is added until the already mentioned coagulation range has been reached, and then the flooks formed are flocculated by the addition of polyelectrolytes.
  • the aqueous phase is also clear and transparent.
  • emulsions of this type can also be coagulated by the addition of ferric chloride sulfate
  • a pH of ⁇ -9 there are still enough free -HCO 3 , -CO 3 ions available to ensure successful coagulation with iron chloride sulfate.
  • flocculation with polyelectrolyte also follows, followed by phase separation.
  • emulsions which, due to their pH, contain -HCO 3 , -CO 3 (pH between 7 and 8), but are nevertheless difficult to coagulate without prior correction.
  • emulsions are primarily drilling emulsions, emulsions for machining, hydraulic emulsions and others, ie emulsions containing emulsifiers in general. It is possible, that in these emulsions the coagulation is inhibited by the emulsifiers despite the presence of -HCO 3 , -CO 3 .
  • the pH must first be raised to 11-11.5 by adding -HCO 3 , -CO 3 , for example in the form of lime milk, and only then is iron chloride sulfate and then polyelectrolyte added.
  • Non-ionic or weakly anionic polyelectrolytes are used as flocculants, for example the weakly anionic Tecprofloc 75 N and the non-ionic Tecprofloc 70 (manufactured by Tecpro, Paris) or the non-ionic Prestol (manufacturer: Stockhausen, Krehfeld).
  • the treated liquid has a weakly acidic pH. In this state it can be added to municipal wastewater. It is also possible to adjust the pH value prescribed for waste water by adding a small amount of milk of lime / Ca (OH 2 ) / and then to drain the water immediately or to use it as industrial water.
  • the drained phase is used or deposited depending on its character.
  • the method according to the invention is illustrated by the figure.
  • the wastewater containing highly disperse emulsions and organic impurities arrives from the storage container 1 by vacuum suction into the flotation reactor 2, where the weakly disperse emulsion portion is removed, if this is not necessary, the liquid can be passed immediately into the reactor 3.
  • the solution required for correcting the pH (hydrochloric acid or lime milk) is added through line 5.
  • the iron chloride sulfate passes through line 6, the polyelectrolyte through line 7 into reactor 3.
  • the liquid is passed into the phase separation device 4, from which the treated waste water and the dewatered sludge are discharged separately.
  • Example 1 The process according to the invention is used to purify emulsion-containing wastewater from a vegetable oil factory which has the following parameters! pH 7.05
  • the pH is low (e.g. 6.0-6.5) and the impurities are in a much higher concentration
  • the pH is increased to 10-11 by adding lime milk raised, and then the feSO 4 Cl is added.
  • the working temperature is around 20oC.
  • Coagulation with iron chloride sulfate takes about 5-10 minutes, the subsequent flocculation takes 1-2 minutes, and treatment with milk of lime (if necessary) 3-5 minutes.
  • the treated water is clear, transparent, clean, its parameters
  • the precipitation phase has an Imhoff number of 210 ml / 1 (30 minutes) and a dry substance content of 1.9 g / l. (The Imhoff number is a measure of the settable solids.)
  • the parameters of the precipitation phase can change depending on the degree of contamination of the raw water.
  • the iron chloride sulfate was used in the form of a solution (Ongroflok, containing 200 g / 1 fe), and 0.5% Tecprofloc 75 N was used as the polyelectrolyte.
  • the coarse emulsions were removed by flotation before treatment.
  • waste water originating from the slaughterhouse is cleaned which is heavily contaminated with blood, fat and a lot of settable substance.
  • the parameters of this pronounced dirty water are pH 6.5 as follows
  • the temperature of the treatment is 20-25 ° C, reaction time in the first step 3-5 minutes, in the second step 5-10 minutes and in the third step 1-2 minutes.
  • the clear water phase has the following parameters: COD (chemical oxygen demand) 220.0 mg / l
  • Dry matter content 32 g / l With less contaminated raw water, the trooke content is around 1.5-3.0 g / l.
  • the method according to the invention has a very high efficiency.
  • a measure of efficiency serves to change the COD Cr value (the chemical oxygen demand, measured in mg / l, measured according to the chromate method) and the OL (the amount of substances that can be extracted with organic solvents, expressed in mg / l), using carbon tetrachloride as the solvent.
  • the OL value could be reduced by 97% or more, and the efficiency with regard to the COD Cr value was always over 60, but in many cases also reached 98%. Further measured values can be found in the following table.
  • the waste water from the car wash contained dimol, the three processing emulsions from mechanical engineering in the order given: Komaromi 1304/85, pyrohydrol emulsion, Kemobil 175/85.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (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

Un procédé de traitement d'émulsions microdispersées et/ou de fluides contenant des impuretés organiques, notamment des eaux usées, comprend l'élimination, si nécessaire, des émulsions grossières par flottation, suivie d'un traitement chimique puis d'une séparation des phases. Après la flottation éventuelle, on corrige si nécessaire le pH, puis on ajoute, afin de casser l'émulsion, du sulfate de chlorure ferrique jusqu'à atteindre un pH compris entre 5,4 et 5,7, puis un polyélectrolyte, afin d'accélérer la floculation, et on finit en séparant les phases les unes des autres.
PCT/HU1987/000015 1986-01-16 1987-03-13 Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques WO1988007026A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/HU1987/000015 WO1988007026A1 (fr) 1986-01-16 1987-03-13 Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU21586A HU200576B (en) 1986-01-16 1986-01-16 Process for producing liquids containing emulsions with high degree of dispersity and organic impurities
PCT/HU1987/000015 WO1988007026A1 (fr) 1986-01-16 1987-03-13 Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques

Publications (1)

Publication Number Publication Date
WO1988007026A1 true WO1988007026A1 (fr) 1988-09-22

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ID=26317176

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/HU1987/000015 WO1988007026A1 (fr) 1986-01-16 1987-03-13 Procede de traitement d'emulsions microdispersees et de fluides contenant des impuretes organiques

Country Status (1)

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WO (1) WO1988007026A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2656812A1 (fr) * 1990-01-09 1991-07-12 Elf France Procede de cassage d'huiles de coupe usagees.
EP0448821A1 (fr) * 1990-03-27 1991-10-02 Bayer Ag Procédé de rupture d'émulsions d'huiles-en-eau
GB2264951A (en) * 1992-03-11 1993-09-15 Allott Environmental Processes Breaking a bitumen-water emulsion
WO2000027759A2 (fr) * 1998-11-07 2000-05-18 The Procter & Gamble Company Procede et composition permettant de recycler l'eau
WO2005092469A1 (fr) * 2004-03-04 2005-10-06 Veolia Water North America Operating Services, Llc Systeme et procede de recuperation de petrole d'un debit concentrat

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4450092A (en) * 1982-06-11 1984-05-22 Nalco Chemical Company Reducing turbidity in turbid waters
GB2157278A (en) * 1984-04-11 1985-10-23 Hydro Int Ltd Water treatment

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4450092A (en) * 1982-06-11 1984-05-22 Nalco Chemical Company Reducing turbidity in turbid waters
GB2157278A (en) * 1984-04-11 1985-10-23 Hydro Int Ltd Water treatment

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2656812A1 (fr) * 1990-01-09 1991-07-12 Elf France Procede de cassage d'huiles de coupe usagees.
EP0448821A1 (fr) * 1990-03-27 1991-10-02 Bayer Ag Procédé de rupture d'émulsions d'huiles-en-eau
GB2264951A (en) * 1992-03-11 1993-09-15 Allott Environmental Processes Breaking a bitumen-water emulsion
WO2000027759A2 (fr) * 1998-11-07 2000-05-18 The Procter & Gamble Company Procede et composition permettant de recycler l'eau
WO2000027759A3 (fr) * 1998-11-07 2000-11-30 Procter & Gamble Procede et composition permettant de recycler l'eau
WO2005092469A1 (fr) * 2004-03-04 2005-10-06 Veolia Water North America Operating Services, Llc Systeme et procede de recuperation de petrole d'un debit concentrat

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