EP0513070A1 - Procede de dissociation d'emulsions huile/eau - Google Patents

Procede de dissociation d'emulsions huile/eau

Info

Publication number
EP0513070A1
EP0513070A1 EP19910902951 EP91902951A EP0513070A1 EP 0513070 A1 EP0513070 A1 EP 0513070A1 EP 19910902951 EP19910902951 EP 19910902951 EP 91902951 A EP91902951 A EP 91902951A EP 0513070 A1 EP0513070 A1 EP 0513070A1
Authority
EP
European Patent Office
Prior art keywords
acid
emulsion
oil
emulsions
compounds
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Withdrawn
Application number
EP19910902951
Other languages
German (de)
English (en)
Inventor
Claus-Peter Herold
Uwe Ploog
Günter Uphues
Brigitte Spei
Volker Wehle
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 EP0513070A1 publication Critical patent/EP0513070A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/047Breaking emulsions with separation aids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means

Definitions

  • the invention relates to a process for splitting oil / water emulsions using organic emulsion splitters.
  • Oil-in-water emulsions used very often in the processing of metallic materials, such as cooling lubricant, deep-drawing, cutting or drilling emulsions, the oil phase of which is predominantly natural or synthetic Oils of different chemical composition and origin are not only subject to wear when used, but are also contaminated by the entry of foreign substances. They must therefore be disposed of regularly.
  • the most important step in the disposal, which may run continuously, is the cleavage of the processed emulsions; This means that the oil phase must be separated as much as possible from the water phase in order either to be able to work up and reuse the separated oil phase or to be able to dispose of it and the likewise separated water phase in an ecologically harmless manner to the usual disposal methods.
  • O / W emulsions are also obtained to a considerable extent in the extraction and extraction of petroleum. These are O / W emulsions, which are often stabilized by finely divided clay components. O / W emulsions also fall in the field of petroleum transportes and further processing in the refinery area. All these emulsions have in common that they have to be split up for disposal or further use of the water phase and for further processing of the oil phase.
  • cleavage agents used in practice are all of a cationic charge character, i.e. corresponding to cationic surfactants.
  • Emulsion splitters of the cationic type based on copolymers of dimethylamine and epichlorohydrin - or other comparable polyamines correspond to the prior art.
  • the influences that make the effectiveness of a cationic surfactant suitable as an emulsion splitter are not known. However, it has been shown in the past that only relatively narrowly limited classes of cationic surfactants are suitable for cleavage.
  • Classic quaternary ammonium compounds, e.g. Cetyltrimethylam onium chloride absolutely unsuitable as a splitting agent.
  • the optimal dosing range is usually determined by visual observation of the gap course in the emulsion splitting.
  • This determination of the optimal dosing range for the splitter i.e. of the end point for the addition of the surface-active compound used as a splitter, is generally carried out in such a way that splitter was added until a doping oil sludge flake forms. In order to avoid overdosing, this has to be done with the addition of small amounts of breaker, which is why the splitting of oil / water emulsions takes a period of several hours when the end point is determined visually.
  • cationic polymers are preferably used as splitters (demulsifiers). These usually indicate
  • compounds based on polyamines, polyamide amines, polyimines, condensation products of o-toluidine and formaldehyde, quaternary ammonium compounds and ionic surfactants are used.
  • polyamines with an average molecular weight in the range from 75,000 to 200,000 or condensation products of o-toluidine and formaldehyde are particularly preferred due to the good splitting results even at low splitter concentrations.
  • Quaternary ammonium salts are known from EP-PS 0 098 802, which are produced from tertiary amines and ethylene oxide. These are particularly suitable for use in hair cosmetics, such as hair conditioners.
  • Corresponding compounds are known from European patent specification 213 601, which are produced from tertiary amines and ethylene oxide and / or propylene oxide.
  • the invention thus relates to a process for splitting oil / water emulsions, which is characterized in that compounds of the general formula (I) are used:
  • R represents a straight-chain or branched-chain alkyl radical having 12 to 18 carbon atoms, R and R each independently of one another
  • the compounds to be used are obtained by processes known per se in the prior art by reacting primary, secondary or tertiary amines with ethylene oxide and / or propylene oxide in the presence of the desired acid.
  • Corresponding methods are known in particular from European patent specification 0098802 and European patent specification 0213601.
  • the abovementioned amines can either be reacted directly with ethylene oxide and / or propylene oxide or can be obtained as random or block polymers from ethylene oxide and propylene oxide by processes known per se. This is also a method known per se in the prior art.
  • the number of propylene oxide and / or ethylene oxide units is adjusted such that only one or two of these units are present in the molecule. Accordingly, n stands for 1 or 2.
  • the alkylamines are neutralized and heated with an inorganic acid or a low molecular weight organic mono-, di- or tricarboxylic acid. Then ethylene oxide and / or propylene oxide is passed through the reaction mixture.
  • the mono-, di- or tricarboxylic acids are selected from formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, Tartaric acid, citric acid and / or aconitic acid.
  • the salts of lactic acid to be used ie the lactates, are of particular importance.
  • the emulsions to be cleaved by the process according to the invention are, without exception, oil-in-water emulsions, as are obtained, for example, when processing metallic materials. These emulsions serve to cool the workpieces and tools in metal cutting, for example when cutting, drilling and turning, or to improve the sliding and separating behavior in metal cutting, for example in deep drawing. In this sense, emulsions are processed or, for experimental purposes, synthetically produced cooling lubricant, deep-drawing, cutting and / or drilling emulsions, emulsion mixtures also falling under the term mentioned.
  • oil-in-water emulsions described are aqueous systems which can contain up to 10% extraneous oil fractions:
  • emulsions in the abovementioned sense also mean the classic alkaline, neutral or acidic degreasing and cleaning baths which: for example in the automotive industry when degreasing or cleaning metal sheets.
  • the amounts of the compounds of the general formula (I) to be used for the cleavage of oil / water emulsions are less critical.
  • the concentration to be used results automatically from the method.
  • Preferred in the sense of the present invention, in particular with regard to the introduction of the substances into the environment, is a concentration of the compounds to be used according to the invention of 0.01 to 10% by volume, based on the emulsion to be split.
  • the compounds of the general formula (I) being present in a concentration of 0.05 to 2% by volume, based on the emulsion to be split , starts.
  • the method according to the invention can in principle be carried out in any temperature range; in which it is possible to mix the compounds of the general formula (I) with the oil-water emulsion.
  • the splitting of the emulsion according to the invention can thus be carried out between the pour point of the emulsion and the boiling point.
  • the process is preferably carried out in the range between room temperature and 80 ° C.
  • an increase in the turbidity of the emulsion occurs when an organic splitter is added.
  • the increase in turbidity is due to the fact that aggregates form between the organic anions of the emulsifier and the preferably cationic polymer ions of the splitter or demulsifier in the split water phase.
  • organic cleavage agents With further addition of organic cleavage agents, the turbidity rapidly decreases. This is based on coalescing of the oil droplets which are now no longer emulsified in the aqueous phase and the associated decrease in the total number of oil particles.
  • the result calculated from the ratio of the two measurement signals of two detectors in accordance with DE-OS 3627 199 is used to automatically interrupt the addition of organic splitter.
  • a maximum of turbidity results in practice, which is followed by a first minimum of turbidity when organic splitter is further added.
  • the amount of splitter added at the time of the measured minimum of turbidity corresponds exactly to the amount of organic splitter required for complete splitting of the emulsion, since at this point the amount of splitter added corresponds to the amount of emulsifier originally present in the emulsion and thus an almost complete splitting of the Emulsion can be achieved.
  • either the ratio of the measurement signals obtained from transmitted light and scattered light can be directly related to this be used to interrupt the addition of organic splitter when the turbidity has reached a first minimum after the maximum.
  • the residual oil content in the split water phase served as a guideline for the result of the emulsion splitting achieved.
  • the petroleum-extractable substances (PE) contained in the split water phase were determined.
  • the experimental setup was the following:
  • a 1 liter beaker was filled with 600 ml of the emulsion to be split and stirred continuously at 500 rpm using a magnetic stirrer.
  • the length of the stir bar was 50 mm.
  • An immersion concentration meter model 25/34, from Monitek, was used as the measuring device for measuring the turbidity.
  • the sensor type 25 (immersion probe) was attached to a tripod. The immersion depth of the probe was adjusted, ie all measurements were carried out at the same immersion depth of the immersion probe.
  • the opacimeter was connected to a recorder to record the measured values (opacity versus added amount of splitter). With a constant stirring speed of the magnetic stirrer, the respective organic splitter was added dropwise at predetermined time intervals or in a continuous, slow flow.
  • Example 2 In the same way as in Example 1, a mineral oil-containing, water-miscible cooling lubricant emulsion was split with an organic splitter.
  • a mineral oil-containing, water-miscible cooling lubricant emulsion was split using the test arrangement described above in accordance with Example 1. "A copolymer of dimethylamine and epichlorohydrin with a molecular weight of 0.5.10 - was used as the splitter, which is called” Ferolin R 18687 "is manufactured by the applicant.
  • the quality of the split water has been significantly improved when using this splitter, the oil phase is less water than in the comparison.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Colloid Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de dissociation d'émulsions huile/eau utilisant des dissociateurs d'émulsion organiques. On obtient ceux-ci par réaction d'alkylamines primaires, secondaires ou tertiaires avec des oxydes de propylène et/ou d'éthylène en présence d'acides inorganiques et/ou organiques. Les composés résultants de formule générale (I) sont utilisés en concentrations de 0,01 à 10 % en volume pour dissocier des émulsions huile/eau.
EP19910902951 1990-01-29 1991-01-21 Procede de dissociation d'emulsions huile/eau Withdrawn EP0513070A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904002472 DE4002472A1 (de) 1990-01-29 1990-01-29 Verfahren zur spaltung von oel-/wasser-emulsionen
DE4002472 1990-01-29

Publications (1)

Publication Number Publication Date
EP0513070A1 true EP0513070A1 (fr) 1992-11-19

Family

ID=6398948

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910902951 Withdrawn EP0513070A1 (fr) 1990-01-29 1991-01-21 Procede de dissociation d'emulsions huile/eau

Country Status (3)

Country Link
EP (1) EP0513070A1 (fr)
DE (1) DE4002472A1 (fr)
WO (1) WO1991011242A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4217985A1 (de) * 1992-05-30 1993-12-02 Hoechst Ag Verfahren zum Trennen von Erdölemulsionen vom Wasser-in-Öl-Typ

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3585148A (en) * 1969-03-26 1971-06-15 Nalco Chemical Co Quaternary ammonium demulsifiers
US4448708A (en) * 1982-01-29 1984-05-15 The Dow Chemical Company Use of quaternized polyamidoamines as demulsifiers
DE3374305D1 (en) * 1982-07-05 1987-12-10 Basf Ag Process for the preparation of quaternary ammonium salts
DE3300866A1 (de) * 1983-01-13 1984-07-19 Basf Ag, 6700 Ludwigshafen Oxalkylierte polyamidoamine, deren herstellung und deren verwendung als erdoelemulsionsspalter
DE3531356A1 (de) * 1985-09-03 1987-03-12 Hoechst Ag Mikrobiozide mittel auf basis von alkyl-di-guanidiniumsalzen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9111242A1 *

Also Published As

Publication number Publication date
WO1991011242A1 (fr) 1991-08-08
DE4002472A1 (de) 1991-08-01

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