EP0699098A1 - Procede pour la deshydratation d'huiles usees a l'aide de composes tensioactifs - Google Patents

Procede pour la deshydratation d'huiles usees a l'aide de composes tensioactifs

Info

Publication number
EP0699098A1
EP0699098A1 EP94916960A EP94916960A EP0699098A1 EP 0699098 A1 EP0699098 A1 EP 0699098A1 EP 94916960 A EP94916960 A EP 94916960A EP 94916960 A EP94916960 A EP 94916960A EP 0699098 A1 EP0699098 A1 EP 0699098A1
Authority
EP
European Patent Office
Prior art keywords
oil
carbon atoms
emulsion
salts
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94916960A
Other languages
German (de)
English (en)
Inventor
Brigitte Spei
Hermann Jonke
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 EP0699098A1 publication Critical patent/EP0699098A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/0226—Quaternisation of polyalkylene(poly)amines
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/04—Working-up used lubricants to recover useful products ; Cleaning aqueous emulsion based

Definitions

  • the invention relates to a process for the dewatering of technical waste oil, which is either an oil-in-water emulsion or a water-in-oil emulsion and which in each case consists of at least 15% oil.
  • technical waste oil which is either an oil-in-water emulsion or a water-in-oil emulsion and which in each case consists of at least 15% oil.
  • Such emulsions are obtained in the processing of technical oil-in-water emulsions, for example by creaming in a mechanical separator, by enrichment using membrane filtration processes or as a result of primary cleavage.
  • Used and disposed oil-in-water emulsions occur in large quantities in the metalworking industry.
  • One source of this are cooling lubricant emulsions, which are used in metal cutting and which have an oil content of about 2 - 5%. Even if such emulsions can be used for a long time - up to several months - they are finally used up and must be disposed of.
  • Another source of waste emulsions are, for example, technical degreasing and cleaning baths, which build up an oil content of about 1 - 5% due to the oil they enter and which have to be continuously de-oiled and / or discarded at the end of their useful life.
  • Waste emulsions of mentioned type are oil-in-water emulsions.
  • the processing and disposal generally begins by carrying out a concentration or primary cleavage into a water-rich and an oil-rich phase.
  • phase separation takes place, for example, in mechanical separators of sewage plants by the action of gravity, an "old oil” in the form of an oil-rich oil-in-water emulsion with an oil content of more than 15% by weight.
  • a further possibility of a primary separation consists in subjecting the emulsion to membrane filtration, for example micro- or ultrafiltration, and splitting it into an oil-rich retentate with an oil content of more than 15% by weight and into a practically oil-free permeate. In both of these cases, an oil-rich oil-in-water emulsion is present after the first separation step.
  • the primary fission can, as described in DE-A-41 26 914, be carried out by an electrolytic charge neutralization of the oil droplets.
  • Thermal splitting by heating the waste emulsion is also possible, but is not very common due to the high energy requirement.
  • the processing of waste emulsions often begins by subjecting the emulsion to primary splitting with chemical emulsion splitters. Either strong acids, inorganic salts and / or organic emulsion breakers can be considered for chemical emulsion breakdown.
  • the organic emulsion breakers which often consist of cationic polymers, have the great advantage that they remain in the oil phase during the breakdown and therefore do not contribute to further contamination of the water phase and do not produce any additional sludge.
  • Emulsion splitters for such primary cleavage are known in large numbers in the prior art, for example DE-A-40 09 760 mentions synthetic polymers based on polyimines, polyether polyamines, polyamines and polyamide amines or quaternized polyamines and quaternized polyamide amines, furthermore cationic copolymers of acrylamide and different proportions of cationic monomers or oligomers and homopolymers of dimethyldiallylammonium chloride.
  • Organic cationic emulsion breakers based on polyamines, polyimines, polyether polyamines and polyamide amines have proven particularly useful.
  • DE-A-40 09 760 describes a two-stage process for the primary splitting of an oil-in-water emulsion using both inorganic and organic emulsion splitters.
  • the emulsions to be split primarily are mixed with an organic cationic emulsion splitter of the type mentioned above and then with an inorganic emulsion splitter based on salts of polyvalent metals, in particular aluminum, iron and calcium.
  • an organic cationic emulsion splitter of the type mentioned above
  • an inorganic emulsion splitter based on salts of polyvalent metals, in particular aluminum, iron and calcium.
  • the oil phase separated in a chemical primary fission is usually in the form of a water-in-oil emulsion with an oil content of more than 15% by weight. If you want to process, deposit or incinerate this water-in-oil emulsion that arises during the primary splitting, the residual water content proves to be a hindrance or at least to drive costs. It is therefore generally advantageous to further rid this emulsion of water by secondary cleavage. The task this poses further dewatering is related to the problem of dewatering crude oil emulsions that occur during oil production either directly or as a result of tenside-assisted tertiary production.
  • this object is achieved by a
  • the compounds from group A) are selected from ethoxylation products of fatty amines or fatty alcohols with 10 to 18, preferably 12 to 16 carbon atoms with 5 to 29 moles of ethylene oxide and from ethoxylation / propoxylation products of fatty amines or fatty alcohols with 10 to 18, preferably 10 to 16 carbon atoms with 4 to 10 moles of ethylene oxide followed by 1 to 4 moles of propylene oxide, the fatty alcohols or fatty amines preferably being saturated compounds and product mixtures obtained from natural fats and oils are, and the alkylene oxide chains are available with conventional or with narrow homolog distribution, and
  • the compounds from group B) are selected from saturated alkyl sulfates or sulfonates, preferably alkyl sulfates, having 10 to 16 carbon atoms, these in the form of their alkali metal, ammonium, alkylammonium or alkanolammonium salts, preferably as lithium -, Sodium, ammonium and / or triethanolammonium salts can be used. Lithium and / or triethanolammonium salts are particularly preferred.
  • the most suitable drainage agent or its combinations for a given drainage task, as well as their optimal concentrations, must be determined on a sample-specific basis. They depend on the water content of the samples, the degree of distribution of the emulsion, and the type and amount of the stabilizers present. In general, amounts between 5 ppm and 60,000 ppm, based on the total amount of the liquid to be dewatered, are effective. It is preferred to work in the concentration range between 100 ppm and 30,000 ppm.
  • the dosing end point for the dewatering agents can be recognized in favorable cases by a change in the optical appearance of the emulsion to be dewatered.
  • the power consumption of the agitator which has a minimum with the optimal dosing, can also provide an indication of reaching the dosing end point.
  • the viscosity of the emulsion to be dewatered indicates the optimal dosing of the dewatering agent Minimum on. It does not matter which of the known methods is used to determine the viscosity. For reasons of easy handling, the Brookfield viscosity determination is preferably used.
  • the drainage agents from group A) can be combined with N-alkylpyridinium salts with an alkyl substituent with 10 to 16 C atoms, trimethylalkylammonium salts with an alkyl radical with 10 to 18 C atoms, dimethylbenzylalkylammonium salts with an alkyl radical with 10 to 16 C atoms, Dimethyldialkylammonium salts with two identical or different alkyl radicals, each with 6 to 12 C atoms, and dimethylalkylammonium betaines with an alkyl radical with 8 to 18 C atoms, and / or with polymers with the assemblies
  • X n- is a single, double or triple negatively charged preferably inorganic anion, in particular Cl, hydrogen sulfate, sulfate, phosphate or mono- or dihydrogen phosphate.
  • the drainage agents of group (s) A) and / or B) can be combined with the agents described in DE-A-4040022: polymers and / or oligomers of ethylene oxide and / or 1,2-propylene oxide, oxyalkylated phenolic resins, with Diisocyanates, dicarboxylic acids, formaldehyde and / or diglycidyl ether crosslinked block or mixed polymers of ethylene and 1,2-propylene oxide, polyether urethanes and / or alkylbenzenesulfonic acid salts.
  • the temperature of the emulsion to be dewatered is chosen to be as close as possible to room temperature for energy-saving reasons, on the other hand, one is dependent on a sufficiently low viscosity.
  • dewatering will be carried out at temperatures between 15 and 95 ° C, preferably between 20 and 80 ° C.
  • the dewatering agents are uniformly distributed in the emulsion by methods well known to the person skilled in the art, for example by stirring.
  • the separation of the Emulsion in a water-rich phase and in a dewatered oil phase can take place under the influence of natural gravity in suitable sedimentation containers.
  • the efficiency of phase separation can be increased by using a continuous or batch centrifuge. If the emulsion to be dewatered still contains sedimentable solids, it is advisable to separate it before carrying out the dewatering, for example by sedimentation, filtration or by centrifugation.
  • Flotates I to III were obtained by primary cleavage with polydiallyldimethylammonium chloride, Flotate IV and V by primary cleavage with a cationically modified polyamine.
  • Retentate I was obtained during the ultrafiltration of the primary mixed emulsions through polyvinylidene difluoride membranes.
  • Waste oils were obtained by mechanical separation of the mixed emulsions in oil separators.
  • the waste oils or comparative substances according to Tables 3 and 4 were added to the waste oils, flotates and retentates.
  • the samples were stirred with a grid stirrer, the dewatering products were added and, after the product had been added, stirring was continued for 5 minutes.
  • the end point of the product addition was determined either via the current consumption of the stirrer, a viscosity measurement or after the optical change of the samples.
  • the samples were either left to stand for 24 hours or with a laboratory centrifuge for one Centrifuged for 5 minutes at a speed of 4000 revolutions per minute.
  • the volume fraction of the oil phase separating hereby was determined. It is included in Table 3.
  • the oil phase was generally subordinate to a mixed phase and / or a water phase, which in practical cases may have to be subjected to further workup, for example by recycling to the primary cleavage or to the membrane filtration.
  • the water content of the samples was determined.
  • the water content of the oil phase obtained after dewatering was also determined.
  • the water contents were determined by evaporating a 10 g sample of the samples to constant weight by the action of microwaves.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé pour la déshydratation d'huiles usées formées d'émulsions soit du type huile dans l'eau, soit du type eau dans l'huile, caractérisé en ce qu'on utilise des composés des groupes suivants: A) produits d'alkoxylation d'alcools gras ou d'amines grasses de 8 à 22 atomes de carbone et/ou B) monoalkylsulfates ou monoalkylsulfonates aliphatiques de 8 à 22 atomes de carbone, et en ce qu'on effectue ensuite une séparation des phases.
EP94916960A 1993-05-21 1994-05-13 Procede pour la deshydratation d'huiles usees a l'aide de composes tensioactifs Withdrawn EP0699098A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4317046 1993-05-21
DE19934317046 DE4317046A1 (de) 1993-05-21 1993-05-21 Verfahren zur Entwässerung von Altöl unter Verwendung von oberflächenaktiven Verbindung
PCT/EP1994/001554 WO1994027701A1 (fr) 1993-05-21 1994-05-13 Procede pour la deshydratation d'huiles usees a l'aide de composes tensioactifs

Publications (1)

Publication Number Publication Date
EP0699098A1 true EP0699098A1 (fr) 1996-03-06

Family

ID=6488654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94916960A Withdrawn EP0699098A1 (fr) 1993-05-21 1994-05-13 Procede pour la deshydratation d'huiles usees a l'aide de composes tensioactifs

Country Status (5)

Country Link
EP (1) EP0699098A1 (fr)
CZ (1) CZ306595A3 (fr)
DE (1) DE4317046A1 (fr)
PL (1) PL311699A1 (fr)
WO (1) WO1994027701A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19733977A1 (de) 1997-08-06 1999-02-11 Henkel Kgaa Verfahren zur Spaltung von Emulsionen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2854975C2 (de) * 1978-12-20 1986-08-07 Hoechst Ag, 6230 Frankfurt Emulsionsspalter
US4384977A (en) * 1981-06-11 1983-05-24 Marathon Oil Company Polyalkyloxyamines as demulsifying agents
DE4040022A1 (de) * 1990-12-14 1992-06-17 Bayer Ag Spaltung von wasser-in-oel-emulsionen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9427701A1 *

Also Published As

Publication number Publication date
WO1994027701A1 (fr) 1994-12-08
DE4317046A1 (de) 1994-11-24
PL311699A1 (en) 1996-03-04
CZ306595A3 (en) 1996-08-14

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