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WO2001045818A1 - Procede de rupture d'une emulsion - Google Patents

Procede de rupture d'une emulsion Download PDF

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Publication number
WO2001045818A1
WO2001045818A1 PCT/US1999/030636 US9930636W WO0145818A1 WO 2001045818 A1 WO2001045818 A1 WO 2001045818A1 US 9930636 W US9930636 W US 9930636W WO 0145818 A1 WO0145818 A1 WO 0145818A1
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WIPO (PCT)
Prior art keywords
oil
emulsion
water
mill
solids
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Ceased
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PCT/US1999/030636
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English (en)
Inventor
Robert Scalliet
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Individual
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Priority to PCT/US1999/030636 priority Critical patent/WO2001045818A1/fr
Priority to AU23793/00A priority patent/AU2379300A/en
Publication of WO2001045818A1 publication Critical patent/WO2001045818A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/063—Arrangements for treating drilling fluids outside the borehole by separating components
    • 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
    • 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
    • B01D17/0208—Separation of non-miscible liquids by sedimentation
    • 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
    • B01D17/0208—Separation of non-miscible liquids by sedimentation
    • B01D17/0211—Separation of non-miscible liquids by sedimentation with baffles
    • 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
    • B01D17/0217—Separation of non-miscible liquids by centrifugal force
    • 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
    • B01D17/041—Breaking emulsions with moving devices
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B39/00—Cooling or quenching coke
    • C10B39/04—Wet quenching
    • C10B39/06—Wet quenching in the oven
    • 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
    • C10G33/06—Dewatering or demulsification of hydrocarbon oils with mechanical means, e.g. by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/322—Coal-oil suspensions
    • 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

Definitions

  • the present invention pertains to an effective, cost efficient method of separating even tightly emulsified oily waste sludges.
  • the method can be used in treating used liquid petroleum products, and wastes generated from petroleum production and refining facilities, manufacturing plants, chemical plants, still mill sludges, municipal facilities, and other similar facilities and operations.
  • waste products that are partial emulsions of water, oil and solids and are referred to as "sludges.”
  • sludges waste products that are partial emulsions of water, oil and solids and are referred to as "sludges.”
  • petroleum refineries and manufacturing plants generate significant quantities of oily waste products that contain a variety of solids, such as suspended carbonaceous matter and inorganic matter such as rust scales, catalysts fines and the like.
  • most of this waste is classified as hazardous and, therefore, must be treated before disposal in regulated landfills to meet concentration limits for certain organic compounds, cyanides and several heavy metals.
  • Refinery waste sludges are among the most difficult emulsions to break. Yet the disposal criteria for solids are expensive to reach, necessitating the separation of the water, oil and solid components to minimize the amount of wastes that require disposal. Further, the hydrocarbons can be recycled in the plant's processes and the water can be treated per normal waste water treatment processes, if sufficient amounts of solids are removed. Therefore, although refinery waste sludges are very difficult to break, it is often the most economical means of treating the waste.
  • An emulsion may be present in oily waste products other than refinery waste sludges. Emulsions may also be present in used oil.
  • drilling fluid may become saturated with cuttings, oil, water, and other materials.
  • the saturated drilling fluid is no longer usable and must be discarded.
  • the saturated drilling fluid may include an emulsion that includes the oil constituent of the drilling fluid. Unless the oil constituent of the saturated drilling fluid can be separated from the emulsion, the oil constituent will be discarded with the remainder of the saturated drilling fluid. If the saturated drilling fluid could be demulsified, the oil of the drilling fluid could be recovered and recycled as drilling fluid.
  • an emulsion may be present in other forms of used or spent oil.
  • the oil may become soiled with dirt and metal particles during use and an emulsion may be formed of the oil and other constituents of the used oil. Unless the oil constituent of the motor oil can be separated from the spent motor oil, the oil constituent will be discarded with remainder of the spent motor oil.
  • An emulsion is an intimate mixture of two immiscible liquids, such as oil and water. Two types of oil and water emulsions are commonly encountered, based on the relative amounts of oil and water. The first is an oil dispersed in water (oil in water) emulsion, and the second is a water dispersed in oil (water in oil) emulsion.
  • a stable oil in water emulsion consists of electrically charged oil droplets dispersed in a polar medium such as water.
  • the violent mixing and shearing of oily wastewater in transfer pumps disperses the minute oil droplets throughout the water, and the friction between the oil and water phases creates static electrical charges at the oil and water interphase and helps to stabilize the emulsion.
  • This emulsion can be further stabilized by a variety of chemical and physical mechanisms.
  • Surfactants such as soaps, cresylates, sulfides, and electrolytes
  • Fine, solid particles may also stabilize an emulsion if the particles are of the correct size and abundance. The solid particles adsorb at the oil/water interface, reinforce the interfacial film and prevent the droplets from coalescing. Thus, solid particles also reinforce the stability of the dispersion.
  • the "breaking,” or “resolution,” of an oil in water emulsion is done by neutralizing the charges at the surface of the droplets. This is performed with a cationic emulsion breaker because the dielectric constants of oil and water cause the oil droplets to carry a negative charge in water. Lowering the pH, with sulfuric acid for example, can also help by converting any carboxyl ions present in the surfactant into carboxylic acid.
  • the phases can be gravity separated in an API or CPI separator. This separation can be significantly accelerated by centrifuging the mixture. Treatments to break waste sludges include also floatation, ultrafiltration, activated carbon adsorption, coalescence and solvent extraction.
  • Water in oil emulsions are viscous, concentrated substances formed when oil comes into contact with water and solids. Where agitation is present, the water becomes dispersed in the oil. Finely divided solids, ranging from colloidal to 100 microns, are particularly effective in stabilizing these emulsions.
  • Other stabilizing agents include soaps, sulfonated oils, asphaltic residue waxes, salt sulfides and mercaptans.
  • the breaking of a water in oil emulsion can be done with physical methods such as heating and centrifugation.
  • Chemical treatment of water in oil emulsions is 'directed at destabilizing the dispersed water droplets and solids or at destroying the emulsifying reagents.
  • anionic reagents are employed to destabilize the water droplets because the water droplets tend to be positively charged. Acidification may also be effective if the acid dissolves some of the solids and thus reduces the amount of stabilizing solids.
  • Another method of treatment involves potent demulsifying agents carrying both hydrophilic and lipophilic groups. The demulsifying agent displaces the original emulsifying agent because it has more potent surface active agents.
  • Heating reduces the viscosity of the emulsion and increases the solubility and diffusion of the demulsifying agent in the emulsion.
  • thorough mixing and heat are both necessary to help disperse the demulsifying agents in the emulsion and to facilitate the separation of the phases once the charges are neutralized.
  • centrifugation is the key to accelerating the separation.
  • the parti culate matter After being separated from the oil and water components of the stream, the parti culate matter leaves the centrifuge at a very high exit speed and the impact of the solids on the exit shield causes attrition of the particle size. This particle attrition makes the solids produced thereby particularly suitable for use in a coker quench stream.
  • U.S. Patent No. 4,810,393 relates to a process for the resolution of oily sludges that consists of heating the suspension at a temperature exceeding 60 °C, and separating the heated suspension in the centrifuge described in the '717 patent into an aqueous phase, an oily phase and into sediments.
  • a flocculent is added to the sediments and, while the temperature is at least 50°C, the water is squeezed out by pressing on a small mesh filter.
  • the sediments are then eliminated either by discharging or by incineration.
  • the heating assists in reducing the viscosity of the oil and increases the solubility and diffusion of the flocculating agent in the emulsion.
  • This process causes particle attrition and therefore the solids can be disposed of in a coker quench stream.
  • the method employs the centrifuge described above, thus contributing to the expense of the method.
  • the invention includes the step of adding a flocculent prior to cooling the mixture.
  • the expansion method of achieving rapid cooling apparently serves to break the emulsion by rupturing the microstructure of solids protecting the oil/water interface. Once the solids settle out of the emulsion, they can be separated by centrifugation, settling or filtration. This method is disadvantaged in that applying pressure to bring water to 115°C and expanding to flash cool necessitates the use of expensive pressure vessels. Further, the efficacy of the process has not been demonstrated on a commercial scale.
  • the process for resolving emulsions in waste sludges comprises treating a waste sludge having oil, water and solids in a tight emulsion by applying a shear force to the waste sludge.
  • the shear force should be sufficient to break the tight emulsion and can be determined empirically.
  • the method comprises separating the oil, water and solids to produce three distinct phases.
  • the oil phase can be recycled as commercial grade oil.
  • the oil phase contains hydrocarbons that are heavier than water and separate with the solid phase.
  • a light oil can be added to the waste sludge to dissolve the heavy hydrocarbons, thus causing them to float, facilitating the complete de-oiling of the solids.
  • a salt such as sodium chloride
  • a salt is dissolved in the emulsion to increase the density of the separated water phase.
  • Most hydrocarbons will float above the brine, which has a density of 1.2 g/1 in normal conditions.
  • the brine can be recycled in order to minimize salt consumption.
  • the method has a particular application to a process for producing a coker quench stream from waste sludge comprising treating a waste sludge having oil, water and solids in a tight emulsion by shearing the waste sludge to break the tight emulsion; separating the oil, water and solids by gravity or centrifugation; and using the solids slurried in water as coker quench stream.
  • the oil can be recycled and heavy hydrocarbons can be separated with the aid of a light oil or salt.
  • the improvement in an improved process for producing a delayed petroleum coke, wherein a coker quench stream is introduced into a delayed coking vessel during quenching, the improvement consists of treating a waste stream containing an emulsion of water, oil and solids by applying a shear force sufficient to resolve the emulsion.
  • the resolved emulsion is separated into a separate water phase, a separate oil phase containing less than 2% BS&W and a separate solid phase containing less than 8% oil.
  • the solid phase is diluted, if necessary, to be a coker quench stream having less than 20% solids and introduced into a coker quench stream during quenching.
  • the invention relies on the fragility of emulsions to high shear forces and employs a ball mill, roller mill, hammer mill, disk attrition mill, pebble mill, double cage disintegrator, vertical stirring or tower mill, such as those produced by SVEDALA or KUBODA, a vibrator mill, such as those produced by SVEDALA, or similar equipment (see e.g., Perry's Chemical Engineer's Handbook, Chp. 8 (6th ed. 1984)) to break the boundary layer that envelops the water droplets, allowing the droplets to coalesce and thus separate from the oil. Any device capable of applying sufficient shear force to break the emulsion, as determined empirically, will suffice.
  • the relatively inexpensive ball mill such as the SRR (solid rubber rolling) mill, manufactured by S ALA, or the vertical stirring mill, also by SALA, are currently preferred.
  • SRR solid rubber rolling
  • the application of shear force breaks the emulsion and simultaneously reduces the particle size of the solids. Separation of the three phases can then be economically achieved with a Cone Bottom Tank, a Corrugated Plate Interceptor or Inclined Plate Separator, or similar equipment.
  • centrifugation with the mere ⁇ factor of a common decanter centrifuge is more than sufficient.
  • demulsifying agents and/or a flocculating agent are added to the waste before or after, preferably after, ball milling.
  • the process described here applies to the resolution of the waste sludges produced by the petroleum and other industries and produces constituents clean enough to be recycled.
  • the method allows the user to treat slop oils, such as tank bottoms, and extract commercial grade oils from the slop oils. It also allows the user to dispose of the solid constituents of a hazardous waste stream in the quench water of a coker in such a manner that the solids are incorporated in the coke without harm to the coking process, as described in U.S. Patent No. 5,443,717 (incorporated by reference herein).
  • the solids can be used as mixed with oil and used as fuel, per U.S. Patent No.
  • oily waste including used oil.
  • the oil constituent of the oily waste can be separated from the other constituents of the oily waste, thereby permitting the oil constituent to be recycled.
  • Waste sludges from industries other than the hydrocarbon processing industry can be treated in the described manner.
  • oil waste sludges are produced in large quantity by the basic metals industry, the automotive and machining industry, the meat and food processing industry, the textile industry and the like.
  • the oil constituent of saturated drilling mud may be separated from an emulsion in the drilling mud so that the oil can be recycled as part of the subsequent production of drilling mud.
  • Sedimentation separates the constituents based on their apparent density. Therefore, oil constituents that are heavier than water sediment with the solids and contaminate them.
  • a modification consists of mixing the sludge with enough light oil, such as coker gas oil, to dissolve the heavy hydrocarbons and create a mixture that is lighter than water. This mixture will thereby float and separate from the solids.
  • the density of the water phase can be increased with a salt, thus causing even the heavy hydrocarbons to float above the dense salt water.
  • reagents such as emulsion breakers, including but not limited to, polyvalent metal salts, mineral acids, adsorbents, polyamines and polyacrylates and their derivatives, alkyl substituted benzene sulfonic acids, alkyl phenolic resins and their derivatives, substituted polyalcohols, and the like.
  • emulsion breakers including but not limited to, polyvalent metal salts, mineral acids, adsorbents, polyamines and polyacrylates and their derivatives, alkyl substituted benzene sulfonic acids, alkyl phenolic resins and their derivatives, substituted polyalcohols, and the like.
  • emulsion breakers including but not limited to, polyvalent metal salts, mineral acids, adsorbents, polyamines and polyacrylates and their derivatives, alkyl substituted benzene sulfonic acids, alkyl phenolic resins and their derivatives, substituted polyalcohols, and the like.
  • Figure 1 is a diagram of the demulsification process of the present invention.
  • oil comprises any oily or greasy material that is generally immiscible with water.
  • oil can be the hydrocarbons that constitute the oily part of refinery waste.
  • solids are organic or inorganic particulate matter, such as components of the refinery soil, some carbonaceous materials, rust scales, catalyst fines, etc.
  • sludge is an emulsion of oil, water and solid matter. Sludges are produced in a variety of industries, but are characterized herein as tight emulsions, difficult to break with high G forces or chemical treatments alone.
  • Sludges may be found, for example, at the receiving end of the refinery sewers, the American Petroleum Institute (API) separator as API bottoms or as Dissolved Air Flotation (DAF) float, tank bottoms, heat exchanger bundle cleaning sludge, secondary emulsions, spills, slops, and the like.
  • API American Petroleum Institute
  • DAF Dissolved Air Flotation
  • the "solids slurry' ' or ' solid phase slurried in water” produced by the present invention may be employed as a "coker quench.”
  • the solids slurry should contain a percentage of solids that does not exceed that above which the slurry's viscosity becomes so high as to make it unpumpable, usually around 5 to 35%, or preferably 25% or 20% by weight when the oil percent is around 6% or less by weight. If necessary, water is added to the solids to ensure pumpability.
  • the maximum level of oil that may remain in a solids slurry to be used as a coker quench is 8% by weight as measured by toluene extraction.
  • the oil content will be less than 4% or less than 2%.
  • the solids slurry to be employed as a coker quench must have undergone attrition of the solid particles in such a way that more than 80% of them have a size less than 100 microns, or preferably, less than 50 microns.
  • the size is important to prevent clogging of the coke pores by large particles and thus depends, to some extent, on the size of the open pores of the coke.
  • the separate oil phase produced contains less than 2% BS&W (bottom sediments and water), preferably less than 1% BS&W and most preferably less than 0.5% BS&W, so as to be recycled as oil.
  • BS&W bottom sediments and water
  • the separate solid phase produced contains less than 8% oil, preferably less than 4% and most preferably less than 2%.
  • the combined oil phase and solid phase can be used as a liquid fuel for industrial furnaces, providing thereby a method for disposing of solid waste that is economical and meets with existing environmental regulations.
  • the liquid fuel is obtained by mixing the solid phase, oily phase, and certain chemicals, and by evaporating the residual water phase.
  • a stable suspension is formed of the solids in the separated oil. The stable suspension can be burned as a liquid fuel.
  • the process of the present invention is described with a particular emphasis on the treatment of waste products generated in the production field or in the refining of petroleum, but it does not have to be so limited.
  • Other wastes generated by industry and municipal facilities that are mixtures of water, oil and solid materials can be treated similarly.
  • the process is particularly adapted, however, to recycling the waste generated in the refining of crude oil to produce purified oil for reuse, purified water for release and de-oiled solid slurries of solids in water for use as coker quench streams.
  • the equipment that is necessary to achieve the results claimed here is much simpler and cheaper to operate and to maintain than sophisticated three phase disk and nozzle centrifuges and ancillary equipment described in the prior art, resulting in lower capital investment and significantly reduced maintenance costs.
  • the refinery waste stream is introduced through line 11 into a cone bottom tank 12 in which it sediments. Free oil and water are decanted out and taken through line 14 to settling tank 21.
  • the concentrated effluent/sludge at the bottom of the cone bottom tank 12 is introduced by line 13 into a ball mill 15.
  • Ball mill 15 has the proper charge of balls both in number and size and grinds the sludge for the proper time to achieve the resolution of the emulsion and achieve simultaneous particle size reduction.
  • Ball mill 15 might optionally be replaced by a less expensive vertical stirring mill or the SRR mill, or similar device.
  • the resulting sludge is then introduced by line 16 into a separator unit 19, which separates its feed into a liquid phase carried by line 20 into settling tank 21, where it separates into oil that goes back to the refinery by line 22 and water that goes to the refinery Waste Water Treatment Plant (WWTP) by line 24.
  • a small part of that water is carried by line 25 into mixing tank 27 where it is mixed with the effluent of the separator unit 19 entering via line 26 to make the solids pumpable.
  • the resulting aqueous slurry is conveyed by line 28 and pump 29 into the finished slurry tank 30.
  • a decanter centrifuge can be used as separator.
  • a demulsifier determined by the lab tests to be the most efficient for that waste stream and/or a flocculent can be added before centrifugation through line 17.
  • An inline mixer 18 insures its proper distribution. In case there is an unacceptable amount of hydrocarbons in mixing tank 27 due to the heavy density of the hydrocarbon (e.g., asphalt), some light oil is introduced by line 17 through the inline mixer 18 into line 16 upstream of the decanter. It dissolves the heavy hydrocarbons and the resulting solution is less dense than water.
  • a tightly emulsified water in oil emulsion containing dispersed solids was obtained from a refinery tank bottom. It was divided into three one gallon canisters to test the efficacy of the application of high shear force for the resolution of refinery emulsified waste sludges. 50 ml were taken from the first canister, 50 ml of water were added and thoroughly mixed, and the sample was heated to 180°F and centrifiiged at 500G for 4 minutes without significant separation of its constituents. This confirmed that it was indeed, a tight emulsion.
  • Sample 1 In initial tests, aliquots of 50 ml of the first canister's contents were mixed with 50 ml of water plus 1000 ppm of several surfactants, thoroughly mixed, heated to 180°F and centrifuged at 500G for 4 minutes. Even with the most efficient surfactant, determined to be Callaway 9884, the centrifuge tube presented a residual rag layer floating between oil and water and a layer of fluffy material below the water and above the more compact solids. Thus the demulsification and centrifugation @ 500G did not ensure total separation.
  • Sample 2 The contents of the second canister were submitted to ball milling for one hour. Then an aliquot of 50ml was taken, mixed with 50 ml of water and 1000 ppm of Callaway 9884, heated to 180°F and centrifuged as indicated above. This time however, the water was clear and the interfaces between phases were surprisingly well defined. Importantly, there was no trace of a rag layer or of fluffy material above the solids. Thus the demulsification and separation were complete. Sample 3: The contents of the third canister were mixed with 1000 ppm of Callaway
  • a second water in oil emulsion was tested as above to ensure that the process was applicable to different refinery waste sludges.
  • the second emulsion was also obtained from a refinery tank bottom, but had no inorganic solids. Therefore, road bed dirt and gravel were ball milled to a small particle size, sieved and the fraction between 45 ⁇ m and 1 mm was added to the water in oil emulsion to produce a 20% solids content. The solids were incorporated into the emulsion with a high speed mixer until they were completely dispersed. The emulsion was then divided into samples and treated as above with comparable results.
  • the high shear forces imparted by ball milling destroy the emulsion with or without the help of the emulsion breaking agents.
  • the emulsion was not completely broken with the demulsifier alone.
  • the constituents did not need 500G to segregate, so while a centrifuge accelerated the sedimentation, it was not essential for the process to work. This is a significant advantage over the prior art, which employ expensive, high speed centrifuges.
  • the demulsification process described herein also may be used in any industrial application that requires that the oil of an emulsion be released from the emulsion for subsequent use.
  • drilling mud is used to lubricate the drill head and bring cuttings to the surface. After a time, the drilling mud becomes saturated with cuttings and other materials. An emulsion may be formed in the saturated drilling mud from a combination of the oil, water, barite, cuttings, and other materials.
  • the oil of the drilling mud may be recovered by demulsifying the saturated drilling mud and physically separating the oil from the other constituents. In this manner, all or a substantial portion of the expensive oil of the drilling mud may be recycled for use as part of a subsequent mixture of drilling mud. This process avoids the problem of having to dispose of the spent drilling mud and allows the recovery of expensive biodegradable materials in the spent drilling mud.
  • the demulsification process described herein may also be used to recycle other forms of oily waste, including used or spent oil.
  • the demulsification process described herein may be used to separate the oil from the other ingredients of the emulsion. In this manner, the oil constituent of the oily waste can be recycled for a subsequent use.
  • One example is the recycling of used or spent motor oil. After a period of use, metal shavings and dirt contaminate motor oil, forming an emulsion of the base oil, particles, and other liquids.
  • the demulsification process of this invention may be used to separate the oil constituent of the emulsion of the used motor oil from the other constituents of the emulsion so that the oil constituent may be recycled.

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  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de séparation d'émulsions, même les plus épaisses, d'huile, d'eau et de solides en appliquant une force de cisaillement suffisante pour rompre l'émulsion. Dans une application particulière, les boues de fond de citerne produites dans l'industrie pétrolière sont traitées avec la force de cisaillement d'un broyeur à boulets ou à paliers jusqu'à la rupture de l'émulsion. La taille des particules des solides diminue simultanément. Ce procédé permet d'obtenir de l'eau, de l'huile et des boues aqueuses de solides de qualité commerciale exempts de composés huileux. La phase de solide exempte d'huile ainsi produite peut être utilisée dans un courant d'extinction de coke. On peut utiliser ce procédé de rupture d'émulsion pour désémulsionner l'huile utilisée, afin de récupérer et recycler ses constituants. En outre, on peut utiliser ce procédé de rupture d'émulsion pour désémulsionner les déchets en vue de produire ultérieurement un combustible liquide à partir de l'huile de déchets.
PCT/US1999/030636 1999-12-22 1999-12-22 Procede de rupture d'une emulsion Ceased WO2001045818A1 (fr)

Priority Applications (2)

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PCT/US1999/030636 WO2001045818A1 (fr) 1999-12-22 1999-12-22 Procede de rupture d'une emulsion
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US7867399B2 (en) 2008-11-24 2011-01-11 Arkansas Reclamation Company, Llc Method for treating waste drilling mud
US7935261B2 (en) 2008-11-24 2011-05-03 Arkansas Reclamation Company, Llc Process for treating waste drilling mud
CN107140800A (zh) * 2017-05-04 2017-09-08 广州市正高环保科技有限公司 一种油泥改性剂及其改性处理油泥转化为新型再生固体燃料的方法
CN114620913A (zh) * 2022-04-27 2022-06-14 中国科学院兰州化学物理研究所 一种轧制油底泥的固液分离方法
WO2023211463A1 (fr) * 2022-04-29 2023-11-02 John Michael Burke Systèmes et procédés d'élimination de microparticules d'un fluide de travail de métaux
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WO2005005776A1 (fr) * 2003-07-09 2005-01-20 Norsk Hydro Asa Procede et dispositif de separation d'un fluide, notamment du petrole, du gaz et de l'eau
AU2004256375B2 (en) * 2003-07-09 2009-02-26 Equinor Energy As A method and device for separation of a fluid, in particular oil, gas and water
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US8012347B2 (en) 2003-07-09 2011-09-06 Norsk Hydro Asa Device for separation of fluid, in particular oil, gas and water
US7867399B2 (en) 2008-11-24 2011-01-11 Arkansas Reclamation Company, Llc Method for treating waste drilling mud
US7935261B2 (en) 2008-11-24 2011-05-03 Arkansas Reclamation Company, Llc Process for treating waste drilling mud
CN107140800A (zh) * 2017-05-04 2017-09-08 广州市正高环保科技有限公司 一种油泥改性剂及其改性处理油泥转化为新型再生固体燃料的方法
CN114620913A (zh) * 2022-04-27 2022-06-14 中国科学院兰州化学物理研究所 一种轧制油底泥的固液分离方法
WO2023211463A1 (fr) * 2022-04-29 2023-11-02 John Michael Burke Systèmes et procédés d'élimination de microparticules d'un fluide de travail de métaux
US12091632B2 (en) 2022-04-29 2024-09-17 Quaker Chemical Corporation Systems and methods for removing micro-particles from a metalworking fluid
US12098349B2 (en) 2022-04-29 2024-09-24 Quaker Chemical Corporation Systems and methods for removing micro-particles from a metalworking fluid

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