Classifications

• • 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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
  • B01D15/08—Selective adsorption, e.g. chromatography
  • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
  • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
  • B01D15/361—Ion-exchange
  • B01D15/363—Anion-exchange
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
  • B01D61/10—Accessories; Auxiliary operations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/04—Processes using organic exchangers
  • B01J41/05—Processes using organic exchangers in the strongly basic form
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J47/00—Ion-exchange processes in general; Apparatus therefor
  • B01J47/02—Column or bed processes
• • 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
  • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
• • 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
  • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
• • 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
  • C10G33/08—Controlling or regulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
  • B01J2204/005—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the outlet side being of particular interest
• • 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
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
• • 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
  • C02F1/30—Treatment of water, waste water, or sewage by irradiation
  • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
• • 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
  • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
• • 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
  • C02F1/72—Treatment of water, waste water, or sewage by oxidation
  • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
• • 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
  • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
  • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
• • 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
  • C02F2101/32—Hydrocarbons, e.g. oil
• • 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
  • C02F2101/32—Hydrocarbons, e.g. oil
  • C02F2101/325—Emulsions
• • 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
  • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
  • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
  • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
• • 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
  • C02F2209/44—Time
  • C02F2209/445—Filter life
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/04—Diesel oil

Definitions

• the present disclosure relates to hydrocarbon-in-water purification systems and particularly to systems that break hydrocarbon-in-water emulsions and remove or separate hydrocarbons from water.
• Water contamination in fuel is a concern as it affects the performance and operation of engines. Water contamination can cause various problems including fuel filter plugging, fuel starvation, damage of engine components through cavitation and corrosion, and promotion of microbiological growth, for example.
• coalescing and separating devices have been employed to first cause the emulsified water to coalesce into larger droplets and then remove the enlarged droplets from the fuel stream.
• a removed or drained hydrocarbon-in-water emulsion stream is an output from this water from fuel separator system.
• the present disclosure relates to hydrocarbon-in-water purification systems and particularly to systems that break hydrocarbon-in-water emulsions and remove hydrocarbons from water, among other aspects.
• the a hydrocarbon-in-water purification system includes a hydrocarbon-in-water purification system having an anion exchange stage having a basic or strongly basic anion exchange resin and an inlet and a water permeate outlet and a hydrocarbon outlet.
• the inlet is in fluid communication with a hydrocarbon-in-water emulsion source.
• an engine fuel and water separation system includes a fuel and water separator system fluidly connected to an engine fuel line and having a water drain outlet, and a hydrocarbon-in-water purification system, as described herein, in fluid communication with the water drain outlet.
• an oil/water separator system includes an oil/water reservoir vessel, and a hydrocarbon-in-water purification system, as described herein, fluidly connected to the oil/water reservoir vessel.
• a method includes passing a hydrocarbon-in-water dispersion or emulsion through an anion exchange element having a basic or strongly basic anion exchange resin to break the emulsion and allow the hydrocarbon to separate from a permeate that is substantially water, and then removing the permeate from the anion exchange element.
• FIG. 1 is a schematic diagram view of a hydrocarbon-in-water purification system
• FIG. 2 is a schematic diagram view of another hydrocarbon-in-water purification system
• FIG. 3 is a schematic diagram view of a skimmer-type hydrocarbon-in-water purification system
• FIG. 4 is a schematic diagram view of another skimmer-type hydrocarbon-in-water purification system.
• hydrocarbon refers to oil or fuel materials that are primarily formed of saturated or unsaturated carbon based molecules.
• hydrocarbon-in-water emulsion refers to an emulsion where water is the continuous phase and hydrocarbon is the dispersed or discontinuous phase.
• the "hydrocarbon-in-water emulsion” described herein include hydrocarbon droplets having an average diameter greater than 5 micrometers or in a range from 5 to 25 micrometers.
• the "hydrocarbon-in-water emulsions” described herein are not thermodynamically stable.
• the “hydrocarbon-in-water emulsions” described herein have some degree of kinetic stability. Hydrocarbon droplets between 5 and 15 micrometers have significant kinetic stability.
• emulsion refers to a fluid system in which liquid droplets are dispersed in a second liquid and the two liquids are immiscible.
• absorption refers to the removal process of hydrocarbons from water and includes absorption, adsorption, and the like mechanisms of removal of hydrocarbons from water.
• high capacity hydrocarbon absorber material and “high capacity material” refer to a material that does not need to clean water to the intended cleanliness, but instead has properties that lead to high saturation capacities.
• the saturation capacity of these materials is preferably greater than 750 mg of hydrocarbon per gram of material or greater than 1000 mg of hydrocarbon per gram of material. Preferred saturation capacities will vary depending on the challenge fluid concentration and makeup.
• the phrase “polishing hydrocarbon absorber material” and “polishing material” refer to a material that can purify water down to the intended cleanliness over a wide range of incoming challenge water concentrations.
• these materials have high loading characteristics at the intended target cleanliness.
• these materials when challenged with 2500 ppm B5-in-water emulsions or dispersions, with a target cleanliness of 2 ppm, these materials have a preferred loading or polishing capacity of greater than 25 mg of hydrocarbons per gram of material or greater than 50 mg of hydrocarbon per gram of material.
• Preferred loading characteristics depend on challenge fluid concentration and makeup, and on target cleanliness.
• the present disclosure describes water purification systems and particularly to systems that break hydrocarbon-in-water emulsions and remove or separate hydrocarbons from water, among other aspects.
• an anion exchange resin breaks the emulsion and allows the hydrocarbon to separate from a permeate that is substantially water.
• Permeate may then be passed through a hydrocarbon absorber stage to adsorb hydrocarbon and form a polished water stream.
• the polished water stream can have less than 5 ppm of hydrocarbons or less than 2 ppm or hydrocarbons or less than 1 ppm of hydrocarbons.
• Hydrocarbons include fuels such as gas or diesel (including bio-diesel) or natural gas or propane or oil.
• the anion exchange resin is a basic or strongly basic anion exchange resin.
• the absorber stage is activated carbon. While the present disclosure is not so limited, an appreciation of various aspects of the disclosure will be gained through a discussion of the examples provided below.
• Fuel cleanliness requirements for fuel injection systems are demanding in order to ensure reliable engine performance.
• fuel filtration is responsible for meeting the fuel cleanliness requirements associated with the control of abrasive particles and non-dissolved water. These filters can coalesce at least a portion of the entrained water from the fuel stream and form a fuel-in-water dispersion or emulsion waste stream.
• Fuel may contain anionic surfactants.
• anionic surfactants e.g., soaps.
• soaps are more water soluble than the carboxylic acids and can encourage and stabilize hydrocarbon-in-fuel emulsions having at least 500 ppm hydrocarbon content.
• contacting stable hydrocarbon-in-water emulsions with an anion exchange material may exchange the carboxylic anion portion of the soap with a water soluble anion such as chloride, for example forming a metal chloride (such as sodium chloride), effectively removing the soap material from the hydrocarbon-in-water emulsions (or dispersions).
• a water soluble anion such as chloride
• a metal chloride such as sodium chloride
• FIG. 1 is a schematic diagram view of a hydrocarbon-in-water purification system 10.
• the hydrocarbon-in-water purification system 10 includes an anion exchange stage 20 containing an anion exchange resin 26 and an inlet 21 configured to receive a hydrocarbon-in-water emulsion 12 from a hydrocarbon-in-water emulsion source.
• the anion exchange resin 26 assists in breaking the hydrocarbon-in-water emulsion 12 allowing the water and hydrocarbon phases to separate based on their specific gravity differences.
• a substantially hydrocarbon stream 24 and a substantially water permeate stream 22 exits the anion exchange stage 20.
• a hydrocarbon absorber stage 40 may be in liquid communication and downstream of the anion exchange stage 20. Permeate 22 may enter hydrocarbon absorber stage 40 and a purified water stream 42 exits the hydrocarbon absorber stage 40.
• FIG. 2 is a schematic diagram view of another hydrocarbon-in-water purification system
• the hydrocarbon-in-water purification system 11 includes an anion exchange stage 20 containing an anion exchange resin 26 and an inlet 21 configured to receive a hydrocarbon-in-water emulsion 12 from a hydrocarbon-in-water emulsion source.
• the anion exchange resin 26 assists in breaking the hydrocarbon-in- water emulsion 12 allowing the water and hydrocarbon phases to separate based on their specific gravity differences.
• a substantially hydrocarbon stream 24 and substantially water permeate stream 22 exits the anion exchange stage 20.
• a high capacity hydrocarbon absorber stage 30 may be in liquid communication and downstream of the anion exchange stage 20.
• a polishing hydrocarbon absorber stage 40 may be liquid communication and downstream of the high capacity high capacity hydrocarbon absorber stage 30.
• Permeate 22 may enter the high capacity hydrocarbon absorber stage 30 and then the polishing hydrocarbon absorber stage 40 and a purified water stream 42 then may exit the polishing hydrocarbon absorber stage 40.
• the hydrocarbon-in-water dispersion source is fuel filter element that can coalesce water and form a hydrocarbon-in-water emulsion stream.
• the fuel filter element forms a portion of a fuel system such as those used in a diesel engine such as a vehicle engine, for example.
• This hydrocarbon-in-water emulsion stream may have hydrocarbon liquid droplets suspended in water.
• This hydrocarbon-in-water emulsion may not be thermodynamically stable but may exhibit kinetic stability.
• These hydrocarbon liquid droplets suspended in water may have an average droplet size or diameter greater than 5 micrometers or in a range from 5 to 25 micrometers.
• the hydrocarbon may be present in the hydrocarbon-in- water emulsion stream in an amount greater than 500 ppm or at least 1000 ppm or at least 5,000 ppm hydrocarbons.
• the hydrocarbon-in-water emulsion stream may include a surfactant.
• the surfactant may be present in the hydrocarbon-in-water emulsion in any emulsion stabilizing amount such as 1 ppm or greater or 10 ppm or greater or 50 ppm or greater or 100 ppm or greater. In some instances the surfactant may be present in the hydrocarbon-in-water emulsion in an amount from 1 to 100 ppm or from 5 to 50 ppm.
• the hydrocarbon-in-water emulsion stream may include a surfactant may include an anionic surfactant.
• Anionic surfactants are surfactants in which the polar portion of the molecule contains an anionic functional group (or groups).
• Anionic functional groups include carboxylate, sulfate, sulfonate, and phosphate.
• Anionic surfactants include, for example, ammonium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium laurate, sodium laureth sulfate, sodium lauroyl sarcosinate, sodium myreth sulfate, sodium pareth sulfate, sodium stearate, potassium lauryl sulfate, and other linear alkylbenzene sulfonates and primary alkylbenzene sulfonates.
• Other anionic surfactants include, for example, salts of pefluorobutanesulfonic acid, pefluorononanoic acid, perfluorooctanesulfonic acid, pefluorooctanoic acid.
• Salts of carboxylic acids may act as surfactants. These include salts of myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, and a-linoleic acid. Molecules with additional degrees of unsaturation are also included.
• the hydrocarbon-in-water purification system 10, 11 can include an antimicrobial agent.
• one or more of the anion exchange stage 20, polishing hydrocarbon absorber stage 40, or the high capacity hydrocarbon absorber stage 30 can include an antimicrobial agent.
• the antimicrobial agent can be any useful material or compound that inhibits microbe growth or kills microbes.
• Exemplary antimicrobial agents include silver, copper, organic biocides (such as quaternary amines, for example), ozone, or UV light.
• FIG. 3 is a schematic diagram view of a skimmer-type hydrocarbon-in-water purification system 100.
• This hydrocarbon-in-water purification system 100 includes an anion exchange stage 20 containing an anion exchange resin 26 and an inlet 21 configured to receive a hydrocarbon-in-water emulsion 12 from a hydrocarbon-in-water emulsion source (such as an oil/water reservoir vessel).
• the anion exchange resin 26 assists in breaking the hydrocarbon-in-water emulsion 12 allowing the water and hydrocarbon phases to separate based on their specific gravity differences.
• a substantially hydrocarbon stream 24 can be skimmed off the top of the anion exchange stage 20 and a substantially water permeate stream exits the anion exchange stage 20 and flows into a hydrocarbon absorber stage 40 via a channel 104 at the bottom of the anion exchange stage 20.
• the hydrocarbon absorber stage 40 is in liquid communication and downstream of the anion exchange stage 20 via the channel 104. Permeate enters hydrocarbon absorber stage 40 from the channel 104 and a purified water stream 42 exits the hydrocarbon absorber stage 40.
• FIG. 4 is a schematic diagram view of another skimmer-type hydrocarbon-in-water purification system 101.
• the hydrocarbon-in-water purification system 101 includes an anion exchange stage 20 containing an anion exchange resin 26 and an inlet 21 configured to receive a hydrocarbon-in-water emulsion 12 from a hydrocarbon-in-water emulsion source (such as an oil/water reservoir vessel).
• the anion exchange resin 26 assists in breaking the hydrocarbon-in-water emulsion 12 allowing the water and hydrocarbon phases to separate based on their specific gravity differences.
• a substantially hydrocarbon stream 24 can be skimmed off the top of the anion exchange stage 20 and a substantially water permeate stream exits the anion exchange stage 20 and flows into a high capacity hydrocarbon absorber stage 30 via a channel 104 at the bottom of the anion exchange stage 20.
• the high capacity hydrocarbon absorber stage 30 is in liquid communication and downstream of the anion exchange stage 20 via the channel 104.
• a polishing hydrocarbon absorber stage 40 is in liquid communication and downstream of the high capacity hydrocarbon absorber stage 30. Permeate enters the high capacity hydrocarbon absorber stage 30 from the channel 104 and then the polishing hydrocarbon absorber stage 40 and a purified water stream 42 exits the hydrocarbon absorber stage 40.
• a housing 102 can contain the hydrocarbon-in-water purification system 100, 101.
• the hydrocarbon-in-water dispersion source is an oil/water reservoir vessel.
• the oil/water reservoir vessel forms a portion of a compressor system.
• a housing 102 contains the anion exchange resin 26.
• the hydrocarbon-in-water purification system 100, 101 can include an antimicrobial agent.
• an antimicrobial agent can be any useful material or compound that inhibits microbe growth or kills microbes.
• Exemplary antimicrobial agents include silver, copper, organic biocides (such as quaternary amines, for example), ozone, or UV light.
• the hydrocarbon-in-water purification system may include a volume of anion exchange resin and a volume of hydrocarbon-in-water emulsion separated by a membrane such as a water permeable layer or element. Water and water soluble components diffuse through the membrane. Over time the water- soluble surfactants diffuse though the membrane and contact the anion exchange resin. This may have the same effect for breaking emulsions as one where the emulsion is in contact or flowing through the volume of anion exchange resin.
• the hydrocarbon-in-water emulsion has at least 500 ppm or at least 1000 ppm or at least 5,000 ppm hydrocarbons.
• the permeate has less than 500 ppm or less and 250 ppm or less than 100 ppm dissolved hydrocarbons.
• the polished water stream includes less than 5 ppm hydrocarbons or less than 2 ppm hydrocarbons, or less than 1 ppm hydrocarbons.
• anion exchange resin refers to a substance or material that contains a functional group for anion exchange.
• Anion exchange can be in the form of beads.
• the anion exchange resin is a basic anion exchange resin (preferably in the hydroxide or halogen form). In many of these embodiments the anion exchange resin is strongly basic.
• anion (or anionic) exchange resins include, but are not limited to, DOWEX
• DOWEX MARATHON A DOWEX MARATHON A MB, DOWEX MARATHON A LB, DOWEX MARATHON A2, DOWEX 11, DOWEX SBR-P, DOWEX SBR, DOWEX SAR, DOWEX MSA-1, DOWEX MSA-2, DOWEX MONOSPHERE 550A, DOWEX SBR-PC, DOWEX SBR C, DOWEX MSA-1C, DOWEX MARATHON WBA, DOWEX WGR-2, DOWEX MWA-1, DOWEX IF-59 PS, or DOWEX MONOSPHERE 600BB, which are manufactured by the Dow Chemical Company, AMBERLITE IRA958 CI, AMBERLITE IRA404 CI, AMBERLITE IRA410 CI, AMBERJET 4600 CI, AMBERJET 4200 CI, AMBERLITE IRA67, AMBERLITE IR96, AMBERLITE 4200 CI, AMBERLITE IRA402 CI, AMBERL
• the anionic exchange resin may be a stongly-basic resin, preferably a polystyrene containing a quatenary ammonium functional group.
• Strong base anion exchange resins are surprisingly efficient since the soaps that stabilize the fuel-in-water emulsion are organic anions that are exchanged during anion exchange to remove the surfactant leaving behind a metal salt.
• these strong base anion exchange resins are quatenary ammonium, macro-porous polystyrene cross-linked with divinylbenzene. Acrylate versions of these strong base anion exchange resins are also useful. These resins are commercially available. Strong base resins can be preferred because of their ability to pull organic acid in dissociated form from the soap to leave behind a metal salt (for example, NaCl).
• weak-base resins can be useful, such as PUROLITE A100 and A03.
• Strongly-basic anion exchange resin may also include styrene-divinyl benzene copolymers containing quaternary ammonium groups such as tetra alkyl ammonium hydroxide groups.
• Representative products of this nature are sold commercially under trade names such as DOWEX 1-XlO, DOWEX 2-XB, AMBERLITE IRA-410, AMBERLITE IRA-4015, AMBERLITE IRA-400, AMBERLITE A-26, AMBERLITE IRA-93, AMBERLITE IRA-94, AMBERLITE IRA-900, AMBERLITE IRA-904, DOWEX MS A- 1, DOWEX SA-2, etc.
• Anionic exchange resins may possess amino or tertiary amine functionality and may be suitable for binding carboxylic ions found in the soaps.
• Non-limiting examples of resins based on crosslinked organic polymers include DOWEX MONOSPHERE 66, DOWEX MONOSPHERE 77, DOWEX MARATHON Wba, DOWEX MARATHON Wba-2, DOWEX UPCORE MONO Wb-500, DOWEX 66, DOWEX M-43, AMBERLITE Fpa53, AMBERLITE FPA55, AMBERLITE IRA67, AMBERLITE Ira96, PUROLITE A- 100, PUROLITE A- 103, PUROLITE A847, DIAION WalO, DIAION Wa21j, DIAION Wa30, SEPABEAD FP-DA, LEWATIT MONOPLUS Mp64, and LEWATIT Vp Oc 1072.
• a hydrocarbon absorbing material includes any material capable of absorbing hydrocarbons.
• Exemplary hydrocarbon absorbing material includes polymeric material, activated carbon, or both.
• the hydrocarbon-in-water composition or water permeate from the anion exchange stage may first contact a high capacity hydrocarbon absorbing material prior to contacting a polishing hydrocarbon absorbing material. It has been found that the overall life of the hydrocarbon absorbing element can be prolonged by having the high capacity hydrocarbon absorbing material upstream of the polishing hydrocarbon absorbing material.
• q is the adsorbent loading in milli-grams of adsorbate per gram of adsorbent (x/m)
• c e is the equilibrium adsorbate concentration in solution
• K f and 1/n are the isotherm parameters that are dependent on the adsorbate, adsorbent, and temperature.
• the Freundlich Isotherm expression can be used to determine the adsorbent loading at a particular target equilibrium adsorbate concentration.
• the equilibrium adsorbate concentration (c e ) is equal to the incoming adsorbate concentration (c 0 ) the material is exhausted.
• the loading capacity under these conditions is called the saturation capacity or q sat -
• the saturation capacity of a material varies with different incoming adsorbate concentrations.
• a material that has high saturation capacity is called a high capacity hydrocarbon absorber material or high capacity material.
• polishing capacity (c t ) is less than the incoming adsorbate concentration.
• the adsorbent loading determined from the Freundlich Isotherm expression at the intended target adsorbate concentration is deemed the polishing capacity or q t .
• the polishing capacity of a material varies with different incoming adsorbate concentrations and target adsorbate concentrations. The polishing capacity is generally less than the saturation capacity.
• a material that has high polishing capacity is called a polishing hydrocarbon absorber material or polishing material.
• the high capacity hydrocarbon absorber material has a greater saturation capacity (q sat ) than the polishing hydrocarbon absorber material and the polishing hydrocarbon absorber material has a greater polishing capacity (q t ) than the high capacity hydrocarbon absorber material.
• the saturation capacity (q sat ) and polishing capacity (q t ) is determined with the same incoming adsorbate concentration.
• a hydrocarbon-in-water purification system containing separate sections of a high capacity material followed by a polishing material has an increased lifetime over a similar sized system of a single material.
• a filter housing containing separate sections of a high capacity material followed by a polishing material can have an increased lifetime over a similar sized filter housing of a single material.
• the high capacity material and the polishing material are configured in serial flow orientation to each other where the polishing material is downstream from the high capacity material.
• Activated carbon is a fine-grained carbon with an extremely large surface area and a highly porous structure. Its adsorption capacity is therefore especially high and is especially pronounced for hydrocarbons in particular. Activated carbon consists primarily of carbon (mostly >90%) with a strongly porous structure. In addition, the internal surface area of the activated carbon is between 500 and 2000 m 2 /g carbon, which explains the high adsorption capacity of the activated carbon.
• a "high capacity" activated carbon is a material that has a loading at saturation (q sat ) of at least 25% or at least 50% or at least 75% greater than a control sample of activated carbon (referred to herein as polishing hydrocarbon absorbing material).
• the high capacity hydrocarbon absorber material has a greater saturation capacity (q sat ) than the polishing hydrocarbon absorber material.
• the high capacity hydrocarbon absorbing polymeric material includes hydrocarbon absorbing polymeric polyethylene, polypropylene, polyurethane, polyester, and combinations thereof. These absorbing polymeric materials can be in the form of a non-woven fabric layer, nanofiber layer, a sponge or polymer foam element or layer. In other embodiments the high capacity hydrocarbon absorbing material is an activated carbon. In some embodiments, the high capacity hydrocarbon absorbing material includes both a high capacity hydrocarbon absorbing polymeric material and a high capacity hydrocarbon absorbing activated carbon material.
• the high capacity hydrocarbon absorbing material includes one or more or two or more different types or kinds of high capacity hydrocarbon absorbing material.
• the two or more high capacity hydrocarbon absorbing materials may be mixed together within a single volume or separated from each other by a divider or spacer element where they are in serial flow orientation to each other.
• the high capacity hydrocarbon absorbing material includes two or more high capacity hydrocarbon absorbing activated carbon materials.
• the two or more high capacity hydrocarbon absorbing activated carbon material may be mixed together within a single volume or separated from each other by a divider or spacer element where they are in serial flow orientation to each other.
• the high capacity hydrocarbon absorbing material includes two or more high capacity hydrocarbon absorbing polymeric materials.
• the two or more high capacity hydrocarbon absorbing polymeric materials may be mixed together within a single volume or separated from each other by a divider or spacer element where they are in serial flow orientation to each other.
• the high capacity hydrocarbon absorbing material includes a high capacity hydrocarbon absorbing polymeric material and a high capacity hydrocarbon absorbing activated carbon material.
• the high capacity hydrocarbon absorbing polymeric material and the high capacity hydrocarbon absorbing activated carbon material may be mixed together within a single volume or separated from each other by a divider or spacer element where they are in serial flow orientation to each other.
• the high capacity hydrocarbon absorbing polymeric material may represent from 10 to 90 wt% of the total high capacity hydrocarbon absorbing material and a high capacity hydrocarbon absorbing activated carbon material may represent from 90 to 10% of the total high capacity hydrocarbon absorbing material.
• the high capacity hydrocarbon absorbing polymeric material may represent from 25 to 50 wt% of the total high capacity hydrocarbon absorbing material and a high capacity hydrocarbon absorbing activated carbon material may represent from 75 to 50% of the total high capacity hydrocarbon absorbing material.
• the high capacity hydrocarbon absorbing polymeric material may represent from 75 to 50 wt% of the total high capacity hydrocarbon absorbing material and a high capacity hydrocarbon absorbing activated carbon material may represent from 25 to 50% of the total high capacity hydrocarbon absorbing material.
• the polishing hydrocarbon absorber material is an activated carbon.
• the polishing hydrocarbon absorbing material includes two or more polishing hydrocarbon absorbing activated carbon materials. The two or more polishing hydrocarbon absorbing activated carbon material may be mixed together within a single volume or separated from each other by a divider or spacer element where they are in serial flow orientation to each other.
• the high capacity hydrocarbon absorbing material and the polishing hydrocarbon absorber material are different materials.
• both the hydrocarbon absorbing material and the hydrocarbon absorber material can be activated carbon, however, they are different types of activated carbon that have different absorption properties.
• the polishing activated carbon has a greater polishing capacity (q t ) than the high capacity hydrocarbon absorber material.
• the hydrocarbon-in-water purification system has about an equal weight or volume amount of high capacity hydrocarbon absorber material as compared to polishing hydrocarbon absorber material.
• the high capacity hydrocarbon absorber material represents from 45 to 55 wt% of the total absorber material (contained within the hydrocarbon-in-water purification system) and the polishing hydrocarbon absorber material is about 55% to 45% of the total absorber material.
• the high capacity hydrocarbon absorber material represents from 55% to 95% wt of the total absorber material and the polishing hydrocarbon absorber material is about 45%) to 5% of the total absorber material.
• polishing hydrocarbon absorber material As compared to high capacity hydrocarbon absorber material has been shown to improve the lifetime of the overall hydrocarbon in water purification system.
• the high capacity hydrocarbon absorber material represents from 15%> to 45%) wt of the total absorber material and the polishing hydrocarbon absorber material is about 85%) to 55% wt of the total absorber material.
• the hydrocarbon-in-water purification system has about 2/3 high capacity hydrocarbon absorber material and 1/3 polishing hydrocarbon absorber material.
• the high capacity hydrocarbon absorber material represents from 60 to 75 wt% of the total absorber material (contained within the hydrocarbon-in-water purification system) and the polishing hydrocarbon absorber material is about 40% to 25% of the total absorber material.
• terms such as “vertical”, “horizontal”, “above”, “below”, “left” , “right”, “upper” and “lower”, “clockwise” and “counter clockwise” and other similar terms refer to relative positions as shown in the figures. In general, a physical embodiment can have a different orientation, and in that case, the terms are intended to refer to relative positions modified to the actual orientation of the device.
• a fuel-in-water emulsion was prepared by grinding 2.0 mL of B5 diesel fuel (5% biodiesel) in 500 mL of distilled water. An additional 1.0 L of distilled water was added to the emulsion. The bottom 1.0 L of this emulsion was gathered for testing. The hydrocarbon drops within the emulsion were visually determined to be between 2.8 and 12 micrometers in diameter with an average diameter of 6.4 micrometers.
• GC-MS testing was used to determine the hydrocarbon content of this emulsion as follows. A sample of emulsion (5.0 mL) was combined with 5 N HC1 (0.5 mL) and extracted in hexane (2.0 mL) for 1 hour. The hexane samples were diluted 1 : 10 and run by a standard GC-MS method. The MS signal was integrated and compared a calibration of a hexadecane (CI 6) standard. The emulsion sample contained 815 ppm hydrocarbons, which includes both dissolved and emulsified hydrocarbons.
• Samples containing anion exchange resin were prepared by placing 1.0 g of resin in a vial with 10 mL of emulsion. Resin samples tested were Purolite A500, Purolite A100, and Purolite A103. A sample containing no anion exchange resin was prepared as a control. The next day the water samples from the Purolite A100 and Purolite A103 resins did not visibly contain an emulsion.
• a concentrated fuel(B5)-in-water emulsion was exposed to a strong base anion exchange resin.
• the hydrocarbon concentration of the fuel-in-water emulsion was approximately 100,000 ppm.
• the addition of strong base anon exchange resin causes a distinct separation of the fuel and water into separate phases.
• a glass column was filled with lOg of Purolite A500 anion exchange resin (available from Purolite Corp. Bala Cynwyd, PA).
• a glass column was filled with lOg of Purolite A103 anion exchange resin.
• a glass column was filled with lOg of Purolite A500 anion exchange resin.
• the hydrocarbon-in-water emulsion was allowed to drain through the anon exchange bed.
• the initial efficiency for the first 200 mL was 77% (949ppm leaving bed).
• the final efficiency for the last 200mL was 92% (223ppm leaving bed).
• the flowrate decreased and a distinct fuel layer formed at the top of the anion exchange bed.
• a hydrocarbon-in-water emulsion was prepared with a soy -based biodiesel fuel (B100 or
• Water condensate from an air-oil separator on a compressor was collected.
• the water was white and hazy with a hydrocarbon emulsion.
• the hydrocarbons are likely from the compressor oil, which was AEON 4000 (available from Gardner Denver) in this compressor system.
• AEON 4000 is a hydrotreated mineral oil containing a proprietary additive package available from a variety of commercial dealers.
• the water condensate (hydrocarbon-in-water emulsion) was placed in a vial with Purolite A500 anion exchange resin. After 18 hours the emulsion had separated and the water was visibly clear. A control sample containing only the water condensate did not separate during this time.
• the Freundlich Isotherm constants, K f and 1/n, are fitting constants that indicate the extent of interaction between the adsorbate and adsorbent.
• the filter is designed to remove diesel hydrocarbons from water.
• the adsorbent properties of various materials were determined as follows. Various masses of each material (50mg - 500mg) were challenged with 20 mL of a B5 diesel fuel-in-water dispersion (typically 1000 - 2500 ppm hydrocarbon content).
• q is the adsorbent loading in mg of hydrocarbons/g adsorbent (x/m)
• c e is the equilibrium hydrocarbon concentration in the water
• K f and 1/n are the isotherm parameters that are material dependent and temperature dependent.
• the isotherm parameters tended to be dependent on the initial fuel-in-water dispersion concentration. Isotherms constants and capacity values for a variety of materials are presented in Table 3 (materials challenged with 2500ppm B5 diesel fuel-in-water dispersion) and Table 4 (materials challenged with lOOOppm B5 diesel fuel-in-water dispersion).
• Norit GCN 1240 is commercially available from Cabot Corporation (Boston, MA).
• Silcarbon K48 is commercially available from Silcarbon Aktivkohle GmbH
• Chemviron Carbosrb 28FB is commercially available from Chemviron Carbon (Feluy,
• Norit GCN 1240 carbon has a higher loading capacity when targeting an outlet hydrocarbon concentration of 2 ppm. Therefore, a hydrocarbon in water purification system including a Silcarbon K48 high capacity stage followed by a Norit GCN 1240 polishing stage will have a longer lifetime than an equal mass system having only Norit GCN 1240 polishing carbon.
• a filter containing 357g of Norit GCN 1240 will purify 68L of water before breaking through the target concentration of 2ppm.
• the optimal lifetime in the multi-batch model is 60% by weight high capacity carbon, and 40% by weight polishing carbon. In this ratio the will purify 82L before breakthrough at 2ppm. This is a 21% increase in hydrocarbon absorber filter lifetime.
• a typical polishing carbon was compared to a polyurethane foam (Restek; Catalog #22957).
• the polyurethane and polishing carbon were challenged with 1000 ppm hydrocarbons (B5) in water dispersion to determine the Freundlich Isotherm parameters Log K and 1/n (Table 2). From these values the loading at saturation and at a target cleanliness (polishing) are computed.
• the target cleanliness is 2 ppm hydrocarbons in water.
• a two-stage filter having a high-capacity polymer stage followed by a polishing carbon has a longer expected lifetime than a filter of carbon alone.
• a calculated lifetime of a 250g polishing carbon element is 112L of before breaking through the target concentration of 2ppm.
• a filter element designed using 50g of Restek polyurethane followed by 200g of polishing carbon has a calculated lifetime to 132L before breakthrough. This is an 18% increase in hydrocarbon absorber filter lifetime.
• the order of the absorbent stages is important to increase the overall lifetime of the hydrocarbon in water purification system. If the stages in the previous example are reversed (200g polishing carbon followed by 50g of Restek polyurethane) the lifetime of the system is decreased to 80L before breakthrough. This is a 29% decrease in hydrocarbon absorber filter lifetime.

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