Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
• • 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
• • 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
  • B01D17/08—Thickening liquid suspensions by filtration
  • B01D17/085—Thickening liquid suspensions by filtration with membranes
• • 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
  • B01D61/14—Ultrafiltration; Microfiltration
  • B01D61/145—Ultrafiltration
• • 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
  • B01D61/14—Ultrafiltration; Microfiltration
  • B01D61/18—Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/12—Composite membranes; Ultra-thin membranes

Definitions

• This invention relates to the treatment of oil emulsions particularly those containing a surface active agent.
• the separation of oil from emulsions in water is of great utility in oil production, in oil shipping where ballast tanks and bilges generate emulsions and in industry where oil emulsions are used for cutting and cooling. If the residual water is to be reused or disposed of in sewers or waterways, the degree of oil removal must be such that the residual water contains less than 10 parts per million of hydrocarbon oil.
• the separated oil be free of water since water often contains salts and causes corrosion. Although oil can contain 40% water and still burn, the chimney steam loss reduces the calorific value and the salts fuse on boiler tubes, leading to tube failure and fusion of furnace walls.
• the "Oil/Water Separation State-of-the-Art" publication prepared for Industrial Environment Research Laboratories in Cincinnati, Ohio by Rutgers State University, New Brunswick, New Jersey, United States Department of Commerce National Technical Information Service P.B. - 280755 is a thorough review of the problem and of updated separation procedures.
• a surface active agent surfactant
• a surfactant can enter the ship system from deck cleaners, oil dispersers, laundry wastes, fire foams and deliberate addition to aid cleaning of massive oil storage tanks.
• a surfactant is an essential ingredient of industrial cutting and cooling emulsions and associated rinsing liquors.
• the surfactant concentration and even the chemical nature of the surfactant are very variable due to sporadic need or uncontrolled dilution with fresh or salt water.
• Ship requirements indicate the need for an on-board system so that water, free of oil, but still containing biodegradable surfactants can be released at sea, rather than be brought to shore where dockside waters cannot accept the detergents and other soluble contaminants which may arise from chemical and biological attack on the oil in the bilges.
• poisonous hydrogen sulphide may be formed and, if so, needs immediate removal along with other biological, soluble products while still at sea.
• ultra-filtration has been used with some success for these surfactant stabilised emulsions.
• S is the oil/aqueous interfacial tension
• a is the contact angle of the continuous phase of the pore fluid with the pore wall
• d is the pore diameter.
• a polymeric porous membrane, cross-flow ultra-filter for use in separating water from an oil emulsion which contains a surface active agent or which is stabilized by the presence of fine interfacial solids characterised in that the membrane is treated with a pre-selected hydrophilic colloid whereby the effective pore size of the composite membrane will be reduced as the surface tension falls in the presence of the surface active agent or the stabilizer in the oil emulsion.
• the invention also provides a method of separating water from an oil emulsion which contains a surface active agent or which is stabilized by the presence of fine interfacial solids comprising the steps of:-
• the invention provides a mechanism which will allow the ultra-filtration membrane to possess rather coarser pores and thus give useful high rates when there is little or no surfactant but will shrink the pore size (or at least produce the equivalent effect) as the surface tension falls.
• This effect can be achieved by the addition of selected hydrophilic colloids to counteract the effect of the surfactants.
• the output falls but only to the minimum imposed by the changing system.
• the invention allows rejection of surfactant so
• purer water may be discharged.
• the amount of hydro ⁇ philic colloid and any associated surfactant discharged with the water is small and may be safely disposed of at sea, in city sewers or by landfill since they can all be made biodegradable.
• the molecular weight and/or the physical characteristics of the hydrophilic colloid to be added to the oil emulsion should be such that the colloid does not permeate the membrane.
• the concentration of hydrophilic colloid is such that a "gel-limited" permeation rate applies, i.e. increase in trans-membrane pressure under the flow conditions gives no increase in permeation rate.
• the colloid is a dynamic super-imposed layer.
• the hydrophilic colloid must be carefully chosen, preferably by trial, according to the nature of the emulsion and the additives thereto.
• the composition of the hydrophilic colloid is generally determined by the chemical ionic classification of the surfactant. If the surfactant is anionic (for example, dodecylbenzenesulphonate) then the hydrophilic colloid must also be anionic to reject the surfactant by Donnan effects.
• the anionic colloid may be mixed with a nonionic colloid but not a cationic colloid. Similarly, for a cationic surfactant the colloid must be cationic. If the surfactant is nonionic the hydrophilic colloid must also be nonionic.
• hydrophilic colloid is nonionic it must not be a substantially complete homologue of the surfactant, thus a polyethyleneglycol surfactant cannot be blocked with a very high molecular weight polyethyleneglycol such as "POLYOL COAGULANT” of Union Carbide Corporation. Indeed, where long chains are involved, even substantial (say 80%) identity of chemical constitution will render the colloid ineffective. This is to be expected since the surfactant can then "dissolve” or "associate” in the colloid gel as a mimic of the colloid which thus accepts it and allows it through.
• hydrophilic colloid for a popular long chain nonionic surfactant such as octylphenylpolyethylene- glycol ether must be a completely different chemical class such as gelatin (protein) or a branched ethyleneglycol derivative such as hydroxyethylcellulose.
• EXAMPLE 1 was repeated with the addition of 0.005% of the anionic surfactant or wetter dodecylbenzenesulphonic acid.
• the 0.2% of nonionic colloid hydroxyethylcellulose failed badly to block the anionic wetter, even at this low dose.
• EXAMPLE 5 EXAMPLE 4 was repeated but the 0.2% hydroxyethyl ⁇ cellulose nonionic colloid was replaced with 0.5% gelatin. Again the oil wet the filter as the gelatin failed to block the anionic wetter dodecylbenzenesulphonic acid.
• EXAMPLE 6 The filter of EXAMPLE 1 was used to filter a 0.2% solution of the anionic hydrophilic colloid, sodium poly- styrenesulphonate of molecular weight above 40,000 when it formed a gel-limited coating under moderate stirring.
• the solution filtered at 40 L/M h which was unchanged on the addition of 0.05% of the anionic detergent sodium dodecyl- benzenesulphonate.
• the permeate then contained only traces of the anionic detergent, the rejection through-out the filtration being 97%. The mixture did not lead to oil penetration of the filter over 20 hours although rapid penetration occurred when the sodium polystyrenesulphonate was omitted.
• EXAMPLE 7 EXAMPLE 7
• EXAMPLE 6 was repeated but with the filter modified to contain 0.5% by weight of the group -CH(OH)S ⁇ 3 .
• the now anionic filter itself rejected between 30% and 80% of the anionic sodium dodecylbenzenesulphonate detergent depending on concentration, pH, salt concentration and temperature.
• 0.2% of the anionic hydrophilic colloid sodium poly- styrenesulphonate was also used to form an anionic gel on top of the anionic filter, the rejection of detergent was over 99% at an initial concentration of 0.05%.
• the under-lying filter did not wet with oil in 24 hours when used continuously.
• the permeate contained only 5 parts per million of detergent although the initial concentration was 500 parts per million.
• EXAMPLE 6 was repeated but the 0.2% sodium polystyrene- sulphonate of ' high molecular weight was replaced by the rather permeable anionic colloid, heparin, of molecular weight 14,000 to 20,000. It was found that the filter adsorbed much of the heparin and the resulting filter gave 43% to 55% rejection of the sodium dodecylbenzenesulphonate. However when the anionic filter of EXAMPLE 7 was used the heparin was not adsorbed strongly. The result was that the joint use of an anionic filter and a too-low molecular weight anionic colloid, heparin, gave zero rejection although, as shown earlier, each individually had given reasonable rejection. Thus, only high molecular weight gel-limiting hydrophilic colloids should be used. Oil wetting of the filters matched exactly poor rejection of the anionic detergent in the individual and joint use of the anionic filter and anionic colloid.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Water Supply & Treatment (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Inorganic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Separation Using Semi-Permeable Membranes (AREA)

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• 1984
  • 1984-11-06 EP EP84904067A patent/EP0162068B1/en not_active Expired - Lifetime
  • 1984-11-06 US US06/758,709 patent/US4655927A/en not_active Expired - Fee Related
  • 1984-11-06 WO PCT/AU1984/000226 patent/WO1985002128A1/en not_active Ceased
  • 1984-11-06 JP JP59504266A patent/JPS61500305A/ja active Granted
  • 1984-11-06 DE DE8484904067T patent/DE3482413D1/de not_active Expired - Lifetime

Patent Citations (6)

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