Abstract:
A membrane that is prepared in a water in oil system and comprises a hydrophobic polymer film having controlled porosity. Such membranes are particularly well suited for use in oil drilling processes; in the separation of oil from the waste water of oil refineries; in the separating of oil from the waste water resulting from cleaning oil tankers; and the separation of oil from water used in cleaning oil tanks or containers for industrial equipment. The membranes can also be used in the dewatering process of edible protein as well as the dewatering of liquid fragrances.

Description:
FIELD OF THE INVENTION 
     The present invention relates to hydrophobic porous membranes that are prepared by water in oil polymerization systems. 
     BACKGROUND OF THE INVENTION 
     Porous membranes have been utilized for a variety of purposes such as ultrafiltration and reverse osmosis. They function as a screen or sieve and retain on their surface particles larger than their pore diameter. 
     There are many potential applications for porous membranes. For example, the smoking of tobacco has been widespread for many years and has resulted in substantial concerns regarding the health hazards caused by toxic components of tobacco smoke. Conventional fibrous filters have not been very satisfactory in reducing the amount of tar, carbon monoxide and other components of smoke. 
     Porous membranes have also been used to treat waste water, purify sewage, separate solvents from solutions containing particulates, and in the desalination of sea water, separate gas components in a gas mixture, and in like applications. 
     A variety of techniques have been utilized to prepare porous membrane filters. U.S. Pat. No. 3,100,721 describes a process for making a microporous film from nylons, polyesters and vinyl polymers by coating a polymer dispersion onto a cellophane sheet, treating the coating with water, drying the coating and stripping it from the cellophane sheet. 
     U.S. Pat. Nos. 3,642,668, 4,203,847 and 4,203,848 describe the production of a porous polyvinylidene fluoride film by coating a polymer solution on a substrate that is immersed in a leaching bath. 
     SUMMARY OF THE INVENTION 
     The present invention relates to a hydrophobic polymeric membrane having controlled pore size that is prepared in a water-in-oil system where an oil phase is the continuous phase and the water phase contains the polymer. The water phase is also referred to herein as the discontinuous phase or polymer phase. 
     A pore forming agent is incorporated into the system. If the pore forming agent is water-soluble it is incorporated into the discontinuous (water) phase. If the pore forming agent is a normally oil soluble material, it is dissolved in the continuous phase. 
     The system is heated to evaporate the continuous phase and concentrate the discontinuous polymer containing phase so that crosslinking takes place. By varying the ionic strength of the pore forming agent one can effect the surface tension between the droplets or discontinuous phase and the continuous phase. This results in controlled porosity. 
     The hydrophobic membranes of the present invention can be used in various oil-water separation processes where the major constituent of the liquid being treated is oil. For example, they may be used to separate oil from water in crude oil drilling, to dewater animal or vegetable oils, or in similar applications. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     In the drawings, 
     FIG. 1 is a cross sectional view of a membrane of the present invention coated on a support; 
     FIG. 2 is a perspective view of a multichannel tubular module incorporating membranes of the present invention; and 
     FIG. 3 is a sectional view of a flat sheet plate and frame module incorporating membranes of the present invention. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The membranes of the present invention comprise a crosslinked, water-insoluble polymer having micropores of a controlled porosity. 
     Suitable polymers include those that are hydrophobic and have an affinity for nonpolar compounds. Such polymers include polyolefins, polysilanes andfluorinated polyolefins. Representative polymers useful in the present invention include those based upon monomers such as vinyltrioxyethylsilane, vinyl trimethoxyoxyethylsilane, vinyltrichlorosilane, ethyltrioxyethylsilane and polymers such as polytetrafluoroethylene, polysulfone, polytrifluorochloroethylene, polytrifluoroethylene as well as compatible mixtures thereof. The polymer is generally present in the water-in-oil system in a concentration rangingfrom 2 to 15 percent by weight. The number average molecular weight of these polymers can range from about 50,000 to about 500,000. 
     Suitable pore forming agents can include water-soluble inorganic salts suchas sodium chloride, calcium chloride and sodium sulfate that are dissolved in the discontinuous phase. Alternatively, liquid pore forming agents suchas polyethylene glycol or sodium dodecylsulfonate form part of the continuous phase. The pore forming agents are generally present in the water-in-oil system in an amount in the range of from about 0.05 to about 30 percent by weight of the total system. When inorganic salts are utilized as the pore forming agent, the ionic strength of the salt-containing solution should be in the range of from about 0.01N to about 1.0N. When polymeric pore forming agents are utilized, their number average molecular weight can range from about 200 to about 100,000. 
     By controlling the ionic strength one can control the relative surface tensions of the discontinuous phase and the continuous phase. Thus, as thecontinuous phase is driven off, the pore forming agent causes the polymer chain to curl and entrap some oil. The pore size can be controlled by varying the ionic strength and the amount of pore forming agent. The diameter of the pores is generally in the range of from about 0.01 to 100 microns. 
     Similarly, as the continuous phase is driven off, the concentration of the crosslinking or bonding agent increases and crosslinking of the polymer orbonding of the polymer film to a suitable support takes place. Conventionalcrosslinking agents or bonding agents such as sodium tetraborate, aluminum hydroxide, acetic acid, boric acid, oxalic acid, potassium dichromate and potassium chromate may be utilized. 
     The resultant pores may form a direct or tortuous path through the film depending on the thickness of the film, the size of the pores and other factors. 
     The system can also contain surfactants if smaller micelles are desired. Suitable surfactants include conventional nonionic, cationic and anionic surfactants, which all perform equally well. Examples of suitable surfactants are dodecyl sodium sulfate and alkylsulfonates. 
     The membranes can be used with or without a support member. If it is desired to use a support member, any suitable porous substrate can be used. The thickness of the support member is generally in the range of 0.02-30 mm and the pores generally have a diameter in the range of 5-100 microns. Representative support members include commercially available high and low temperature support members that are fabricated from aluminumoxide, stainless steel graphite, polypropylene and polyvinyl chloride. It may also be desirable to pretreat the support member with an oxidizing agent to promote adhesion of the membrane film to the support member. 
     The size and porosity is measured by the mercury pressing technique. 
     The membranes can be formed by conventional techniques such as casting by coating techniques such as immersion, spraying or by dynamic forming techniques when a support member is utilized. 
     When the porous membranes of the present invention are prepared by casting techniques, a 5 to 25 weight percent concentration of the desired polymer in a water, organic solvent or mixed solvent system is prepared. From 1 to8 percent by weight of a suitable pore forming agent is added and thoroughly mixed in the polymer solution. A layer having a thickness in the range of from about 0.1 to about 0.5 mm is applied to the surface of the support member or a substrate from which the membrane can be removed. A cross linking agent or coagulant is initially present or then added to cure the membrane. The pore forming agent is then washed away. The membrane is then dried and may be used. 
     If immersion techniques are utilized, the support member can be immersed ina 0.5-10 weight percent polymer solution for 3-300 seconds. The polymer coated support member is then immersed in a solution of a coagulant or cross linking agent for 3 to 10 minutes, rinsed and dried. 
     Sprays containing 0.5-5 weight percent polymer can also be used. The thickness of the membrane can be controlled by varying the spraying time and the polymer concentration. 
     When dynamic forming techniques are utilized, the porous support member is placed in a pressurized cylinder. Polymer in a concentration of about 3 to200 ppm and a pore forming agent in a concentration of about 1 to 800 ppm are added to a feed tank wherein they form a suspension. The suspension isthen pumped into the pressurized cylinder until the porous support member is treated to the desired degree and dried. 
     Emulsions made from silicone polymers can be used as materials in fabricating dynamically formed membranes. The emulsion consists of a soluble organic solvent such as alcohol, and another solvent such as acetone, and a cross-linker such as acetic acid or boric acid. Lauric acid-tin is a suitable catalyst, and water is used to dilute the mixture. When the membrane materials are insoluble organic silicone polymers, the solvent used is a petroleum ether having a boiling point of about 30° to 90° C. 
     After the dynamic membrane has been formed a process of post treatment mustbe carried out. This includes heating the membrane support body for at least 30 minutes at a temperature of between 40°-100° C. Representative systems include: 
     
         ______________________________________Ingredient             Concentration______________________________________I - a) Emulsion of organic silicone                       0.1-5% polymers and organic polymers (e.g., polydimethyl siloxane and benzyltriethyloxide) Emulsion agent         95-99.9%b)    Cross linker          0.1-4% Primer               0.02-2% Solvent                94-99.88%II - a) Organic silicone polymers and                       0.1-5% organic polymer (e.g., polydimethyl siloxane and benzyltriethyloxide) Solvent                95-99.9%b)    Cross linker          0.1-4% Primer               0.02-2% Solvent                94-99.88%______________________________________ 
    
     The subcomponents of the system are designated by small letters; the concentrations total 100% for each subcomponent. 
     Fluorinated polymers such as polytetrafluoroethylene, polytrifluorochloroethylene and polytrifluorothylene and polysulfones suchas poly (4phenoxy 8-propyl 13-phenoxy) sulfane may also be used to produce dynamically formed membranes. Post treatment such as (a) direct heating and (b) submerging under fluorinated acid or oxynated agent followed by heating should be used. A representative fluorinated polymer system is as follows: 
     
         ______________________________________Ingredient             Concentration______________________________________Fluorinated polymeric emulsion                    5-5000 ppmAdhesive (e.g. epoxy resin)                  0.2-500 ppmIndicator (e.g. phenol red or                  0.1-50 ppmxylenol blue)______________________________________ 
    
     The Fluorinated polymeric emulsion contains ingredients in the same proportions as in Formulation I above, with a fluorinated polymer substituted for the organic silicone polymer in that example. The concentrations are the concentration, in parts per million, of the particular ingredient in the entire system. The adhesive is used to enhance the ability of the membrane material to stay in place within the pores of the supporting material. The pore size is regulated by observing the fading or absence of the indicator, which can be either phenol red or xylenol blue dye. 
     When the post treatment technique of submerging under fluorinated acid or oxynated agent followed by heating is used, the concentration of acid or agent is 1-80% and the heating temperature is between 100°-300° C. 
     EXAMPLE 
     A hydrophobic membrane is dynamically formed using the fluorinated polymeric emulsion disclosed above which is a mixture of polytefrafluroethylene and polyvinyl alcohol in a 4 to 1 ratio. The concentration of the emulsion is approximately 15 ppm. The mixture of emulsion, adhesive and indicator is then placed on a pourous ceramic module with a chute. When the color imparted by the indicator diminishes or disappears entirely the proper pore size is attained. The membrane is then dynamically formed under a pressure of 20 Kg/cm 2 . 
     The membrane is then removed from the module and submerged under 5% H 2 SO 4  for 30 minutes at a temperature of not to exceed 100° C. The color of the membrane changes from white to dark brown at this point. The membrane is then rinsed under water in order to wash away any traces of acid that remain on the surface before replacing it in the module. 
     A membrane made according to the above example was tested by pumping a mixture of coal oil and water in a ratio of 6:1 through the module with the membrane therein. The temperature was elevated to 80° C. at a pressure of 1 Kg/cm 2 . The separation of the oil from the water was 99.68%. 
     FIG. 1 is a sectional view of a membrane 1 coated on the surface of a fibrous support member 2. 
     FIG. 2 illustrates the use of porous membranes of the present invention in a tubular multichannel module 30. The module 30 contains a plurality of hollow thin walled tubular membranes 31 and rings 32 at both ends of the module 30 to fix the tubular members 31 in an appropriate position in the module 30. 
     FIG. 3 illustrates the use of porous membranes of the present invention in a plate and frame device 40. Flat sheets of membrane 41 are mounted in thedevice 40. The liquid being treated enters through inlet 42 and flows through channels 43. The permeate passes through the membranes 41 and exists through outlets 44 and 45. Retentate exits through outlet 46. 
     While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.