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Publication numberUSRE30125 E
Publication typeGrant
Application numberUS 05/951,352
Publication dateOct 23, 1979
Filing dateOct 13, 1978
Priority dateApr 13, 1970
Publication number05951352, 951352, US RE30125 E, US RE30125E, US-E-RE30125, USRE30125 E, USRE30125E
InventorsNorman N. Li, Robert P. Cahn, Adam L. Shrier
Original AssigneeExxon Research & Engineering Co.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Liquid membrane process for the separation of aqueous mixtures
US RE30125 E
Abstract
This invention relates to a process for the removal of dissolved species from aqueous solutions, which comprises contacting said aqueous solution with an emulsion, said emulsion comprising an exterior phase which is characterized as being immiscible with said aqueous solution and yet permeable to said dissolved species, and an interior phase which contains a reactant capable of converting said dissolved species to a non-permeable form. The dissolved species permeate the exterior phase, into the interior phase where they are converted into nonpermeable forms and thus retained in the interior phase of said emulsion. The aqueous solution, depleted in said dissolved species, is separated from said emulsion and the emulsion cycled for reuse. In one preferred embodiment said dissolved species are ions, and an ion exchange compound is incorporated in the exterior phase of the emulsion, to promote the permeation of said ions through the exterior phase.
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Claims(22)
What is claimed is:
1. A process for removal of a dissolved species from an aqueous solution which comprises, contacting said aqueous solution with an emulsion, said emulsion comprising an interior phase, surrounded by a surfactant containing exterior phase, said exterior phase being immiscible with said aqueous solution and said exterior phase being permeable to said dissolved species, and said interior phase comprising a reactant capable of converting said species to a nonpermeable species, whereby said species permeates the exterior phase and is converted to a nonpermeable species in the interior phase.
2. The process of claim I, wherein said exterior phase comprises from about 0.01 to 10 weight percent of an oil soluble surfactant.
3. The process of claim 2 wherein said interior phase is aqueous.
4. The process of claim 3 wherein said dissolved species is converted to a nonpermeable form by complexing with a reactant in the interior phase.
5. The process of claim 3 wherein said dissolved species is an ion.
6. The process of claim 5 wherein said exterior phase comprises an ion exchange compound.
7. The process of claim 6 wherein said ion is a cation.
8. The process of claim 7 wherein said exterior phase comprises a compound selected from the group consisting of sulfonic acids, organophosphoric acids and carboxylic acids.
9. The process of claim 6 wherein said ion is an anion.
10. The process of claim 9 wherein said exterior phase comprises an amine.
11. The process of claim 3 wherein said dissolved species is converted to a nonpermeable form in the interior phase by neutralization.
12. The process of claim 11 wherein said dissolved species is a weak acid and is neutralized in the interior phase by a strong base.
13. The process of claim 12 wherein said weak acid is selected from the group consisting of CO2, SO2, acetic acid, H2 S, phenol, HCN and citric acid.
14. The process of claim 11 wherein said dissolved species is a weak base and is neutralized in the interior phase by a strong acid.
15. The process of claim 14 wherein said dissolved species is selected from the group consisting of NH3 and nitrogen containing organic compounds.
16. The process of claim 3 wherein said dissolved species is converted to a nonpermeable form by precipitating in the interior phase.
17. The process of claim 16 wherein said dissolved species is selected from the group consisting of metal ions.
18. The process of claim 17 wherein said metal ion is selected from the group consisting of Ag, Cu, Cd and Hg.
19. The process of claim 3 wherein said surfactant is Span 80.
20. The process of claim 7 wherein said ion exchange compound is selected from the group consisting of sulfonated styrene copolymers, petroleum sulfonic acids, napthenic acids, sulfonated phenol formaldehyde copolymers, styrene-maleic acid copolymers, and styrene acrylic acid copolymers.
21. The process of claim 9 wherein said ion exchange compound is selected from compounds having the general formula: ##STR6## wherein R and R1 are independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl and C7 to C20 alkaryl radicals and R2 is selected from the group consisting of C6 to C30 alkyl, C6 to C20 aryl and C7 to C20 alkaryl radicals; and ##STR7## wherein R3, R4, R5, R6, R7, R8, R9 and y are independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl, C7 and C20 alkaryl radicals and substituted derivatives thereof, and x is an integer of from 1 to 100.
22. The process of claim 21 wherein R3 and R4 together form an alkyl succinic radical having the general formula ##STR8## wherein m is an integer varying from 10 to 60, x varies from 3 to 10, and y is selected from the group consisting of hydrogen and oxygen containing hydrocarbyl radicals having up to 10 carbons.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. Nos. 28,094 and .Badd..[.99,267.]. .Baddend..Iadd.36,686 .Iaddend.filed on Apr. 13, 1970 and .[.Dec. 17, 1970.]. .Iadd.May 12, 1970 .Iaddend.respectively, in the names of Li, Cahn and Shrier. Application Ser. No. 28,094 has issued as U.S. Pat. No. 3,617,546, and application Ser. No. .Badd..[.99,267.]..Baddend. .Iadd.36,686 .Iaddend.has issued as U.S. Pat. No. .Badd..[.3,710,519.]..Baddend. .Iadd.3,637,488. .Iaddend.

BACKGROUND OF THE INVENTION

This invention relates to a process for the removal of dissolved species (solute) from aqueous solutions, which comprises contacting said aqueous solution with an emulsion, said emulsion comprising an exterior phase which is characterized as being immiscible with said aqueous solution and yet permeable to said dissolved species, and an interior phase which contains a reactant capable of converting said dissolved species to a non-permeable form. The dissolved species permeate the exterior phase, into the interior phase where they are converted into non-permeable forms and thus retained in the interior phase of said emulsion. The aqueous solution, depleted in said dissolved species, is separated from said emulsion and the emulsion cycled for reuse. In one preferred embodiment said dissolved species are ions, and an ion exchange compound is incorporated in the exterior phase of the emulsion, to promote the permeation of said ions through the exterior phase.

Liquid surfactant membranes, as disclosed in U.S. Pat. No. 3,454,489, may be utilized to separate dissolved compounds from their aqeuous solutions. The process described therein is based on diffusion through the liquid surfactant membrane, and thus the limit of separation was reached when the concentration of the dissolved compounds on both sides of the membrane became equal.

It has now been unexpectedly discovered that a dissolved species may be efficiently removed from an aqueous solution by contacting said aqueous solution with an emulsion, said emulsion comprising an exterior phase which is immiscible with said aqueous solution and permeable to said dissolved species, and an interior phase comprising a reactant which is capable of converting said dissolved species to a form in which it is no longer permeable. The dissolved species in its non-permeable form is thus trapped in the interior phase and the concentration gradient of the permeable form of said compound between the aqueous solution and the interior phase is maintained. The concentration gradient acts to drive the dissolved compound efficiently through the exterior phase of the emulsion into the interior phase. By use of this technique small volumes of emulsion may be used to treat large volumes of aqueous solution efficiently. Thus the instant process, although not limited thereto, is useful in water pollution control, wherein large bodies of water must be treated to remove small amounts of dissolved impurities, e.g., the dissolved species.

The exterior phase of the emulsion will comprise one or more surfactants, a solvent, if needed, and/or various other additives, as further elucidated below. The exterior phase is designed to be immiscible with said aqueous solution, and to form an effective emulsion, must also be immiscible with the interior phase and with the reactant in the interior phase. The exterior phase acts as a liquid membrane through which selected, dissolved species may permeate into the interior phase where they are converted to nonpermeable forms.

The dissolved species which may be removed by the instant process include inorganic and organic, neutral and ionic, acidic and basic compounds. In each specific case the exterior phase of the emulsion must be chosen so that the dissolved species is at least slightly soluble therein. It will be obvious to the skilled artisan which exterior phase may be used for any specific dissolved species. The exterior phase may be specially adapted to solubilize any dissolved species by use of a solubilizing additive. For example, hydrocarbon soluble ion exchange compound can be dissolved in a hydrocarbon exterior phase to promote the solubility of ionic species therein.

The choice of reactant will be made in view of two factors. It must be capable of converting the dissolved species, e.g., compound, which has permeated into the interior phase, into a nonpermeable form, thus trapping said dissolved compound and keeping the concentration of said compound low in the interior phase. Also, said reactant must itself remain trapped in the interior phase. Usually the reactant will be soluble in the interior phase, but the use of insoluble reactants, i.e., solid adsorbents, or slightly soluble reagents like lime in an aqueous interior phase is feasible.

In a typical example of how the instant process may be utilized, a water immiscible solvent containing a surfactant soluble therein, is mixed with an aqueous solution containing a reactant under high shear conditions to form a stable water in oil emulsion. Said emulsion is then contacted with an aqueous stream containing a dissolved species by any of various methods, i.e., agitating a mixture of the emulsion and the aqueous stream together in a batch process, cocurrent containing in a continuous flow reactor; countercurrent contacting by bubbling said aqueous stream through a column containing said emulsion, or vice versa. In all of these procedures a difference in density between said aqueous stream and said emulsion is maintained in order to permit separation of the emulsion and the aqueous stream after contact.

During contact, the dissolved species present in the aqueous stream permeates through the exterior phase of the water in oil emulsion, into the interior phase, which comprises the reactant-containing solution, wherein said dissolved species reacts with said reactant and is converted into a nonpermeable form (thus keeping the concentration of the permeable form low in the interior phase). If the reactant was not present, the dissolved species would continue to permeate into the interior phase until the concentration of said dissolved species in the interior phase was equal to its concentration in the aqueous stream. At this point further permeation into the interior phase would cease.

By providing a reactant capable of converting said permeable species into a nonpermeable form, in the interior phase, the concentration of the permeable form of the dissolved species in the interior phase is held below the concentration in the aqueous stream. The dissolved species is thus continuously forced into the interior phase by the resulting concentration gradient.

The various dissolved species which may be separated from their aqueous solutions include weakly basic compounds, e.g., NH3, various amines, and other nitrogen-containing organic compounds. In general these are reacted in the interior phase with a strong acid, e.g., H2 SO4, HCl, HNO3, which neutralizes said basic compounds and converts them into an ionic, i.e., nonpermeable form. By maintaining a pH difference between the aqueous solution and the interior phase, the concentration of the permeable, un-ionized form of said compounds can be maintained high in the aqueous stream and low in the interior phase.

Weakly acidic compounds, e.g., CO2, SO2, acetic acid, H2 S, phenol, HCN, citric acid and many other organic acids are reacted in the interior phase with a strong base, e.g., NaOH, K2 CO3, KOH and are converted to ionic i.e., nonpermeable forms.

Various dissolved species may be precipitated in the interior phase, and thus converted to a nonpermeable form. Examples include the removal of H2 S by reaction with copper ions, and the removal of HCN by reaction with silver ions, said ions being dissolved in the interior phase.

Ionic species may also be separated from their aqueous solutions by use of the instant process, the only proviso being that said ionic species be at least somewhat soluble in the water immiscible exterior phase of the emulsion.

For example, ions of tin, iron and copper, being slightly soluble in aromatic and olefinic solvents, may be separated from aqueous solution, by utilizing a water in oil emulsion comprising an aromatic or olefinic solvent as the exterior phase.

Generally, various solubilizing additives, i.e., compounds which are soluble in the water immiscible exterior phase and are capable of interaction with ions to solubilize them, are added for the promotion of the permeation of ions through the exterior phase.

If it is desirable to remove cations from an aqueous solution, a compound selected from the group consisting of sulfonic acids, organo phosphoric acids, and carboxylic acids, may be incorporated in the exterior phase. It should be noted that compounds chosen from this group may also function as surfactants. However, best results, i.e., balancing the emulsion stability with the rate of transfer of ions across the membrane, are obtained when a nonionic surfactant as hereinafter described is combined with one of these compounds.

In general, when removing cations from an aqueous solution, the water immiscible exterior phase will comprise a non-ionic surfactant and a compound selected from the group consisting of polyfunctional sulfonic acids, polyfunctional carboxylic acids, and polyfunctional organo phosphoric acids said polyfunctional compounds are known in the art as ion exchange compounds. Said ion exchange compounds generally have a molecular weight of from 200 to 10,000 and will have a ratio of carbon atoms to functional group of greater then 5.

Examples of ion exchange compounds which are useful for transfer of ions through the membrane include: sulfonated styrene copolymers, petroleum sulfonic acids, naphthenic acids, sulfonated phenol formaldehyde copolymers, styrene-maleic acid copolymers, styrene-acrylic acid copolymers, etc.

When it is desirable to remove anions, then amines may be incorporated in the exterior phase. Amines may, likewise, function as surfactants, but as previously noted, the best balance of emulsion stability and ion transfer, requires a non-ionic surfactant and an amine.

The useful amines are also known in the art as ion exchange compounds and will contain more than 4 carbon atoms per nitrogen atom.

Useful amines include styrene copolymers containing pendant quaternary ammonium groups, including derivatives of trimethylamine or dimethylethanolamine.

A preferred group of amines are compounds of the general formula ##STR1## wherein R and R1 are independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl and C7 to C20 alkaryl radicals and R2 is selected from the group consisting of C6 to C30 alkyl, C6 to C20 aryl and C7 to C20 alkaryl radicals. Specific examples within the above definition include di-n-decylamine, dilaurylamine, methyldioctylamine, tri-n-octylamine, tri-iso-octylamine, tribenzylamine, tri-p-butylbenzylamine, tricaprylamine, 1-amino-1,1,3,3,5,5,7,7,9,9-decamethyl decane (Primene JM-T) didodecenyl-n-butylamine, trilaurylamine, etc.

Most preferred compounds, within the above definition are Primene JM-T and Amberlite LA- 2 a N-lauryl trialkyl methylamine, both available from Rohm and Haas Co.

Various polyamine derivatives are useful within the scope of the instant invention. The preferred polyamine derivatives are those having the general formula: ##STR2## wherein R3, R4, [R5, R6, R7, R8, R9 and y] are chosen from the group consisting of hydrogen, C1 to C20 alkyl, C6 to C20 aryl, C7 to C20 alkaryl radicals and substituted derivatives thereof; and x is an integer of from 1 to 100. More preferably R5, R6, R7, R8, and R9 are hydrogen, and x varies from 3 to 20.

The substituted derivatives previously mentioned are preferably selected from the group consisting of oxygen, nitrogen, sulfur, phosphorous, and halogen containing derivatives.

In the most preferred polyamine derivative, R3 and R4 together form an alkyl succinic radical having the general formula ##STR3## wherein n varies from 10 to 60, x varies from 3 to 10, R5, R6, R7, R8 and R9 are hydrogen, and y is selected from the group consisting of hydrogen and oxygen-containing hydrocarbyl radicals having up to 10 carbons e.g., acetyl, etc.

Once the ions permeate into the interior phase, they may be converted into a nonpermeable form by precipitation, complexing, etc. with a reactant maintained in the interior phase. Examples of such conversions include precipitation of Ag, Cu, Cd, and Hg ions with sulfide ions; precipitation of Ca ions with phosphate ions and vice versa; reduction of nitrate ions with ferrous ions and complexing of nitrogen oxide with ferric sulfate. Any of the well known ion complexing agents such as ethylene diamine tetra acetic acid may be utilized as reactants.

An interesting variation of the above process for separating ions from aqueous solution involves maintenance of a pH differential between the interior phase and the aqueous solution, whereby the pH at the aqueous solution-exterior phase interface promotes the solubility of the ions in the ion exchange compound containing exterior phase, and the pH at the exterior phase-interior phase interface promotes the desorption of the ions from the exterior phase and subsequent solubilizing in the interior phase.

The process of this invention contemplates the separation of dissolved compounds from aqueous solution, and thus [in order to maintain the emulsion as a phase separate from said aqueous solution] it is necessary that the emulsion be of the water in oil type. The surfactants utilized will be of the oil soluble type. In general the surfactants must have low solubility in both the aqueous solution and the interior phase. Also, the surfactant preferably promotes the permeability of the dissolved species of interest through the membrane. Specific surfactants which may be used include anionic, cationic, or nonionic surfactants.

The following anionic surfactants are useful for the process of the instant invention:

Carboxylic acids, including fatty acids, rosin acids, tall oil acids, branched alkanoic acids, etc.

Sulfuric acid esters, including alcohol sulfates, olefin sulfates, etc.

Alkane and alkylaryl sulphonates, including alkyl benzene sulfonates, alkyl naphthalene sulphonates, etc.

Phosphoric acid esters, including mono and dialkyl phosphates.

The following cationic surfactants are useful for the process of the instant invention:

Quaternary amine salts.

Nonionic surfactants are the preferred surfactant type for the practice of the process of the instant invention. A useful group of nonionic surfactants include the polyethenoxyether derivatives of alkyl phenols, alkylmercaptans, and alcohols, e.g. sorbitol, pentaerythritol, etc.

Particular nonionic surfactants for use in the instant process include compounds having the general formula ##STR4## wherein R10 may be C8 H17, C9 H19, or C10 H21 and m is an integer varying from 1.5 to 8.

The most preferred nonionic surfactant is Span 80, a fatty acid ester of anhydro sorbitol condensed with ethylene oxide.

Short-chain fluorocarbons with polar groups are frequently sufficiently soluble in hydrocarbon oils to function as surfactants. Long-chain fluorocarbons attached to a hydrocarbon chain of sufficient length are soluble in hydrocarbon oils.

Silicone oils differ broadly in their chemical structure and surface-active properties. Those of sufficiently low molecular weight to be soluble in the hydrocarbon solvent and which contain only CH3 groups attached to silicon in the (Si--O)n skeleton can be expected to be surface-active.

Since the number of surfactants is extremely large, it is not intended to burden this application with numerous examples. The following publications may be referred to for further examples: Surface Chemistry by Lloyd I. Osipow, Reinhold Publishing Company, New York (1962) chapter 8 and Surface Activity, Moilliet et al, Van Nostrand Company, Inc. (1961) Part III.

Generally the exterior phase of the emulsion comprises a water immiscible solvent, as well as one or more surfactants. The solvent may be chosen from the class consisting of hydrocarbons, halogenated hydrocarbons, ethers, higher oxygenated compounds such as alcohols, ketones, acids and esters.

The various additives which have been previously mentioned as useful for transporting ions across the membrane may function as the water immiscible solvent. In particular the various amines previously mentioned are useful solvents for the formation of water in oil emulsions.

The solvent, of course, must be liquid at the conditions at which the instant process is operated, and also must be capable, in conjunction with the surfactant, of forming a stable water in oil emulsion with the interior phase. Conveniently the interior phase is aqueous but any solvent which forms and maintains the interior phase of a stable emulsion with the selected surfactant-solvent exterior phase mixture may be used.

The interior phase exists as droplets surrounded by the solvent-surfactant exterior phase. When the water in oil emulsion is contacted with the aqueous solution, the exterior phase acts as a liquid membrane which allows certain dissolved species to permeate into the interior phase where a reactant contained therein converts them to a form which cannot permeate back through the "liquid membrane."

The water in oil emulsion must be stable so that the exterior phase coating the droplets of the interior phase does not rupture and thus allow mixing of the components of the interior phase with the aqueous solution.

It should be noted that a variation of the above process is possible wherein the aqueous solution comprises the interior phase of the water in oil emulsion, which is then contacted with a solution containing a reactant for the dissolved species. This variation although possible is not economically favored for treating pollution, where large volumes of aqueous solution would have to be emulsified, but may be of interest where small streams must be treated with large volumes of reactant.

The emulsion used in the instant process may be prepared by various methods. Weight ratios of from 0.1 to 1.8, preferably of from 0.5 to 1.0, of a reactant solution is mixed with a water immiscible solvent in which is dissolved at least about 0.0001 percent by weight, preferably from about 0.01 percent by weight to 10 percent by weight, most preferably from 0.1 percent by weight to 5 percent by weight of an oil soluble surfactant. The reactant solution is preferably aqueous with a concentration that is dependent primarily on the solubility of the reagent in the aqueous solution. Preferably the aqueous solution is saturated with the reactant or may be a slurry containing undissolved reactant. The above mixture is emulsified by use of high speed stirrers, colloid mills, valve homogenizers, ultrasonic generators or mixing jets.

When an ion exchange compound is incorporated in the exterior phase of the water in oil emulsion, it may comprise from about 1 to 99.9 percent by weight of said exterior phase. Preferably said ion exchange compound will comprise from about 4 to about 40 percent by weight of said exterior phase.

A typical water in oil emulsion, for use in separating ions from aqueous solutions, will thus comprise from 0.01 to 10 percent by weight nonionic surfactant, from 5 to 75 percent by weight ion exchange compound, and from 25 to 75 percent by weight of an aqueous solution containing a reactant for the aforesaid ion.

The emulsion is then contacted with an aqueous solution containing dissolved compounds, in a manner as previously described, whereby the dissolved compounds permeate through the "liquid membrane" exterior phase into the reagent-containing interior phase, wherein said dissolved compounds are converted to nonpermeable forms. The emulsion is then separated from the aqueous solution, which is now depleted in the dissolved compounds, and optionally the emulsion is cycled to a recovery area, where it may be regenerated. For example, the emulsion may be broken, the surfactants and solvent reused for making fresh emulsion, and the reactant regenerated for reuse.

The above process may be operated at any temperature at which the emulsion and the aqueous solution are fluid and stable; conveniently, ambient temperature is used. The pressure must likewise be sufficient to maintain the fluidity of various phases; conveniently, ambient pressures are used.

The following are specific embodiments of the instant process. The above process is general in scope, and thus there is no intention of being limited to said specific embodiments.

EXAMPLE 1

In the following runs, phenol was removed from an aqueous solution. The solution was introduced into a separation zone which was provided with a mixer. The zone was maintained at a temperature of 25 C. and a pressure of 1 atmosphere. The surfactant used was Span 80, a commercial name for sorbitan monooleate with a viscosity of 1,000 cps at 25 C., in an amount of 2 percent by weight. The mixture of surfactant, sodium hydroxide solution and surfactant solvent (a high molecular weight isoparaffin having a carbon number range of from about 25 to about 35) was emulsified and then contacted with the phenol-containing aqueous feed. After the emulsion and the aqueous solution were mixed at a rate of 100 rpm for about 50 minutes, the emulsion and the aqueous solution were separated and analyzed. The results and additional details of the experiments are included in Table I. The aqueous solution was analyzed by UV spectrography method for phenol concentration and by titration with acid for caustic concentration.

The Table indicates that in Run 1 where no sodium hydroxide was added, a high phenol concentration remained after 43 minutes of agitation. On the other hand, in Run 2 where 0.4 wt. percent of caustic was used, at the end of 19 minutes only 3 parts per million of phenol remained. In Run 3 where the caustic concentration was increased slightly to 0.5 wt. percent, phenol was reduced from 1,000 to 33 parts per million in just 53 minutes.

It should be noted that the Na content of the waste water rose very slowly, indicating very little permeation of Na-ion from the "inside" of the emulsion to the outside waste water stream.

EXAMPLE 2

In this example phosphoric acid and mono sodium phosphate were removed from aqueous solutions. The aqueous solution of phosphate was introduced into a separation zone which was provided with a mixer. The zone was maintained at ambient temperature and pressure. The surfactant used was Span 80. The mixture of emulsion containing surfactant, calcium compounds, surfactant solvents, high molecular weight amines with molecular weight below 1,000, and the phosphate-containing aqueous feed was stirred at a rate of 100 rpm for about 50 minutes. The results and additional details of the experiments are included in Table II. The feed recovered was analyzed by colorimetric method for phosphate concentration and by titration method for chloride concentration when calcium chloride was used.

              Table I______________________________________EXPERIMENTAL PHENOL REMOVALFROM WASTE STREAMS          Run number          1      2        3______________________________________Aqueous phenol solution: Ce              250      250      250. Phenol, p.p.m   1,000    200      1,000.Emulsion: Exterior phase  Iso-     Iso-     Iso-            paraffin paraffin paraffin. Volume of exterior phase, cc            200      200      200. Surfactant      2%       2%       2%            Span 80  Span 80  Span 80. Interior aqueous phase, cc            100      96.8     97. Caustic conc., wt. percent            0        0.4      0.5.______________________________________

__________________________________________________________________________RUN DATA    Phenol in      Phenol in      Phenol in    aqueous        aqueous        aqueousTime,    solution,     Percent          Time,              solution,                    Percent                         Time,                             solution,                                   Percentmin.    p.p.m.     removed          min.              p.p.m..sup.1                    removed                         min.                             p.p.m..sup.2                                   removed__________________________________________________________________________0   990   0    0   200   0    0   1,000 02   730   26   1   83    59   2   652   355   667   33   2   60    70   5   288   718   615   38   3   36    82   18   41   9628  606   39   5   17    92   38   44   9643  612   38   19  3     98   53   33   97__________________________________________________________________________ .sup.1 No NaOH in aqueous phase .sup.2 Na in final aqueous phase=43 p.p.m.

The example is representative of using an ion exchange compound to promote the permeation of ionic compounds through the exterior emulsion phase, and the subsequent conversion to a nonpermeable form by precipitation with reagent.

The Table indicates that in Runs 2 and 5 where there were no calcium compounds inside the droplets, a high phosphate concentration remained after 44 minutes of agitation. Although the membranes themselves did remove some phosphate, such process is highly inefficient and therefore not economical. On the other hand in Run 1 where 6.0 wt. percent of calcium chloride was used, at the end of 18 minutes only 0.05 percent of phosphate remained. In the other experiments where 15 percent CaCl2 and 5 percent Ca(OH)2 where used, phosphate was reduced from 0.273 percent to 0.004 percent in 44 minutes in Run 3 and from 0.273 percent to 0.018 percent in 44 minutes in Run 4.

It should be noted that the Cl content of the waste water rose very slowly, indicating slow permeation of Cl-ion from the "inside" of the emulsion to the outside waste water stream.

                                  TABLE II__________________________________________________________________________EXPERIMENTAL PHOSPHATE REMOVAL FROM WASTE WATER       Run number        1              2       3                4    5__________________________________________________________________________(1)  Aqueous feed (gm.)       107                    500(2)  Phosphoric       NaH.sub.2 PO.sub.4 . H.sub.2 O                              NaH.sub.2 PO.sub.4 . H.sub.2 O +                              H.sub.3 PO.sub.4  compound                         (1:1 by wt.).(3)  Emulsion used(gm.)       97                     281(4)  Surfactant solvent       49% JMT primene plus 49%                              95% isoparaffin (see Example 1);       polyamine derivative..sup.a                              Amberlite LA-2.sup.b plus 2%                       (1) to (7)                              polyamine derivative..sup.a                                                (1) to                                                     (1) to (7)(5)  Wt. percent organic       66.9            are same                              67                are                                                     are same  surfactant solution       as Run 1.                as Run                                                     as Run 3.  in emulsion.(6)  Surfactant       2% Span 80             1% Span 80(7)  Wt. percent aqueous       33.1                   33  phase in emulsion.(8)  Reagents (wt. per-       6% CaCl.sub.2 + 6%                       None   15% CaCl.sub.2 + 5% Ca(OH).sub.2                                                     None  cent in aq. phase).       NH.sub.4 OH (0.1 N)__________________________________________________________________________

__________________________________________________________________________(9) RUN DATATime,  PO.sub.4.sup.-3 (wt.        Cl.sup.-  (wt.             PO.sub.4.sup.-3 (wt.                   PO.sub.4.sup.-3 (wt.                         Cl.sup.-1 (wt.                              PO.sub.4.sup.-3 (wt.                                    PO.sub.4.sup.-1 (wt.)min.   percent)        percent)             percent)                   percent)                         percent)                              percent)                                    percent__________________________________________________________________________Feed   0   0.565 0    0.565 0.273 0    0.273   2   0.265 0.084             0.338 0.123 0.036                              0.133 0.204   5   0.200 0.0168             0.314 0.073 0.065                              0.120 0.205   18  0.050 0.0110             0.316 0.016      0.075 0.206   44             0.204 0.004 0.103                              0.108 0.204__________________________________________________________________________ ##STR5## m is an integer of about 40, giving said polyamine derivative a molecular weight of about 2,000. .sup.b Amberlite LA-2 is a trade name for high molecular weight (mol. wt. 353-393) primary and secondary amines which are oil-soluble but not water-soluble, have anion exchange resin properties, possess a neutralization equivalent of 360-380, an ion exchange capacity of 2.7 meq./gm., a viscosity of 18 cps. at 25 C. and a density of 0.83 gm./ml.
EXAMPLE 3--Separation of nitrate.

279 gm of liquid membrane emulsion are mixed with 465 gm of an aqueous nitrate solution at 200 RPM. The emulsion was made by emulsifying 100 gm reagent solution composed of 50 percent H2 SO4, 20 percent Fe SO4, and 30 percent H2 O in 200 gm surfactant solution (2 percent Span 80 and 98 percent isoparaffin [See Example 1]). The aqueous solution contained 219.3 ppm of NaNO3 in water. After the feed and the emulsion were contacted for 2 minutes, the concentration of NaNO3 in the feed dropped to 35.64 ppm. The concentration only increased slightly to 41.12 ppm after continuous mixing for 53 minutes more, thus indicating that there was very little membrane rupture during the mixing period.

A blank run was made in which 282 gm of liquid membrane emulsion was mixed with 492 gm. feed. The emulsion, containing no reagent, was made by emulsifying 100 gm pure water in 200 gm of the same surfactant solution. The same aqueous solution was used in the run. After the aqueous nitrate solution was continuously mixed with the emulsion for 68 minutes the concentration of NaNO3 was only reduced from 219.3 ppm to 205.6 ppm, indicating the removal of the nitrate in the absence of reagent was insignificant.

EXAMPLE 4-- Separation of Ammonia

Aqueous solution: Water containing NH4 OH (690 ppm)

Surfactant solution= 2 percent Span 80+ 98 percent isoparaffin (see Example 1) 200 gm.

Reagent solution= 2 percent HCl in water-- 100 gm.

Mixed 237 gm. of the water in oil emulsion with 500 gm feed at 250 RPM. Samples were taken from time to time from the aqueous solution.

______________________________________             NH.sub.4 OH Concentration             inMixing time       Aqueous solution(Min)             (ppm)______________________________________0                 6902                 2505                 13018                <3038                <3053                <30Total Time ofmixing = 53 minutes.______________________________________
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US6387279 *Oct 30, 2000May 14, 2002Siemens AktiengesellschaftMethod for removing nitrate ions from a solution
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Classifications
U.S. Classification210/638, 210/643
International ClassificationC02F1/66, C02F1/26, C10G21/00, B01D61/40, C10G31/11
Cooperative ClassificationC02F1/26, C10G31/11, C10G21/00, C02F1/66, B01D61/40
European ClassificationC02F1/26, B01D61/40, C10G31/11, C10G21/00, C02F1/66