JPS5948642B2 - Novel liquid film formulations and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a water-in-oil emulsion in which the oil phase consists of a sulfonated polymer having a main chain that is substantially non-aromatic, such as up to 10 mole percent aromatic. This invention relates to certain novel liquid film formulations and their use in high temperature liquid film processes.

The present emulsion is useful in liquid film water treatment processes, particularly in water treatment processes where it is desirable to carry out the process at high temperatures. In the most preferred embodiment,
This composition is used in a liquid film sour water treatment process.
In this case, ammonia permeates through the external phase of the emulsion into the acidic internal phase where it is converted into non-permeable form, e.g. ammonium ions, while H2S is continuously stripped from the waste solution by an inert gas such as water vapor. The ammonium sulfide-containing wastewater stream is converted into a liquid film emulsion, under conditions where it is removed with
That is, it is brought into contact with the emulsion of the present invention. This type of process is most effectively carried out at high temperatures above 80° C., at which temperatures the emulsions of the invention are extremely stable. February 6, 1975
German Patent Publication No. 2,434,590 published by Tako includes U.S. Patent No. 3,410,7, which is cited here.
No. 94, No. 3, 617, 546, No. 3, 779, 90
7 describes a method for removing salts of weak acids and bases from solutions by liquid film technology.

The method described in DOS No. 2,434,590 involves permeating through the external phase of a liquid film emulsion and converting it into an impermeable form in the internal phase in order to remove weak acids or weak bases or their hydrolysis products from solutions. It uses liquid film technology. The weak acids or bases or their hydrolysis products can be simultaneously stripped from the solution by means of an inert gas or by applying vacuum to the system. This method has been found to be most effective when carried out at high temperatures, for example 80°C. However, in this temperature range, many liquid film formulations or water-in-oil emulsions are unstable. In the method of the present invention, the above problem is solved by a new formulation that has been found to be stable at temperatures up to 100°C. The present invention relates to novel liquid film formulations in which the oil phase is a water-in-oil emulsion consisting of a sulfonated polymer having a backbone that is substantially non-aromatic.

The new formulation also includes a water-immiscible solvent for the sulfonated polymer and, although not required, an oil-soluble surfactant can also be used in the formulation. The internal aqueous phase of the emulsion can consist of a base or an acid. The emulsions of the invention are particularly suitable for use in liquid film processes in which aqueous solutions are treated with liquid film formulations at elevated temperatures. Furthermore, when this emulsion is utilized in the preferred treatment of sour water, the emulsion usually consists of a strong acid or a renewable acid. The renewable acids used in forming the compositions of the present invention are DOS No. 2,434,590.
Details are given in the issue. In general, sulfonated polymers useful in the compositions and methods of the present invention are described and claimed in US Pat. No. 3,642,728, which is incorporated herein by reference.

In the present invention, the term "substantially non-aromatic" means that the main chain consists of 25 mol% or less, preferably 10 mol% or less of aromatic groups.

This is a necessary restriction. This is due to the unexpected discovery that aromatic-containing sulfonated polymers do not form stable emulsions with the solvent systems utilized in certain high-temperature liquid film processes, such as liquid film Sawa-Isui processing. be. Preferred sulfonated polymers of the present invention are selected from the group consisting of sulfonated butyl polymers and sulfonated ethylene-propylene copolymers.

Most preferably, the composition of the invention comprises a sulfonated butyl polymer. The butyl polymer is made by copolymerizing isobutylene, isoprene, and optionally a third monomer, such as cyclopentadiene. Preferred sulfobutyl polymers of the present invention contain 0.25 to 10 mol% of sulfonic acid groups, more preferably about 0.5 to 5 mol%. Contains sulfonic acid groups. This copolymer is covered by U.S. Patent No.
, 642,728. Preferred sulfobutyl polymers of the invention have at least 1,0
00, preferably from 5,000 to 50,000. Other sulfonated polymers useful for making the compositions of the invention consist of sulfonated copolymers of isobutylene and piperylene, isobutylene and cyclopentadiene, isobutylene and methylcyclopentadiene, isobutylene and β-pinene. You can choose from a group.

Is the diene content of these polymers 0.5 to 30 moles? , preferably in the range of 1 to 25 mol%. Various sulfonated terpolymers are also useful in making the compositions of this invention. For example, U.S. Patent No. 3,642,72
According to the teaching of No. 8, isobutylene is converted into two of the above conjugated dienes.
The sulfonated polymers useful in the present invention can be obtained by copolymerizing with a species and sulfonating the resulting copolymer. Other copolymers that are less preferred but useful in the present invention include copolymerizing ethylene and propylene with dienes such as synchropentadiene, ethylidene norbornene, or 1,6-hexadiene and preparing the copolymers as described above. Produced by sulfonation.

This terpolymer is 0.2 to 10 mol% before sulfonation.
The degree of unsaturation is more preferably 0.5 to 7 mol %. Finally, highly unsaturated non-aromatic polymers can be sulfonated and used in making the compositions of the invention. For example, polybutadiene and polyisoprene homopolymers can be utilized. The polymers generally contain from 0.25 to 20 mol%, preferably from 0.5 to 5 mol%, of sulfonic acid groups, with at least 1,000, preferably 5,000 sulfonic acid groups.
It has a number average molecular weight of ~50,000.

The use of emulsions made from sulfonated polymers is not limited to sawa water treatment.

These have very wide applicability to other liquid film methods. In systems containing strong acids and/or strong bases, the sulfonated polymers described above act as emulsifiers and, unlike many surfactants, do not tend to hydrolyze under the conditions of use.
The emulsions mentioned above are particularly advantageous. When using high temperatures and strong acids or bases, it is important to use good judgment in choosing the solvent for the sulfonated polymer.

Therefore, solvents such as esters that can be easily hydrolyzed should not be used. Another limitation is the volatility of the solvent. Therefore, hydrocarbons and other solvents that are volatile or steam distillable at 80° C. cannot be used. Another criterion for solvent selection in water treatment processes is toxicity. Solvents that leave toxic residues in the water should be avoided. It is also important that the solvent used in this process should be liquid at the operating conditions and give a film, and should not have a tendency to solidify during use. To facilitate separation of the emulsion from the feed, the solvent should be chosen such that the specific gravity of the formulated emulsion differs by at least 0.025 from the specific gravity of the feed stream with which the emulsion is to be contacted. . Therefore, if the difference in specific gravity between the feed stream and the emulsion is too small, their separation will take a long time. Other considerations will be apparent to those skilled in the art.

For the above reasons, preferred solvents are selected from the following group: 2
Petroleum distillates with boiling points above 00'C.

Unless mixed with other solvents to lower the melting point,
High boiling n-paraffins with melting points of 70° C. or higher must not be used. A halogen such as chlorine or a benzene ring or a cycloalkyl ring, i.e. 10
Paraffinic solvents that can be substituted by mole % or less.

Preferred solvents have a molecular weight of about 10 to about 100, most preferably 3
Contains petroleum distillates known as isoparaffins having an average carbon number of 0 to 75. An example of this type of solvent is purified isoparaffin, known as Solvent Neutral, available from Exxon Chemical Company. Almost all of these, such as Solvent Neutral 100, Solvent Neutral 150), Solvent Neutral 600, and various intermediate grades are suitable for the present invention (numbers indicate SUS viscosity at 100F). Brightstock, COray
Other petroleum fractions such as 90 and the like are also suitable. These are petroleum lubricants having viscosities of 479.4 and 412.2 centistokes at 100F, respectively. For many applications, it may be desirable to use mixed solvents, such as a combination of Solvent Neutral 100 and Solvent Neutral 600. Although the most preferred form of the sulfonated polymer used to make the compositions of this invention is its free acid, long chain amines or polyamines can be used as neutralizing agents.

Amines useful as neutralizing agents include, for example, triamines containing C6-Cl6 hydrocarbyl groups, such as trioctylamine; diamines containing, for example, C8-Cl6 hydrocarbyl groups, such as didodecylamine. This amine is chosen for its lack of solubility in water. When these amines or their salts have significant solubility in water, they are susceptible to loss when utilized in the internal phase with strong acids and bases.
As discussed below, salts of these sulfonic acids, such as ammonium, potassium, sodium, etc., are not thermally useful in this application due to their lack of solubility in the solvent system used.
The copolymer, e.g. isobutylene-isoprene copolymer, is first sulfonated and then the solvent used for its synthesis, such as methylene chloride, volatile hydrocarbons and methanol, quenching agent, is mixed with the desired solvent for the emulsion formulation, e.g. By substitution with Solvent Neutral 100 or Solvent Neutral 600, polymers containing free sulfonic acid groups are made.

This method is known in the art as solvent displacement.
An alternative method is to neutralize these sulfonic acid polymer salts with an acid such as sulfuric acid and extract the polymer with the desired solvent. This polymer solution is stable indefinitely when stored in an amber bottle. The concentration of the sulfonic acid polymer used to make the compositions of the invention can vary from 0.05 to 40% by weight, preferably from 0.1 to 30% by weight in the solvent. In many liquid film processes, such as sour water treatment, it is desirable to maximize the rate of transfer of ammonia to the internal phase and the removal of H2S by an inert gas such as water vapor or by reduced pressure.

This can be accomplished by operating at higher temperatures than ambient temperature, where the vapor pressure of H2S increases substantially and its solubility in water decreases. The solubility of H2S in water is 0.34% at 25℃
and 0.04% at 90°C. It is clear that when carrying out the process at normal pressure, temperatures of 80 DEG to 85 DEG C. are very practical. One of the significant advantages of using the sulfonic acid polymers described above is that no additional surfactants are required to stabilize the emulsion.

The risk of hydrolysis and/or decomposition at high operating temperatures is thus avoided. The present sulfonated polymers provide both additive and surfactant properties necessary for liquid film processes. Moreover, the present sulfonic acid polymer has an operating temperature of, for example, 80 to
It has a suitable hydrophilic-lipophilic balance at 100°C. Unlike many other additives commonly used at the above operating temperatures, such as polyisobutylsuccinic anhydride-tetraethylenepentamine, the present sulfonic acid polymers are shown to be inert to hydrogen sulfide attack in the liquid film process. I understand. ．． All of the above factors make the sulfonic acid polymers particularly suitable for forming emulsions useful in high temperature liquid film processes, especially liquid film sour water treatment processes.

The above components, i.e. sulfonated polymers with or without surfactants and solvents, take into account their interaction to form stable emulsions at high temperatures, especially in the presence of strong acids and strong bases. are selected as such.

The selection of particular combinations will be apparent to those skilled in the emulsion art with the teachings of this description. Generally, emulsions of the invention are made by methods known in the art. For example, the sulfonated polymer can be dissolved in a solvent and then the surfactant can be added and dissolved. However, the components can be mixed in any order. The aqueous internal phase can then be added to the oil phase while stirring with equipment known in the art to create a stable emulsion. For example, ingredients can be emulsified using a paddle with an agitator that can move at high speed. Other known emulsion forming techniques that may be used include the use of colloid mills that break large droplets with high shear forces.

A homogenizer can also be used after pre-emulsification in a mixing vessel, colloid mill, or other equipment. In this type of operation, a coarse emulsion is pumped at high speed through the mouth of a Jiyanome valve. The droplets are crushed partly by the simple "sieving action" and partly by the strong shearing force that starts at the eye orifice of the sieve. Other emulsifying devices similar to the above-mentioned high-power types include, for example, special mixing pumps, centrifugal emulsifiers, ultrasonic generators, grooved mixers, and those that generate ultrasonic vibrations, such as mixing dinits, which produce turbulent coarse emulsions. A turbulent flow device that causes flow along a tube at a velocity faster than the critical velocity of the flow. Generally, the compositions of the present invention are 10-90% by weight. of the oil phase, preferably 30 to 60% by weight, with the remainder being an aqueous internal phase. This internal phase can consist of a strong acid or base or any other agent described in US Pat. No. 3,779,907.

However, as mentioned above, these emulsions are
34,590. Therefore, in the composition of the present invention, preferably the internal phase is that described in the above-mentioned patent. Most preferably the internal phase consists of an acid (a strong acid or a renewable acid) or a strong base. The concentration of acid or base in the internal phase of the emulsion is adjusted so that the emulsion can be used economically. Generally, considering the stability of the emulsion, the above concentration may be as high as possible, even up to saturation concentration, for example concentrations of 1 to 30% by weight can be used. The present invention further provides a novel liquid film formulation comprising an aqueous inner phase and a water-immiscible outer phase, said water-immiscible outer phase comprising an ethylene monovinyl acetate copolymer and a type of ethylene monoacetate copolymer for said polymer. It concerns an emulsion consisting of a solvent.

The composition preferably further comprises a water-insoluble surfactant for emulsion stabilization. In a preferred embodiment, the aqueous internal phase is a strong acid, e.g. 1 to 30% by weight. of sulfuric acid, preferably from about 1 to about 10% by weight. This emulsion is useful in liquid film methods for the separation of dissolved components from aqueous solutions. The emulsions of the invention are characterized by a very low swelling when brought into contact with aqueous solutions, especially at high temperatures, and are therefore particularly useful for the treatment of sour water feed streams by liquid film technology. In the liquid film process, the emulsion is brought into contact with an aqueous feed stream containing the dissolved substances to be removed by permeation through the external phase of the emulsion (liquid film) into the internal phase under constantly agitated conditions. let

The emulsion is then separated by stopping stirring and allowing the emulsion to settle. Emulsions useful in water treatment processes are characterized as water-in-oil emulsions and can be stabilized by incorporating oil-soluble surfactants into the external phase of the emulsion.

Due to the hydrophilic and lipophilic nature of surfactants, rapid settling of the emulsion after contact with an aqueous feed stream is not always obtained. Furthermore, emulsions are known to swell when brought into contact with aqueous feed streams, especially at high temperatures, e.g. 80°C, and in some cases the entire mass, i.e. feed stream and emulsion, gels. .

Finally, it has been observed that in some liquid film processes, after settling of a large portion of the emulsion, the product feed stream remains hazy due to the formation of very small emulsion particles that do not settle with the majority of the emulsion. It was done. When using the liquid film method for water pollution removal, residual haze in the treated water is completely unacceptable. The composition of the present invention can be used in liquid film water treatment methods to solve all of the above problems.

The ethylene-vinyl acetate copolymers used to form the compositions of the present invention are characterized as having a molecular weight of about 500 to about 100,000, preferably about 500 to 10,000. These polymers can be synthesized by copolymerizing ethylene and vinyl acetate at high temperature and pressure using a free radical method.

This polymer is described in U.S. Pat. No. 3, '6, incorporated herein by reference.
38,349 and German Patent No. 1,914,756. The percentage of vinyl acetate in this copolymer can vary from 1 to 75% by weight;
Preferably it is 5 to 40% by weight. In the above polymerization,
Instead of vinyl acetate, other esters of vinyl alcohol containing 1 to 20 carbon atoms in the alkanoate portion of the ester can be used.

Examples of the above monomers include vinyl formate, vinyl propionate, vinyl neopentanoate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate,
Contains vinyl stearate, vinyl benzoate, vinyl salicylate, thiol vinyl acetate, vinyl pivalate, vinyl neodecanoate, etc. Similarly, esters of acrylic acid and methacrylic acid can be copolymerized with ethylene instead of or in combination with the vinyl esters mentioned above. Examples of the above monomers include methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, dodecyl acrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, and the like. In this case, acrylic acid and methacrylic acid can also be used instead of or in combination with the above-mentioned esters of acrylic acid and methacrylic acid. Many other vinyl monomers can be copolymerized with ethylene and will be apparent to those skilled in the art. Non-vinyl monomers such as allyl acetate and itaconic acid can also be used. Materials obtained by copolymerizing one or more monomers also yield terpolymers suitable for this application.

For example, ethylene in combination with vinyl acetate and methacrylic acid, vinyl propionate and methacrylic acid, vinyl acetate and dibutyl fumarate, and vinyl acetate and monooctyl maleate provide copolymers useful in this invention. The only limitation on the above polymers is that they contain at least 25% by weight, preferably 25 to 7% by weight in combination with the copolymerizable polar monomers.
It contains 5% by weight of ethylene.

This polar monomer is necessary to achieve a suitable hydrophilic-lipophilic ratio in the copolymer. Oil-soluble surfactants that can be used include anionic, cationic, or nonionic surfactants.

Anionic surfactants useful in the method of the invention include:

Carboxylic acids, including fatty acids, rosin acids, tall oil acids, and branched alkanoic acids. These include alkali metal salts of alkanes and alkylarylsulfonic acids, including alkylbenzenesulfonates, alkylnaphthalenesulfonates, and the like. Cationic surfactants useful in making the compositions of the invention include quaternary amine salts. Nonionic surfactants, which are a preferred type of surfactant for making the compositions of this invention, include polyethyleneoxy-ether derivatives of alcohols such as alkylphenols, alkylmercaptans, sorbitol, pentaerythritol, and the like.

Particularly preferred nonionic surfactants for use in the present invention have the following general structural formula (where R1o is C8Hl7, C9Hl9
, or ClOH2l, where m is 1.5 to
is an integer of 8).

The most preferred nonionic surfactant is Atlas Chemical's Span 80, a fatty acid ester of anhydrous sorbitol.

Since the number of surfactants is extremely large, there is no intention to burden this application with numerous examples.

The following publications may be cited as examples thereof: Lloyd (
LlOyd)1. Osip0w, "Surface Chemistry", Reinhold Publishing Co., New York (1962), Chapter 8 and MOillier.
et) et al., “Interface Chemistry”, Van Nostrand, (1
961) Part.

Generally, the aqueous internal phase constitutes 10-80% by volume of the emulsion, preferably 20-60% by volume.

A surfactant is added to the external phase of the emulsion at 0.01 to 20% by weight,
Preferably 1 to 5 weight? It can be combined with The copolymer is incorporated into the external phase in an amount of 1 to 40% by weight, preferably 3 to 30% by weight. The following provides specific embodiments of the invention.

Example 1 To a vigorously stirred (1,000-2,000 RPM) solution of butyl rubber 13.69 sulfonated to the 2% level in Solvent Neutral 100 186.59 at 85°C is added dropwise 186d of a 10% aqueous sulfuric acid solution. did.

Stir the emulsion 1809 thus created (150
~250 RPM), NH4+ as ammonium hydroxide
Sulfide 2,800 as 1,720ppm<15H2S
It was added to 740 ml of water containing ppm. Aqueous samples were taken with a pipette at 1 minute, 5 minute, 15 minute, 30 minute, 60 minute, and 90 minute intervals by settling into the emulsion and taking samples of the lower aqueous layer.

The temperature was maintained at 80-85°C during the experiment. The ammonium concentration accordingly decreased to 42 ppm in 30 minutes and the emulsion remained stable for the entire experimental period (90 minutes). Example 2 The experiment of Example 1 was repeated.

The concentrations of NH4+ and S- were 1,700 ppm and 2, respectively.
, 240 ppm. In this experiment, steam was passed through the stirred mixture at 850C. The ammonium ion concentration was 34 ppm in 30 minutes, and the sulfide ion concentration was 20 ppm.
It decreased to less than ppn1. The emulsion remained stable for the entire experimental time (90 minutes). Example 3 The experiment described in Example 1 was repeated using 2.5% by weight of sulfonated butyl rubber in the oil phase.

The internal phase contained 2.13% by weight of sulfuric acid. The emulsion was left in contact with the feed for 5 minutes. The concentration of NH4+ was measured at the beginning and end of the experiment. After this time, the feed was removed and the same emulsion was contacted with fresh feed for 5 minutes. This process was repeated two more times. The temperature was kept at 85° C. for the entire experimental time. The NH4+ concentration in the four feeds is 118,137
, 143, 186 ppm, respectively 1, 1, 1.75, 2
ppm.

This shows that one emulsion can be used multiple times. Comparative Example 1 In the formulation described in Example 1, 12% LubrizOl 3702 (
The experiment of Example 1 was repeated using Lubrizol (product of Lubrizol).

The ammonium ion concentration was 2,040 ppm and the sulfide ion concentration was 1,970 ppm. Within 15 minutes of the start of the experiment, the entire mass gelled and no sample could be taken for ammonium analysis. Comparative Example 2 Using 4% PIBSA-TEPA, the reaction product of polyisobutylene-succinic anhydride and tetraethylenepentamine, and 1% SPAN 80, Example 1
The experiment was repeated.

Within 15 minutes, the entire reaction mixture gelled and no sample could be taken for ammonium analysis.

Example 4 The experiment of Example 1 was repeated with an initial NH4+ concentration of 1,900 ppm, but without H2S.

Within 30 minutes the NH4+ concentration decreased to 3 ppm.

Comparison of the effectiveness of polymers sulfonated to different levels.

Example 5 Butyl rubber (5 mole % copolymer of isoprene and isobutylene, the same as that used to make the sulfonated polymer) in 182.49 of Solvent Neutral 100 1
A 10% sulfuric acid solution 1669 was added dropwise to a vigorously stirred solution of No. 3,69 and Surfactant Span 80 No. 49.

The resulting emulsion, which appeared normal at room temperature, was heated to 85° C. for Sawa Issui treatment. During heating, the emulsion began to break down and the organic layer completely separated from the aqueous layer when the temperature reached 80°C. This shows that the emulsion has no stability under the operating conditions even in the presence of external surfactants. Example 6 1 mole? The experiment of Example 1 was repeated using the same concentration of butyl rubber sulfonated to the 1 mole percent level.

The initial concentration of NH4+ is 1,960 ppm, which increases to 4 ppm within 30 minutes.
m, and the emulsion remained stable over the experimental period (40 minutes). Example 7 4 moles? The experiment of Example 1 was repeated using the same concentration of butyl rubber sulfonated to the 4 mole percent level.

The resulting emulsion was very thick. NH4 in feed
+ The initial concentration was 2,040 ppm. Within 15 minutes the entire mass gelled and further experiments could not be performed.

The experiments described above indicate that about 1 mole percent sulfonation is desirable in the sulfonic acid polymers used to make the compositions of the present invention.

A level of about 4% or higher is not as effective as a 1% level. The experiments of Examples 7, 8, and 9 were designed to determine the effect of lower amounts of sulfonated polymer at the 4% level on membrane stability.

Example 8 Polymer Sulfonated to 4 Mol% Level Solvent Neutral 10 of 198.59 at 85°C
An emulsion was made by encapsulating a 10% sulfuric acid solution 1869 in a solution of 1.59 butyl rubber sulfonated to a 4% level in 0.0.

Add 1/2 of this emulsion to 1 part of ammonium hydroxide in the usual way.
, 960 ppm. The emulsion tended to stick too much to the side of the reaction vessel and had significantly poor separation from the feed water. In effect, no significant portion of the emulsion could be made to come into contact with the feed solution. What makes an emulsion workable is that it can be easily dispersed into small droplet form, providing a very large surface area for efficient and rapid removal of contaminants. In this case, the NH4+ concentration is 80pp in 30 minutes.
m, but increased to 100 ppm in 60 minutes, indicating the weakness of the membrane. Example 9 Polymer sulfonated to 4 mole level The experiment of Example 7 was repeated using butyl rubber sulfonated to the 4% level shown in the previous example, using 3.09 instead of 1.59. .

The NH4+ concentration in the feed was 2,160 ppm. This concentration decreased to 90 ppm in 30 minutes. However, the emulsion completely gelled in 55 minutes. From these experiments,
A level of at least 1% by weight sulfonated polymer in the external phase is found to be desirable. Comparison of the effects of sulfonated polymers with different molecular weights.

The experiments of Examples 10-12 were designed to determine the effect of molecular weight on membrane strength and efficiency in sour water treatment.

At polymer concentrations in the range of 3-6%, emulsions are very thick pastes that cannot be handled, whereas emulsions containing very low concentrations of sulfonated high molecular weight polymers lack dimensional stability. It had a tendency to gel easily.

Example 10 Molecular weight 150,000 (sulfonated to 1 mol % level)
6.8% isobutylene-isoprene copolymer (number average)
High molecular weight sulfobutyl (number average 150,000) instead of low molecular weight sulfobutyl (number average 15,000XI) 0.
An emulsion was made by the procedure of Example 1 using 85%.

This was contacted with a feed solution containing 2,400 ppm NH4+. N.H. The ten concentration decreased to 21 ppm in 30 minutes, but the entire mass gelled soon after this time. Example 11 Example 9 using 0.40% high molecular weight sulfobutyl
The experiment was repeated.

This was contacted with a feed solution containing 2,080 ppm NH4+. N.H. +Concentration decreased to 145 ppm in 15 minutes. However, the entire mass gelled in 25-30 minutes. Example 12 1% by weight sulfo-EPT (number average molecular weight 0,000) 1
The experiment of Example 9 was repeated using ethylene-propylene-ethylidene norbornene (produced by sulfonation to the mole % level).

N.H. The concentration ranges from 2,040ppm to 12pp in 15 minutes.
decreased to m. However, after 60 minutes, the entire mass became emulsified and NH.
The concentration increased to 25.4 ppm. From these experiments,
To make the composition of the present invention, for example, 5,000 to
It can be seen that low molecular weight sulfonic acid polymers with a molecular weight of 50,000 are desirable.

Salts of sulfonated polymers. In order to examine the efficiency as an additive to liquid films, we used low molecular weight (number average molecular weight 15,000
) 1% and 2% of isobutylene-isoprene copolymer
The sodium, ammonium, and potassium salts were prepared by neutralizing the sulfonated compounds with the corresponding bases.

5% of these salts in Solvent Neutral 100
I tried to make a solution. All these salts are at 250℃,
It was insoluble at 80°C. Among these, the potassium salt of the sulfonated polymer at the 2% level showed the best solubility behavior. Its use in liquid films is described in Example 13. Example 13 Sulfobutyl potassium salt (containing 2 mole percent sulfonate groups) by heating to 850° C. in Solvent Neutral 100 and adding 0.5 CC of Bryj3O from Atlas Chemical Co., Wilmington, Delaware.
A 5% solution of

An emulsion was made from this solution by encapsulating 1% sulfuric acid solution 839. This emulsion is NH4+109
It was contacted with a feed containing ppm. NH4+ in 60 minutes
The concentration was reduced to 46 ppm.

However, the feed was extremely cloudy. This indicates that these salts have near-limit utility as membrane additives for Sawa water treatment. Use of acids other than sulfuric acid for Sawa water treatment.

Example 14 A solution of sulfonylbutyl 6.89 in Solvent Neutral 100 as the oil phase and 1009 as the internal phase.
．． An emulsion was made from 9% polyacrylic acid (number average molecular weight 50,000, a product of Polysciences, Warrington, Pa.) 839.

This emulsion was contacted at 85° C. with aqueous feed 7409 containing 2,400 ppm NH4+. NH within 30 minutes
The 4+ concentration decreased to 37.5 ppm and the emulsion remained stable for the entire experimental time (90 minutes).

Example 15 The experiment of Example 14 was repeated using 28% aqueous daltaric acid as the internal reagent.

The operating temperature is 85℃ and the feed is NH4+2,020p.
It contained pm, H2Sl, and O4Oppm. After 29 minutes, the NH4+ concentration decreased to 78 ppm, and the H2S decreased to below 20 ppm.

Similar results were obtained when using phosphoric acid or succinic acid in the above experiments. Example 16 Low molecular weight sulfobutyl 6 weight as membrane phase? , trioctylphosphine oxide 4 weight? , trioctylamine 0.1% by weight, 90% solvent neutral 100
weight? An emulsion was prepared using 4.2% by weight sodium hydroxide as the aqueous internal phase.

The weight ratio of external to internal phase was 1:1. This emulsion 19
Stir 09 and add PHL. 6 was contacted with 800 ml of feed containing Chromium JMoVPpm as sodium dichromate. Within 5 minutes, the chromium concentration in the feed was 0.5
It decreased to below ppm.

The following example illustrates the difficulties encountered in attempting to use sulfonated polystyrene, an aromatic sulfonate.

It is clear that these polymers are not soluble in the desired solvent system used and, even when dissolved in a suitable solvent, will precipitate on addition of the desired solvent. Example 17100m1 of solvent
0.81 mole in neutral 100? Polystyrene 29, which had been sulfonated to a level of .

The mixture was stirred magnetically for 24 hours and then discharged. The residue was washed with isopropanol. This was dissolved in benzene and propanol was added to precipitate it. The precipitated solid was collected and dried. The weight of the recovered polymer was 2.09, which was quantitatively recovered. Example 18 Polystyrene sulfonated to a level of 0.81 mole %1.
A solution was prepared by dissolving 5 g in 100 ml of xylene.

To this solution was added 100r1L1 of Solvent Neutral 100. The polymer precipitated out as an oil. The supernatant was decanted. The polymer was dissolved in 50 ml of benzene, reprecipitated in isopropyl alcohol, collected and dried. The weight of the recovered polymer was 1.1 g.
Example 19 In this example, various emulsions are utilized in a liquid film process for Sawa water treatment in order to compare the effectiveness of emulsion formulations.

Additives were dissolved in the weights shown in Table 1. In this example,
The foreign minister has a capacity of 55? Emulsion 1839, the internal phase of which consisted of a 1% by weight aqueous sulfuric acid solution, was contacted with an aqueous feed stream containing varying amounts of ammonia and ammonium ions. The emulsion and feed streams were contacted at a volume ratio of 1:4. The contact was carried out at 85° C. under agitation conditions (200 RPM). As can be seen from the results in Table 1,
The whole emulsion was effective in removing ammonia. These particular emulsion formulations have been found to be the most effective formulations for ammonia removal through the liquid film, the external phase of the emulsion, and into the internal phase. Emulsions with ethylene-vinyl acetate copolymers settled very quickly.

When the agitator was then turned off, the oil phase and aqueous feed separated instantaneously, leaving behind no haze caused by the suspension of very fine droplets of oil in the feed. Other additives required long settling times to give a clear feed. Example 20 In this experiment, Example 19 was used except that a 10% sulfuric acid internal phase was used.
Swelling rates were compared using emulsions similar to those tested.

At this high concentration of sulfuric acid, which has commercial significance in liquid membrane sour water treatment processes where the ability of the emulsion to neutralize ammonia is important, ethylene monovinyl acetate copolymer was superior. The next best composition based on sulfonated butyl rubber showed about three times more swelling, while Lubrizol 370
The sample based on 2 gelled in 5 minutes and was completely ineffective. In this example, swelling was measured by contacting the emulsion with an ammonia-containing feed stream in a manner similar to Example 19.

Claims (1)

[Scope of Claims] 1. As the oil phase of the emulsion: (a) a sulfonated polymer having a main chain that is substantially non-aromatic and having a sulfonic acid content of not more than 20% by mole, or at least 25% by weight; and (b) the above sulfonated polymer or the above ethylene copolymer.
A water-in-oil emulsion containing a copolymer solvent.