JPH01224038A - Novel amphoteric surfactant and water-in-oil type emulsion and method of separating and concentrating metal ion by using emulsification type liquid film. - Google Patents

Abstract

PURPOSE:To improve the stability of a water-in-oil type emulsion by emulsifying a metal extractant-contg. water insoluble phase and metal ion concentrating agent-contg. water phase in the presence of a specific amphoteric surfactant, thereby forming the emulsion. CONSTITUTION:The metal extractant-contg. water insoluble phase and the metal ion concentrating agent-contg. water phase are emulsified in the presence of the amphoteric surfactant expressed by formula I (R, R' denote a hydrocarbon group of 8-20C; (m), (n) denote integer in the range of 1-10; X denotes a halogen atom.) to form the water-in-oil type emulsion. This emulsion is dispersed under stirring into a metal ion-contg. aq. soln. to extract the metal ions so that the metal ions are concentrated into the water phase in the emulsion. The emulsion is then separated and demulsified to separate the water phase of the concentrated metal ions from the water insoluble phase.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel amphoteric surfactant, particularly an emulsified liquid film used for recovering metals from an aqueous solution,
It is particularly advantageously used for reverse phase emulsions of water-soluble or water-swellable polymers.

Conventional technology Separating and recovering useful metal components contained in aqueous solutions5
The process of separating and removing metal components that are difficult to release as wastewater is industrially important, and various methods have been used since ancient times. In recent years, methods of performing these separations using emulsified liquid membranes have attracted attention and have been put into practical use due to their ease of separation and economic efficiency.

As an emulsion type liquid film, an O/W10 type liquid film obtained by dispersing an oil-in-water (0/W) type emulsion in an organic phase has been developed, but this film is mainly used for aromatic and aliphatic hydrocarbons. It was used for separation and was not used for metal separation or recovery.

Later, a W10/W type liquid film was developed, which is obtained by dispersing a water-in-oil (W/O) type emulsion, which is called reverse phase, in an aqueous phase. Attempts are being made to use it to recover uranium from phosphorus and various metals from wastewater.

For the purpose of recovering a metal using a W10/W type liquid film, a stable W10 type emulsion is first prepared and dispersed in an aqueous phase containing the metal.

At this time, it is necessary to stir vigorously to increase the extraction efficiency, but it is important to produce a stable W10 emulsion that will not be destroyed even under such vigorous stirring conditions. However, in order to subsequently recover the metal components concentrated in the internal aqueous phase of the emulsion, the emulsion particles must have the property of being easily destroyed (demulsifying), and these contradictory properties are required. The selection of surfactant to be applied is very important.

Also, during the extraction operation, water may permeate through the liquid film due to the osmotic pressure caused by the difference in salt concentration between the inner and outer aqueous phases in the W10 emulsion droplets, and especially from the outer aqueous phase. Water permeation into the internal aqueous phase will reduce the cWJ rate of the metal. Therefore, it is desirable to use a surfactant that suppresses the permeation of water through the membrane, but promotes the permeation of the target metal through the membrane.Moreover, since the liquid film phase is circulated and used repeatedly in industrial processes, The activator is preferably one that is chemically stable and can be easily produced.

As mentioned above, the surfactants used in emulsified liquid films are:
Due to the large number of maneuvers required, the types actually used are currently relatively limited.A representative example is the polyamine described in U.S. Pat. No. 3,897,308 (see formula (2) below), sorbitan esters (for example, a mixture of sorbitan monooleate, hishioleate, trioleate, sorbitan stearate, etc.), and there are many products, but a typical product name is 5pan, Sorbitan monooleate, which is the main component of 5pan80, has the structure of the following formula (3).

(However, n = 10 to 80, W1 using
It is known that the e-editing method for separating metals using an O/W type liquid film has the following problems.

(1) When the W10 emulsion produced using the above surfactant is vigorously stirred and extracted in the aqueous phase,
The speed at which the emulsion droplets are destroyed is high, making it difficult to stably perform the intended extraction operation. Therefore, in order to further stabilize the formed W10 emulsion, it is necessary to increase the amount of the surfactant used, and by using it at a concentration of 40 ol/g or more, it is finally possible to achieve practical stability. can be obtained.

However, using surfactants at high concentrations in this way is not only economically disadvantageous, but also susceptible to effects such as swelling, which can significantly reduce the efficiency of the intended extraction operation. Become.

(2) The extraction rate of metal ions by an emulsified liquid film is easily affected by the surfactant used, and this is likely due to the fact that the charge state at the interface has a large effect on the extraction rate. With known nonionic surfactants, the rate of extraction of the target metal is not necessarily high, and from a practical standpoint, it is desired that the rate be further increased.

(3) Furthermore, in the separation and concentration process of metal ions using an emulsifying liquid membrane, the demulsification step is also important, and at present, an electrical demulsification method is generally used. The ease of demulsification varies depending on the surfactant used, but demulsification is not easy with conventionally known surfactants, and it is necessary to use a relatively high applied voltage in electrical demulsification. Therefore, if a surfactant that can be easily demulsified and can reduce the applied voltage can be obtained, the process can be made more industrially advantageous.

Means to Solve the Problem In order to effectively separate and concentrate metal ions using an emulsified liquid membrane, the most important thing is to select an appropriate surfactant, and we have investigated known surfactants in detail. Within the range of research conducted, no solution to the above-mentioned problem was found. Therefore, in order to carry out the metal ion separation and concentration process using an emulsified liquid membrane, we believe that an amphoteric surfactant that has two long-chain alkyl groups is the most effective surfactant. , synthesized many surfactants of this type,
As a result of continuing to confirm the effects, it was discovered that the following compounds exhibited significantly superior performance, and the present invention was completed.

That is, the present invention provides a novel amphoteric compound (
However, here, R represents a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, and may be the same or different from each other.
(m and n represent integers of 1 to 10, and may be the same or different from each other, or represent a halogen atom) Furthermore, the present invention provides an in-oil surfactant using a novel amphoteric surfactant represented by the general formula (1). It is a water (W/O) type emulsion.

Furthermore, the present invention emulsifies a water-insoluble phase containing a total pressure extractant and an aqueous phase containing a metal ion concentrator in the presence of a novel amphoteric surfactant represented by the general formula (1), and emulsifies the water-in-oil phase. (W/O
) type emulsion is formed, the emulsion is dispersed and stirred in an aqueous solution containing metal ions as the phase to be extracted, the emulsion is separated and demulsified, and the aqueous phase enriched with metal ions is converted into a water-insoluble phase. This is a method to obtain it by separating it from

Below, the content of the present invention will be described in further detail.

The present invention is a novel amphoteric surfactant represented by general formula (1). R in general formula (1) has 8 to 20 carbon atoms.
saturated or unsaturated hydrocarbon groups, specifically octyl, nonyl, decyl, lauryl, myristyl,
Cetyl, stearyl, oleyl, etc. are the main ones, and branched alkyls in addition to linear ones can also be used. In addition, m and n are integers from 1 to lO, but especially m is from 1 to 5, and n is from 2
~9 is preferred, and X is a halogen atom selected from chlorine, bromine, iodine, and fluorine.

The amphoteric surfactant of the present invention can be synthesized by various methods, and there are no particular restrictions on the starting materials, production routes, types of intermediates, etc. An example of the production method is as follows. Become.

Glutamic acid and an aliphatic (saturated or unsaturated) alcohol are esterified in the presence of a fermentation catalyst to produce a diester (salt) of glutamic acid in the first stage. The above aliphatic long chain alcohols may be used as a mixture or monoesterified with one type of alcohol and further diesterified with another type of alcohol. Specifically, stearyl alcohol is used as the aliphatic long chain alcohol. If there was,
(As per formula 0, ■ is obtained.

(2) The obtained diester (salt) of glutamic acid is reacted with an ω-halocarboxylic acid halide and then reacted with N,N-dimethylamino alcohol to be quaternized. As a specific example, when chloroacetic acid chloride and N,N-dimethylaminoethanol are used for (1), the reaction proceeds as shown in equation (5) to obtain (2).

The quaternized triethylamine product is further reacted with phosphorus oxychloride to form a monoester, which is then hydrolyzed to form the desired glutamic acid diester-quaternary ammonium bond type phosphoric acid monoester.
An amphoteric surfactant is obtained. To give a specific example, the reaction between ■ and phosphorus oxychloride and subsequent hydrolysis results in
Amphoteric surfactant (2) is obtained according to formula (8).

The above is an example of the method for producing the novel amphoteric surfactant of the present invention, but the production method is not limited to this example.

Furthermore, the present invention is a water-in-oil (W/O) emulsion using a novel amphoteric surfactant represented by general formula (1). The water-insoluble phase forming the oil phase of the emulsion can be used without any particular restriction as long as it is a liquid that does not uniformly mix and dissolve with water, but aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons are used. Specific examples include mineral oil, paraffin oil, kerosene, light oil, naphtha, perchlorethylene, benzene, toluene, xylene, hexane, heptane, cyclohexane, etc., and mixtures of two or more of these can also be used.

The oil phase may contain a metal ion extractant, a stabilizer, a viscosity modifier, etc. depending on the surfactant and purpose.

The aqueous phase can contain anything that is soluble in water depending on the use and purpose. For example, for metal extraction, citric condensation,
Mineral acids such as sulfuric acid, hydrochloric acid, etc. may be included, and for the purpose of polymerizing water-soluble monomers, water-soluble monomers, initiators, etc. may be included. It can also contain various ions and salts.

Furthermore, water-soluble enzymes can be included for immobilization of enzymes.

The ratio of the oil phase to the water phase can be varied over a wide range as long as the emulsion remains stable, but it is usually within the range of oil phase: water phase = 30: 70-95: 5 (volume ratio). Implemented.

The W10 type emulsion can be produced by stirring the above oil phase and aqueous phase at high speed in the presence of the surfactant of the present invention.

High-speed stirring can be carried out using various homomixers, emulsifiers, colloid mills, in-line mixers, etc., and is often more effective when carried out under ultrasonic irradiation.

The concentration of the amphoteric surfactant represented by formula (1) used in the W10 emulsion of the present invention varies depending on the type of oil phase and aqueous phase, the substances contained, the purpose of use, etc. 1-100mol/m'' as standard
The range is more preferably 5 to 50 mol/m''.

Furthermore, the present invention emulsifies a water-insoluble phase containing a novel amphoteric surfactant represented by general formula (1) and a metal extractant and an aqueous phase containing a metal ion concentrator to form a W10 emulsion. , the emulsion is dispersed and stirred in an aqueous solution containing metal ions as a phase to be extracted, the metal ions are extracted with the emulsion, concentrated in the internal aqueous phase of the emulsion, and then the emulsion is separated and demulsified. , a method in which an aqueous phase enriched with metal ions is obtained by separating it from a water-insoluble phase.

There are no particular limitations on the metal ions that can be used in the method of the present invention, but examples include gold, silver, copper, zinc, cadmium, mercury, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, beryllium, magnesium, and calcium. , aluminum, gallium, indium, germanium, tin, lead, titanium, zirconium, hafnium, chromium, molybdenum, tungsten, manganese, uranium,
Niobium, tantalum, other rare earth metals, thorium,
Ions of metals such as lithium and potassium are used.

These are sometimes used as a hydrometallurgical process for the purpose of manufacturing pure products, sometimes as a method for recovering useful metals from wastewater, and sometimes for the purpose of removing harmful metals from wastewater. It is also used as a wastewater treatment method.

The metal ion extractants used in the method of the present invention include:
All known metal extractants can be used as long as they are soluble in organic solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Specifically, N-8-quinoline sulfonamide, E-2-hydroxy-5-7ylbenzophenone oxime, tri-n-octylphosphine oxyto, bis(2°4.4-trimethylpentyl)phosphinic acid,
Bis(2,4,4-)limethylpentyl)phosphinodithionite, triisobutylphosphine sulfide, bis(2,4,4-)limethylpentyl)n-octylphosphine, etc. are used, and the trade name is CYANEX2.
72, 321.301.471X, 825 (all Mitsui Cyanamid U), LIX85N (Gener
al Mills), Kelexloo (As
hland Co., Ltd.) are known.

The amount of metal extractant used in the method of the present invention varies widely depending on the moisture content of the metal ions to be extracted, the required extraction rate, etc., and is not particularly limited. ~100mo]/m'' is usually used.

The method for producing the W10 emulsion has already been described.

The extraction operation used in the method of the present invention is usually carried out by stirring, but countercurrent contact, shaking, etc. may also be used. Fine emulsion droplets are sufficiently uniformly dispersed in the liquid to be extracted. After the extraction operation is completed, it is preferable to
The emulsion is separated, but this can usually be easily done using the difference in specific gravity, and after extraction, the emulsion is separated into an upper layer simply by allowing it to stand still.

In a continuous process, it is preferable to separate the upper emulsion and drain the extraction residual liquid from the lower part. Also, if the difference in specific gravity between the emulsion and the liquid to be extracted is not large, the emulsion can be easily separated by centrifugation. .

To demulsify the emulsion after separation, an electrical method of applying a voltage, a method of adding an oil-in-water (0/W) type surfactant, etc. are used. In the former case, the applied voltage is effective whether it is DC or AC, but AC is usually 0.1 to 50KV.
range is used. In the latter method, Griffin
A surfactant with an HLB value of 8 to 14 is preferable, but when the oil phase is used continuously, the 0/W used for demulsification
The next emulsification may not proceed well due to the effect of the type surfactant.

The obtained metal ion concentrate is further purified and concentrated to obtain the desired metal as a product, or is reused. In other cases, it is simply concentrated and disposed of.

Effect: It has been revealed that the amphoteric surfactant represented by formula (1) of the present invention has a greater effect of stabilizing the W10 emulsion than conventionally known surfactants. This is because the amphoteric surfactant of the present invention has two characteristic long-chain aliphatic groups, which fully penetrate into the oil phase, and on the other hand, a highly polar quaternary ammonium bond and a phosphoric acid group. , it appears that it penetrates deeply into the aqueous phase and maintains the interface between the two very stably.

Therefore, a very stable W10 emulsion is formed, and when metal ions are extracted using this emulsion, even if sufficient stirring is performed, the emulsion hardly breaks down.
Unlike conventionally known surfactants, the prospect of use in stable industrial processes was obtained. Furthermore, since surfactants are usually expensive, reducing the amount used has a significant effect.

Furthermore, the W10 emulsion using the amphoteric surfactant represented by the formula (1) of the present invention is easily demulsified, and particularly in the electrolytic demulsification method, demulsification progresses with a low applied voltage. This is in contrast to the conventional W10 emulsion using a known surfactant, which is difficult to demulsify. The W10 emulsion is used not only for metal extraction but also for the production of polymers by polymerizing water-soluble monomers, but all of these applications require the stability of the W10 emulsion, and it is easy to demulsify. is required. In particular W1 containing an amphoteric surfactant of the invention
The reason why the 0 emulsion is easily electrically demulsified is thought to be because the molecule contains an ionic quaternary ammonium salt bond and has a highly polar phosphoric acid monoester structure.

In addition, separation of metal ions using an emulsion-type liquid membrane using the W10 emulsion using the amphoteric surfactant of the present invention, c! It was confirmed that when used in III, it has the effect of increasing the extraction rate of metal ions. This is also 3 to 5 times faster than conventionally known nonionic surfactants, and the interfacial reaction between the extractant and metal ions on the outer surface of the W10/W emulsion is enhanced by the amphoteric phosphate group of the present invention. It was revealed that the reaction progresses quickly when the surfactant is contained.

Therefore, when using the amphoteric surfactant of the present invention, W10/
It has become clear that the separation of metal ions using a W emulsion type liquid membrane, the HWa process, can be carried out significantly more effectively and stably than when conventionally known surfactants are used.

Production Example 1 20.0 g (0,138 mol) of glutamic acid was dissolved in 800 g of toluene, and 9 g of stearyl alcohol H was dissolved.
(0,299 mol) and 25.4 g (0,13 mol) of l/p-)luenesulfonic acid (1 aquarium) were added,
Attach a Dien-Staak liquid separator and reflux for 4 hours.
After the reaction was completed, the toluene solution was cooled, washed with water, dried over sodium sulfate, and the toluene was distilled off to obtain a solid. Furthermore, this was recrystallized from ethanol to produce a colorless P-1 luenesulfonate of distearyl glutamate.■
100.7g (yield 90.1%, ■, p, ?2.0
~73.0°C) was obtained.

P-) of distearyl glutamate obtained as above
In a flask, 59.4 g (0,072 mol) of luenesulfonate was added to tetrahydrofuran (THF).
500. Q, cooled and kept at 0°C.

Chloroacetic acid chloride 9 dissolved in 50 cc of THF
．． 8 g (0,087 mol) and triethylamine 8
．． 0 g (0,078 mol) was added dropwise into each stirred flask, stirring was continued for 1 hour at 0° C., and further stirred for 6 hours at room temperature. Thereafter, THF was distilled off, and the distilled residue was dissolved in chloroform, washed with water, dried over magnesium sulfate, dissolved under heating in n-hexane, filtered to remove insoluble materials, and recrystallized to obtain a colorless solid, n.

The obtained crystals were dissolved in THF 500.1 in a flask, and 7-7 g of N,N-dimethylaminoethanol was added.
(0,088 mol) was added, and the mixture was allowed to react for 8 hours under reflux. After the reaction was completed and cooled to room temperature, THF was distilled off and the residue was recrystallized from ethyl acetate to obtain 49 g of the compound corresponding to (1) (yield 83.1%, (2), p.

78.0-79.0°C) was obtained.

Bottle...(5) Dissolve 45.7 g (0,0559 mol) of the compound corresponding to (1) above in THF500- in a flask, add 5.7 g (0,056 mol) of triethylamine, and cool on ice. did. Phosphorus oxychloride 8.8 g (0,0
58 mol) was added dropwise from a dropping funnel into a water-cooled flask over 1 hour with stirring, and 100% of ice water was added and stirred. After the reaction was completed, THF was distilled off, and the remaining aqueous layer was diluted with chloroform. After extraction and adding magnesium sulfate to the chloroform layer and leaving it for half a day, chloroform was distilled off, and the resulting residue was further recrystallized with acetone.
28 g (yield 54.2%) of the desired colorless solid was obtained. The following measurement values confirmed that the obtained colorless solid had a structure (■).

The obtained compound (2) is a quaternary ammonium salt-bonded phosphoric acid monoester of glutamic acid distearyl ester, and for convenience, it will be designated as 2 G , 8 G E Q APA.

The following measurements were performed on the obtained 2 C1s G E Q A P A .

(1) m, p, 83-65°C (2) Elemental analysis measurement value (%) CBo, 50 Hlo, 37 N
3.07C4wa HQ4N209 PCu 1.5H2
Theoretical value (%) as 0 CB105 Hlo, 57
N 3.03 (3) I R (Nujol, cm
-' ) See Figure 1 720.1000 (Broad,
υp-o), 1210 (Broad, ?/P-0)
3200 (Broad, υ-0H) 3350 (B
road, υ-0H) (4) NMR (CDCu3.
PP ■) See Figure 2 0.92 (C-C island, 6H),
1.25 (alkyl chain -C-CEI, -C1C4H)
, 1.88 (glutamic acid β-CH,,2H),
2.2-2.3 (glutamic acid-c-cu, -c-, 2
H), 3.4-3.5 (N-CH3, EiH),
3.9-4.2 (carboxylic acid ester -〇H, -0-
, Phosphate ester -〇H2-0-1 Example 1 An aqueous solution containing a tracer (nickel nitrate) of 5 ■o l/rn'' and amphoteric surfactant 2 of the present invention obtained in Production Example 1. An equal amount of the n-hebutane solution of C18G E Q A P A was taken and irradiated with 22 KH2 ultrasonic waves (output 800 W) for 5 minutes while stirring at 1000 rpm to prepare a W10 type emulsion.

Immediately after preparation, W10 emulsion 100- was collected using a specially made whole pipette, and was heated isothermally (3
03K) and stirred with a 200rpm 700
The mixture was poured into the aqueous phase (outer aqueous phase) of the water and dispersed. The stirring tank is a flat bottom glass container with an inner diameter of 10 cm and a depth of 15 cm.
Four stainless steel baffles with a radius of 1c+s and a length of 15c layers are installed, and the agitating element is a 6-blade stainless steel turbine with a diameter of 5.30 cm.

After the end of the charging, 3 to 4 samples were collected from the stirring tank into test tubes at fixed *l''J! intervals, and after being allowed to stand for a certain period of time, they were separated into a W10 emulsion phase and an external aqueous phase.

The emulsion phase was homogenized by adding a certain amount of dioxane, and the water content was measured by the Karl Fischer method and the concentration of nickel (n) nitrate (used as a tracer) by atomic absorption spectrometry. The tracer concentration in the external aqueous phase was also measured in the same manner.

The membrane breakdown rate ε is calculated from the concentration of nickel (II) nitrate CN+e in the outer aqueous phase broken from the inner aqueous phase of the emulsion,
It is determined by the following formula.

ε= VweCNie/Vwi"CNi"
* * (7) Here, Vwe is the external water phase volume, Vwi
'' is the initial volume of the internal aqueous phase, and CNi is the initial concentration of nickel nitrate (IT) in the internal aqueous phase. Here, assuming that the membrane destruction rate ζ± is proportional to the undestructed rate, equation (8) is obtained.

Field (1−ε)=−kbr −−・(8) where k
b is the membrane breakdown rate constant.

The membrane breakdown rate ε and membrane breakdown rate constant were calculated from the above measurement results.

Similarly, 5p shown in formula (3), which is a commercially available surfactant,
The membrane breakdown rate ε and the membrane breakdown rate constant kb were measured and calculated in the same manner using an80 and the polyamine shown by formula (2).

The results are summarized and shown in Figure 3. From this, the amphoteric surfactant 2C into which two long-chain alkyl groups of the present invention are introduced
ra G E Q A PA is a commercially available surfactant.
It has become clear that the liquid film can be stabilized at a concentration as low as 1/10 compared to pan80 and polyamine.

Example 2 A copper extraction experiment using an emulsified liquid film operation was conducted under the following conditions. 50 mo of copper extraction ligand LIX85N
2 C1a, which is an amphoteric surfactant of the present invention.
Equal volumes of n-hebutane solution containing a predetermined amount of G E Q A P A and lN11iE acid aqueous solution were placed in a container and heated at 22 KH for 5 minutes while stirring at 1000 rpm.
A W10 type emulsion was prepared by irradiating ultrasonic waves (output: soow).

The stirring tank described in Example 1 contained copper ions at a concentration of 0.5 kg/m'' (500 pp++).
Take 700% of IN acetic acid aqueous solution (pH = 2.88),
It was maintained at 303°K while stirring at 200 rpm.

The above W10 emulsion 100- is made into a special whole bee.
The sample was collected at 200 rpm and poured into an aqueous phase (outer aqueous phase) in a stirring tank, which was stirred at 200 rpm, and thoroughly dispersed. The external aqueous phase was sampled according to the stirring time, and the concentration of copper ions was determined by atomic absorption spectrometry. In a similar manner, copper extraction was carried out using 5pan80 and polyamine instead of the amphoteric surfactant of the present invention for comparison.

The above results are shown in FIG. 4 as copper raffle rate E=Ccu/Ccuo. Here, Ccu is the copper ion concentration at the time of measurement, and Ccuo is the initial concentration of 0.5 kg/m''.

As is clear from FIG. 4, the amphoteric surfactant 2 of the present invention
C18GEQAPA is a conventionally known surfactant5
It has been revealed that it is effective in improving the copper extraction rate compared to pan80 and polyamine.

It is presumed that the membrane permeation of metal ions in an emulsified liquid membrane is mainly controlled by the interfacial reaction rate on the surface of the emulsion droplet in a low pH region as in this example. Considering that the back extraction rate is sufficiently fast and the extractant concentration is close to the initial concentration, the interfacial reaction rate R on the outer surface can be approximated by the following equation.

R= kf'c cu/αH・・Φ (9) Here kf
' is the interfacial reaction rate constant, and Ccu and αH are the copper ion concentration and hydrogen ion activity in the aqueous phase, respectively.

Further, the change in the concentration of copper ions in the stirring tank is expressed by the following equation.

-d Ccu/dt= a kf'ccu/αHII・
・(10) Here, a= (VE /Vwe) (8
/da), VE is the emulsion phase volume in the stirring tank, Vwe is the external aqueous phase volume, and dE is the W10 type emulsion droplet diameter.

The hydrogen ion activity αH in the external aqueous phase can be expressed by the following formula.

αH=αH□+ 2 yH(Ccuo −Ccu) e
*e (11)yH is the hydrogen ion activity coefficient.

From equations (10) and (11), equation (12) is obtained, and based on this, the apparent interfacial reaction rate constant (a kf'/7
H) (mol/ln''s) was determined.

((αHo/ yH+ 2 Ccuo) * Qa (
Ccu/Ccuo) + 2 (Ccuo -Ccu)
) = −(a I f'/y H) 1
(12) The interfacial reaction rate constants when three types of surfactants including the amphoteric surfactant of the present invention were used were as shown in Table 1. However, it was confirmed that the interfacial reaction rate constant was larger than that of other commercially available surfactants.

Table 1 Comparison of interfacial reaction rate constants Example 3 Aqueous phase consisting of IN sulfuric acid aqueous solution containing 100 mol/rn' of copper sulfate, and n- containing surfactant and 50 mol/rn' (7) purified LIX 85N An equal volume of the butane solution was taken, and while stirring at 11,000 rpm, 22 KHz ultrasonic waves (output soow) were irradiated for 5 minutes to prepare a W10 emulsion.

This was placed in an emulsion storage tank, and while stirring to the extent that phase separation did not occur, it was transferred to a flow-through type waste pipe removal device (inner volume 53.5 J) using a metering pump at a flow rate of 10.7 s/win.
Demulsification was attempted using an AC applied voltage of 1 to 5 KV.

Using 2C1 and GEQAPA of the present invention and commercially available 5pan80 and polyamine as surfactants, the relationship between applied voltage and demulsification 1t-Z (Z=C2J)/CLO" (where Cw is the water content in the emulsion) was investigated. , the result in the fifth
0 Surfactant of the present invention shown in 2 C,8GEQAP
Although A was used in a smaller amount than 5pan80, a typical commercially available surfactant, and polyamine, it was found that demulsification progressed at a low applied voltage and completed at 2 KV. Thus, although the amphoteric surfactant of the present invention forms a very stable emulsion and emulsion film as shown in Example 1, it is not electrically demulsified very easily. It was confirmed that it can be effectively used for total flexural separation, concentration, and other emulsion-based processes.

In addition, the surfactant concentration in the organic layer in Fig. 5 is 2Cts.
GEQAPA10mol/rn”, polyamide 742mo
l/m゛, 5pan8039鵬o1/rri” There is.

Manufacturing example? An amphoteric surfactant was obtained in exactly the same manner as in Production Example 1 except that undecanoic acid and dicyclohexylcarbodiimide were used instead of chloroacetic acid chloride. It was confirmed by elemental analysis, IR, and NMR spectra that this had the following structure.

The obtained 1L type amphoteric surfactant was 2 Ct8G EC
It will be expressed as 1゜Q A C2P A.

Production Example 3 An amphoteric surfactant was obtained in exactly the same manner as in Production Example 2 except that cetyl alcohol was used instead of stearyl alcohol. This was confirmed by elemental analysis, IR, and NMR spectra, and as a result, it was confirmed that it had the following structure.

The obtained amphoteric surfactant of the above formula was 2C,,GEC+o
It will be expressed as Q A C2P A.

Production Example 4 An amphoteric surfactant was obtained in exactly the same manner as in Production Example 1 except that 6-N,N-dimethylamino n-hexanol was used instead of N,N-dimethylaminoethanol. This was confirmed by elemental analysis, IR, and NMR spectra, and as a result, it was confirmed that it had the following structure.

The amphoteric surfactant of the above formula obtained by
We will display it as AC & FA.

Production Example 5 An amphoteric surfactant was obtained in exactly the same manner as in Production Example 2 except that 6-N,N-dimethylamino n-hexanol was used instead of N,N-dimethylaminoethanol. This was confirmed by elemental analysis, IR, and NMR spectra, and as a result, it was confirmed that it had the following structure.

The obtained amphoteric surfactant of the above formula is 2C,,G EC1
It will be expressed as ゜QAC,FA.

Example 4 The amphoteric surfactant of the present invention obtained in Production Example 1.2.3, 5 was added to lomo1/rn'', and the purified 1.1X85N was added to 5Qm.
n-heptane solution containing al/g and an equal volume of l
A W10 type emulsion was prepared by placing an aqueous N sulfuric acid solution in a container and irradiating it with 22 KHz ultrasonic waves (output 800 W) for 5 minutes while stirring at 11000 rpm. The droplet diameter of the internally dispersed water droplets in the obtained emulsion was measured using a Microtrac particle size analyzer Model 7995 (manufactured by Nichimso Co., Ltd.), and the obtained body area average diameter dP32 is shown in Table 2. For comparison, polyamine, a commercially available surfactant, was
The results obtained using wt% (42 o1/m'') are also shown.

It has been revealed that all of the amphoteric surfactants of the present invention form stable emulsions, and even when compared with commercially available surfactants, relatively fine droplet sizes have been obtained.

Example 5 The amphoteric surfactant of the present invention obtained in Production Example 2.3.5 was used at 1O O l/m'', and the film breakdown rate constant Kb was obtained under exactly the same conditions and method as in Example 1. was measured and the results are shown in Table 3.

As shown in Example 1, the commercially available surfactant 5pa
Compared to n80 and polyamines, Kb at the same concentration is l/
10 or less, indicating that a very stable emulsion was formed.

Example 6 Copper was extracted in the same manner as in Example 2 using each of the amphoteric surfactants of the present invention obtained in Production Example 2.3.5 at a concentration of 10*ol/m'. The interfacial reaction rate constant shown in 4 was obtained.

As shown in Table 1 of Example 2, the interfacial reaction rate constant of commercially available surfactant 5pan80 and polyamine is 10.
2(a kf'/yH) are 1.3 and 1.2, respectively. ? mo
l/rn"s, it is clear that the extraction rate with the amphoteric surfactants shown in Table 4 of the present invention is excellent. Example 7 2C1θGEC1 obtained in Production Example 5 An attempt was made to demulsify the emulsion using QAC, PA in the same manner as in Example 3. As a result, the applied voltage VCt required to demulsify the prepared emulsion by 99% was 2.6 KV. .The vCr of commercially available surfactant 5pan80 and polyamine are 3.1 and 3.31V, respectively.
It has become clear that demulsification can be more easily achieved than with commercially available surfactants.

Table 2 Measurement results of droplet diameter Table 4 Measurement results of interfacial reaction rate constant Effects of the invention When metal ions are separated and concentrated using a water-in-oil emulsion using the amphoteric surfactant of 14, A stable emulsion can be obtained with a small amount of surfactant used. Furthermore, the extraction rate of metal ions can be increased by using an emulsified liquid film using the present surfactant.

Furthermore, by using the surfactant of the present invention, demulsification is easy.

As described above, the present invention enables industrially advantageous separation and concentration of metal ions.

[Brief explanation of the drawing]

Figure 1 shows the IR of 2C,8GEQAPA obtained in the production example.
Figure 2 shows the spectrum (Nujoule method), Figure 2 shows the same NMR spectrum) Figure 3 shows the effect of surfactant concentration on the stability of the liquid film, Figure 4 shows the influence of the surfactant concentration on the stability of the liquid film. FIG. 5 is a diagram showing the influence of surfactants on the extraction rate, and FIG. 5 is a diagram showing the demulsification rate depending on the type of surfactant.

Claims (1)

[Claims] 1. A novel amphoteric surfactant represented by general formula (1). ▲There are numerical formulas, chemical formulas, tables, etc.▼...(1) (However, R and R' here represent a saturated or unsaturated hydrocarbon group having 8 to 20 carbon atoms, and may be the same or different from each other. m and n represent integers of 1 to 10, and may be the same or different from each other. X represents a halogen atom.) 2. A water-in-oil emulsion characterized by using an amphoteric surfactant. 3. A water-insoluble phase containing a metal extractant and an aqueous phase containing a metal ion concentrator are emulsified in the presence of a novel amphoteric surfactant represented by general formula (1), and water-in-oil (W/O ) type emulsion is formed, the emulsion is dispersed and stirred in an aqueous solution containing metal ions as the phase to be extracted, the metal ions are extracted with the emulsion, concentrated in the internal aqueous phase of the emulsion, and then the emulsion is A method for separating and concentrating metal ions, which comprises separating and demulsifying the metal ions, and separating an aqueous phase in which metal ions are concentrated from a water-insoluble phase.