KR20170015656A - Method for recovering multivalent metal ion from leaching solution containing sulfuric acid in which metal ions are leached, and composite membrane therefor - Google Patents

Abstract

The present invention relates to a method to collect polyvalent metal ions from a sulfuric acid-containing extract from which metal ions are extracted and a complex membrane. In order to collect polyvalent metal ions from a sulfuric acid-containing extract from which metal ions are extracted and generated during wet nonferrous refinement using sulfide ore as a raw material; the present invention uses the complex membrane including a polyamide coating layer formed by interfacial polymerization between a polyfunctional acid halide compound and a compound of aromatic polyvalent amine and aliphatic polyvalent amine. As such, the present invention is capable of improving chemical stability to sulfuric acid as well as improve water penetration flux and increase a recovery rate of rare metals by having an elimination rate of the polyvalent metal ions higher than an elimination rate of univalent metal ions.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing metal ions and a composite membrane therefor,

The present invention relates to a method for recovering polyvalent metal ions from a leaching solution containing sulfuric acid in which metal ions are leached, and a composite membrane therefor.

The smelting industry is an industry that produces raw materials containing rare metals and valuable metals by refining them with high purity materials using various methods. In the nonferrous smelting industries such as copper smelting and zinc smelting, since most of the raw materials are sulphide ores, waste sulfuric acid containing impurities with a sulfuric acid concentration of 2 to 15% is generated during the smelting process. The waste sulfuric acid generated during the smelting process contains various rare metals, but in the process water, the recovery of rare metals is neutralized due to the lack of processing technology.

In general, the mother liquor (leach solution) in the wet smelting process is in the form of sulfuric acid (10 to 15%) solution and the valuable metals (Cu, Zn etc.) and rare metals (In, Se, Re etc.) %. Conventionally, a neutralization method, a substitution method, an adsorption method, and an ion exchange method are mainly used for recovering the oil / rare metal dissolved in the mother liquor. However, these methods are disadvantageous in that they are costly in most cases or are not environmentally friendly due to a large amount of waste. Particularly, in applying the separation membrane to the recovery process, since the mother liquor containing the rare metal contains a large amount of monovalent ions (Na, Cl, F) and polyvalent ions (Ca, Mg, Pb, As) , And the chemical stability of the acid is most important for continuous separation / concentration.

On the other hand, a typical polyamide membrane can be obtained by interfacial polymerization of a polyfunctional amine and a polyfunctional acyl halide. One example of the aforementioned reverse osmosis composite membrane is US Pat. No. 4,277,344 (Registered on July 1, 1987), filed by Cadotte. This patent relates to an aromatic polyamide thin film obtained by interfacial polymerization of an aromatic polyfunctional amine containing two primary amine substituents and an aromatic acyl halide having three or more acyl halide functional groups. Specifically, the following steps are followed. M-phenylenediamine is coated on the microporous polysulfone support. The excess of the metaphenyldiamine solution is removed on the supporting layer, and then reacted with trimethoyl chloride (TMC) dissolved in Freon (trichlorotrifluoro ethane, Freon TF, DuPont) on the coated support layer. The contact time is about 10 seconds, and the actual reaction time is within 1 second. At that time, the performance was excellent. In addition to the above-mentioned patents for controlling the concentration and the components of the monomers and additives forming the polyamide layer, methods for controlling physical properties through post-treatment of membranes have also been studied. U.S. Patent No. 5,755,964 discloses a method of post-treating a reverse osmosis membrane or nanofiber having a polyamide separation layer with ammonia or alkyl amines to increase the flux. Flux and rejection of the reverse osmosis membrane or nanofiltration membrane prepared by the above method can be controlled and it is also possible to convert the reverse osmosis membrane into nanofilm. On the other hand, U.S. Patent No. 6,280,853 discloses a membrane obtained by grafting a polyalkylene oxide onto a polyamide membrane to reduce rejection to NF levels and to improve resistance to contamination.

Conventional techniques available for treatment of acid feeds are inefficient due to costs associated with environmental waste treatment and the disposal of contaminated acid as well as loss of useful extracted components. In addition, there is a continuing need for a separation medium and / or technique which, amongst others, makes it possible to recover useful components from the acid feed stream and / or to recover the acid for regeneration.

However, there is still a lack of semipermeable membranes that can remove dissolved metal cations and organic compounds from the liquid base feed stream with exceptional stability and permeability to acids.

An object of the present invention is to provide a method for efficiently and economically recovering valuable metals and rare metals generated in a smelting process, and a highly permeable composite membrane excellent in acid resistance that can be applied to the method.

A first aspect of the present invention is a method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions,

A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,

Here, when the leach solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the permeation flow rate of the composite membrane is 40 gallon / ft ² · day or more ≪ / RTI >

A second aspect of the present invention provides a porous polymer scaffold comprising: a porous polymer scaffold; And a polyamide coating layer formed on the surface of the porous polymer substrate by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound,

Characterized in that the permeate flow rate of the composite membrane is at least 40 gallon / ft ² · day when fed at a pressure of 15 kgf / cm 2 and at a temperature of 25 ° C, wherein the leachate containing 2,000 ppm sulfuric acid, And a composite membrane for recovering polyvalent metal ions from the leached sulfuric acid-containing leaching solution.

A third aspect of the present invention provides a water treatment apparatus comprising a composite membrane according to the second aspect.

Hereinafter, the configuration of the present invention will be described in detail.

The process water generated from the non-ferrous smelting process using sulphide ore as raw material contains various rare metals. Therefore, the separation and recovery technology of rare metals is needed. For this purpose, the rejection rate of the polyvalent metal ions, which are mainly rare metals, should be higher than the rejection rate of the monovalent metal ions and be excellent in the water permeation flow rate. In addition, since the above process contains sulfuric acid at a level of 2 to 15%, chemical stability to sulfuric acid is required for continuous separation / concentration.

The present invention relates to a polyamide coating layer formed by interfacial polymerization of a polyhydric amine and a polyfunctional acid halide in the recovery of polyvalent metal ions from a sulfuric acid-containing leach solution containing metal ions leached during wet nonferrous smelting using a sulfide ore as a raw material, And that the chemical stability to sulfuric acid can be improved by using an aromatic polyamine as a polyhydric amine. Furthermore, it has been found that by using aliphatic polyvalent amines in combination with aromatic polyvalent amines at this time, the chemical stability against sulfuric acid can be improved and the water permeation flow rate can be improved. Further, by using the composite membrane, it has been found that the rejection rate of polyvalent metal ions is higher than the rejection rate of monovalent metal ions, so that the recovery rate of rare metals can be increased. The present invention is based on this.

As described above, the method for recovering polyvalent metal ions from the leaching solution containing sulfuric acid from which the metal ions are leached according to the present invention,

A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,

Here, when the leached solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the water permeation flow rate of the composite membrane may be 40 gallon / ft ² · day or more.

The leachate containing sulfuric acid in which the metal ions are leached may be generated, for example, during non-ferrous smelting using a sulphide ore as a raw material. The process water or wastewater generated during the smelting process may be a sulfuric acid-containing leaching solution in which the metal ions are leached, which mainly include monovalent ions (H ⁺ and HSO ₄ ^- ), and include multivalent metal ions having two or more valences. In the present invention, the composite membrane has the ability to more easily retain the polyvalent metal ions while allowing the inherently monovalent sulfuric acid to permeate better. Specifically, in the composite membrane used in the present invention, the rejection rate of the polyvalent metal ion was higher than the rejection rate of the univalent metal ion (Table 1).

As described above, the composite membrane for recovering polyvalent metal ions from the leaching solution containing sulfuric acid from which the metal ions are leached according to the present invention comprises a porous polymer scaffold; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold, wherein the leached solution containing 2,000 ppm sulfuric acid in which the metal ions are leached is treated with 15 kgf / Cm < 2 > and a temperature of 25 DEG C, the water permeation flow rate of the composite membrane may be 40 gallon / ft < ² > day or more.

The composite membrane according to the present invention can be produced by a manufacturing method comprising the following steps.

a) preparing a porous polymer scaffold;

b) immersing the porous polymeric support in an aqueous solution containing a mixture of an aromatic polyamine and an aliphatic polyamine; And

c) immersing the porous polymer scaffold in an organic solution containing a polyfunctional acid halide compound to form a polyamide coating layer by interfacial polymerization;

Preferably, between step b) and step c) further comprises the following step.

b-1) removing an aqueous solution containing a mixture of an excess of an aromatic polyamine and an aliphatic polyamine remaining in the porous polymer scaffold immersed in the step b).

Preferably, after step c), the method may further comprise the steps of:

c-1) drying the porous polymer scaffold immersed in step c).

In the present invention, the porous polymer scaffold may have an average pore size of 10 nm to 1 m.

In step a) above, the preparation of the porous polymer scaffold can be accomplished by purchasing a commercialized porous polymer scaffold known in the art, or by using the method of manufacturing porous polymer scaffolds known in the art without limitation. Preferably, the first step is a vapor-induced phase separation (VIPS), a non-solvent induced phase separation (NIPS), a thermally induced phase separation (TIPS) Or a combination thereof.

According to the steam-induced phase separation method, a polymer solution in which a polymer resin is dissolved in a good solvent is formed, and the formed polymer solution is exposed to water vapor to form a phase transition. According to the non-solvent-derived phase separation method, a polymer solution in which a polymer resin is dissolved in a good solvent is formed, and the formed polymer solution is brought into contact with a solution containing a non-solvent, And solidification is induced to produce a film. On the other hand, according to the heat-induced phase separation method, the polymer solution is prepared by forcibly dissolving the polymer resin in a poor solvent at a temperature higher than the phase separation temperature. The polymer solution is molded, and the polymer solution is contacted with a cooling liquid at a phase separation temperature or lower to coagulate the polymer solution to produce a film.

The material of the porous polymer scaffold can be formed into a porous polymer scaffold, and as long as the surface of the porous scaffold can be polyamide-interfacial polymerized, the polymer used in the production of the porous polymer scaffold known in the art can be used without limitation. In the present invention, as the porous polymer scaffold, polysulfone, polyethersulfone, cellulose acetate, polyamide or a combination thereof may be used.

In the present invention, the porous polymer scaffold may be in the form of a film. The thickness of the porous polymer scaffold may be 20 to 150 μm, preferably 30 to 100 μm. In addition, the porous polymer scaffold may be reinforced with a nonwoven fabric.

In the step b), when a polyamide coating layer is formed by interfacial polymerization of a polyfunctional amine and a polyfunctional acid halide compound, the use of a mixture of an aromatic polyamine and an aliphatic polyamine as a polyamine increases the chemical stability of the acid A good water permeation flow rate can be secured.

In the present invention, the weight ratio of the aromatic polyamine to the aliphatic polyamine in the mixture of the aromatic polyamine and the aliphatic polyamine may be from 1: 1 to 1.9: 0.1, preferably from 1.5: 0.5 to 1.8: 0.2. That is, the aromatic polyhydric amine may be used at a ratio of 1 to 1.9 parts by weight: 0.1 to 1 part by weight of an aliphatic polyvalent amine. In the present invention, as the polyvalent amine, an aromatic polyvalent amine is used as a main component and an aliphatic polyvalent amine is used in combination to increase the permeation flow rate. If the weight ratio of the aromatic polyvalent amine to the aliphatic polyvalent amine is less than 1 part by weight, the chemical stability to the acid may be deteriorated. If the weight ratio of the aromatic polyvalent amine is more than 1.9 parts by weight, the water permeation flow rate may be decreased.

Specifically, in the examples of the present invention, it was confirmed that when a mixture of an aromatic polyamine and an aliphatic polyamine as a polyamine amine monomer was used, the chemical stability to the acid was excellent and the water permeation flow rate could be improved (see Tables 1 and 2 ). On the other hand, in Comparative Example 1, when the aliphatic polyamine was used as an aliphatic polyamine, the acid resistance was poor (Table 2), and when the aromatic polyamine was used as the polyamine monomer in Comparative Example 2, the acid resistance was improved (Table 2) It was confirmed that the permeation amount dropped sharply (Table 1 and Table 2).

In the present invention, the mixture of the aromatic polyamine and the aliphatic polyamine is used in the form of an aqueous solution containing 0.1 to 10% by weight, for example, 1 to 5% by weight, specifically 2% by weight, .

As used herein, the term "aromatic polyvalent amine" may refer to an aromatic compound containing two or more amine groups. In the present invention, the aromatic polyvalent amine is at least one selected from the group consisting of metaphenylenediamine, paraphenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylene Diamino, 3-chloro-1,4-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol, xylenediamine or combinations thereof , But is not limited thereto.

The term "aliphatic polyvalent amine " used in the present invention may mean an aliphatic compound containing two or more amine groups. In the present invention, the aliphatic polyvalent amine may be ethylenediamine, 1,3-diaminopropane, tris (2-aminoethyl) amine or a combination thereof, but is not limited thereto.

In the step b), the aqueous solution containing a mixture of the aromatic polyamine and the aliphatic polyamine may further comprise a hydrophilic compound, i.e., a compound containing a hydrophilic group, in order to provide a polyamide coating layer having improved stain resistance. At this time, the compound containing the hydrophilic group may be present in an amount of 0.001 to 8% by weight, more preferably 0.01 to 4% by weight, in the aqueous solution.

The hydrophilic compound added to the aqueous solution containing the mixture of the aromatic polyvalent amine and the aliphatic polyvalent amine is at least one selected from the group consisting of a hydroxyl group, a sulfonated group, a carbonyl group, a trialkoxysilane group, an anion group and a tertiary amino group Is a hydrophilic compound having a hydrophilic functional group. More preferably a hydrophilic amino compound.

More specifically, non-limiting examples of the hydrophilic compound having a hydroxy group include 2-ethyl-1,3-hexanediol, 1,3-diamino-2-propanol, ethanolamine, diethanolamine, -Propanol, 4-amino-1-butanol, 2-amino-1-butanol or mixtures thereof.

Non-limiting examples of hydrophilic compounds having a carbonyl group include aminoacetaldehyde dimethylacetal, a-aminobutylolactone, 3-aminobenzamide, 4-aminobenzamide, N- (3-aminopropyl) Or mixtures thereof.

In addition, non-limiting examples of hydrophilic compounds containing a trialkoxysilane group include (3-aminopropyl) triethoxysilane, (3-aminopropyl) trimethoxysilane, and mixtures thereof.

Non-limiting examples of the hydrophilic compound having an anionic group include camphorsulfonic acid, 3-amino-1-propanesulfonic acid, 4-amino-1-butanesulfonic acid, 2-aminoethylhydrogensulfate, 3- Amino-3-hydroxybenzoic acid, 6-aminohexanoic acid, 6-aminohexanoic acid, 3- amino-4-hydroxybenzenesulfonic acid, Aminobutanoic acid, 4-amino-2-hydroxybutanoic acid, 4-aminobutanoic acid, glycine, taurine, glutamic acid, or a mixture thereof.

Examples of the hydrophilic compound having one or more tertiary amino groups include triethylamine, 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, 4- (2-aminoethyl) - (2-aminoethyl) piperazine, 3,3'-diamino-N-methyldipropylamine, 1- (3-aminopropyl) imidazole or mixtures thereof.

In the above step b-1), the removal of the aqueous solution containing the mixture of the excess aromatic polybasic amine and the aliphatic polybasic amine can be achieved by using a roller or by leaving at room temperature or both.

In the present invention, the polyfunctional acid halide compound may be a polyfunctional acyl halide, a polyfunctional sulfonyl halide, a polyfunctional isocyanate, or a mixture thereof, but is not limited thereto. Preferably, the polyfunctional acid halide is selected from the group consisting of trimesoyl halide, benzophenone tetracarboxylic acid halide, trimellitic acid halide, pyromellitic acid halide, isophthalic acid halide, terephthalic acid halide, Naphthalene dicarboxylic acid halide, dicarboxylic acid halide, 1,3,5-cyclohexanetricarboxylic acid halide, 1,3-cyclohexanedicarboxylic acid halide, 1,4-cyclohexanedicarboxylic acid halide Or a mixture thereof.

In the present invention, the polyfunctional acid halide compound can be used in the form of an organic solution containing 0.01 to 2% by weight, for example, 0.05 to 0.5% by weight, specifically 0.1% by weight, of the total organic solution in interfacial polymerization .

In the present invention, an organic solution containing a polyfunctional acid halide compound is a C _{8 -12} isoparaffin (isoparaffin) type solvent, specifically, ISOL-c (SK Energy, Republic of Korea, CAS No. 64741-66-8) as the organic solvent Can be used.

In the above step c-1), drying of the porous polymer scaffold can be performed at a temperature of 40 to 80 ° C, for example, at a temperature of 50 to 70 ° C for 1 minute to 30 minutes, for example, 5 minutes to 15 minutes .

As described above, in the composite membrane according to the present invention, the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion. Specifically, when the leaching solution containing 2,000 ppm sulfuric acid in which the metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of the polyvalent metal ion Rate. Preferably, the composite membrane according to the present invention may have a rejection rate of polyvalent metal ions of 50% or more. When feeding a composite membrane leachate containing 2,000 ppm sulfuric acid, the metal ion is leached according to the invention to a pressure and a temperature of 25 ℃ of 15 kgf / ㎠, the permeate flux of the composite membrane 40 gallon / ft ² · day Specifically, 40 to 120 gallon / ft < ² > day. Therefore, by using the composite membrane according to the present invention, the rejection rate of the polyvalent metal ion in the first step is higher than the rejection rate of the monovalent metal ion, and also excellent water permeation flow rate, for example, 40 gallon / ft ² · day The permeate flow rate can be shown. For example, when the leaching solution containing 2,000 ppm sulfuric acid in which the metal ions are leached in the first step is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of the polyvalent metal ion Higher water permeation flow rate, for example, a water permeation flow rate of 40 gallon / ft < ² > day or more.

In addition, the composite membrane according to the present invention has excellent chemical stability to an acid as described above. Preferably, the composite membrane according to the present invention has a leach solution containing 2,000 ppm sulfuric acid in which metal ions have been leached even after immersing in a 15 wt% sulfuric acid aqueous solution for 10 days or more, for example, 3 weeks or more and 10 days to 100 days When it is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the rejection rate of polyvalent metal ions of 80% or more can be shown. Specifically, in the present invention, the composite membrane is immersed in a 15 wt% sulfuric acid aqueous solution, and after 28 days, the leached solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / As a result of examining the rejection rate of the ions, it was confirmed that the rejection rate of the polyvalent metal ions was 80% or more. Thus, it can be seen that the composite membrane of the present invention can exhibit excellent polyvalent metal ion recovery without damaging even when exposed under acidic conditions for a long time.

The composite membrane according to the present invention can be used for a water treatment apparatus, specifically an apparatus for providing an acidic environment, for example, a smelting water treatment apparatus.

The present invention relates to a method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions, which occurs during non-ferrous smelting using a sulfide ore as a raw material, in which an interface between a mixture of aromatic polyvalent amine and aliphatic polyvalent amine and a polyfunctional acid halide By using a composite membrane comprising a polyamide coating layer formed by polymerization, it is possible not only to improve the chemical stability to sulfuric acid but also to improve the water permeation flow rate. In particular, the rejection rate of the polyvalent metal ion The recovery rate of rare metals can be increased.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Example  One: Acid resistance  Polyamide Composite membrane  Manufacturing 1

First, 1.5 wt% of metaphenylenediamine (MPD, Sigma-Aldrich) and 0.5 wt% of ethylenediamine (ED, Sigma-Aldrich) were used as the polyamine amine monomer and 1 wt% of triethylamine TEA, Sigma-Aldrich), 1.1 wt% camphorsulfonic acid (CSA, Sigma-Aldrich) and 0.2 wt% 2-ethyl-1,3-hexanediol (EHD , Sigma-Aldrich) were further dissolved in water to prepare 500 ml of a polyfunctional amine aqueous solution. On the nonwoven fabric, a porous polysulfone support having pores having a pore size of 30 nm, which had been cast, was immersed in 500 ml of the above-prepared polyfunctional amine aqueous solution for 2 minutes.

Then, excess polyfunctional amine aqueous solution remaining in the porous polysulfone support immersed in the polyfunctional amine aqueous solution was removed using a rubber roller, and then left at room temperature to be completely removed.

Then, 0.1% by weight of trimesoyl chloride (TMC, Sigma-Aldrich) was dissolved by using ISOL-c (SK Energy, Korea, CAS No. 64741-66-8) as an organic solvent to prepare a polyfunctional acyl halide organic solution 500 ml were prepared. Thereafter, the porous polysulfone support from which the excess aqueous solution was removed was immersed in the polyfunctional acyl halide organic solution for 1 minute.

Then, the porous polysulfone support immersed in the polyfunctional acyl halide organic solution was dried in an oven at a temperature of 60 DEG C for 10 minutes to obtain a polyamide composite membrane.

Example  2: Acid resistance  Polyamide Composite membrane  Manufacturing 2

(MPD, Sigma-Aldrich), 0.5% by weight of paraphenylenediamine (PPD, Sigma-Aldrich) and 0.2% by weight of ethylenediamine as a polyamine monomer in Step 1 of Example 1 (ED, Sigma-Aldrich) was used instead of the polyimide composite membrane.

Example  3: Acid resistance  Polyamide Composite membrane  Manufacturing 3

(MPD, Sigma-Aldrich), 0.7% by weight of paraphenylenediamine (PPD, Sigma-Aldrich) and 0.2% by weight of ethylenediamine as a polyamine monomer in Step 1 of Example 1 (ED, Sigma-Aldrich) was used instead of the polyimide composite membrane.

Example  4: Acid resistance  Polyamide Composite membrane  Manufacturing 4

(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.1% by weight of 1,3-propanediol as monohydric amine monomers in Step 1 of Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.

Example  5: Acid resistance  Polyamide Composite membrane  Manufacturing 5

(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.2% by weight of 1,3-propanediol dianhydride as a polyamine monomer in Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.

Example  6: Acid resistance  Polyamide Composite membrane  Manufacturing 6

(PPD, Sigma-Aldrich), 0.2% by weight of ethylenediamine (ED, Sigma-Aldrich) and 0.3% by weight of 1,3-propanediol dianhydride as a polyamine monomer in Example 1, Dianaminopropane (DAP, Sigma-Aldrich) was used in place of di-aminopropane (DAP, Sigma-Aldrich) to prepare a polyamide composite membrane.

Comparative Example  One

A polyamide composite membrane was prepared in the same manner as in Example 1, except that 2 wt% piperazine (PIP, Sigma-Aldrich) was used as the polyamine amine in Step 1 of Example 1 above.

Comparative Example  2

A polyamide composite membrane was prepared in the same manner as in Example 1 except that 2 wt% of metaphenylenediamine (MPD, Sigma-Aldrich) was used alone as a monomer in Step 1 of Example 1 above.

Experimental Example  1: polyamide Composite membrane  Measurement of permeation characteristics

In order to confirm the permeation characteristics of the separator according to the present invention, the polyamide composite membranes prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were impregnated with sodium chloride at a concentration of 2,000 ppm at a temperature of 25 ° C. and a pressure of 15 kgf / cm ² (NaCl) and an aqueous solution of magnesium sulfate (MgSO ₄ ) at a concentration of 2,000 ppm were measured. The results are shown in Table 1 below.

Condition NaCl MgSO ₄ Water permeability
(gallon / ft ² .day) Exclusion rate (%) Water permeability
(gallon / ft ² .day) Exclusion rate (%) Example 1 50.45 77.04 50.80 93.66 Example 2 75.54 81.79 75.65 95.38 Example 3 96.08 89.53 90.98 94.99 Example 4 94.16 72.19 90.66 88.88 Example 5 118.28 50.72 109.67 73.36 Example 6 112.97 41.64 102.15 66.85 Comparative Example 1 79.5 44.98 73.39 85.95 Comparative Example 2 22.74 97.97 25.21 99.66

Experimental Example  2: Polyamide Composite membrane Acid resistance  Measurement of retention capacity

The polyamide composite membranes prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were immersed in a 15 wt% aqueous solution of sulfuric acid (H ₂ SO ₄ , Sigma-Aldrich) in order to confirm the acid- And the rejection rate after 28 days was measured. At this time, physical properties of the membrane were measured using an aqueous solution of magnesium sulfate (MgSO ₄ ) at a concentration of 2,000 ppm at a temperature of 25 ° C and a pressure of 15 kgf / cm ² . The results are shown in Table 2 below.

Condition MgSO ₄ exclusion ratio (%) Example 1 98 Example 2 98 Example 3 96 Example 4 94 Example 5 82 Example 6 80 Comparative Example 1 30 Comparative Example 2 99

In the case of using piperazine as a polyamine monomer in Comparative Example 1, the water permeation rate was high, the rejection rate of NaCl was low, and the rejection rate of MgSO ₄ was high. In the case of using metaphenylenediamine as the amine monomer in Comparative Example 2, the water permeation amount was low, the rejection rate of NaCl was high, and the rejection ratio of MgSO ₄ was also high. However, in the case of Comparative Example 1, the acid resistance test showed that it was easily broken by acid, and that it was easily broken (Table 2). Comparative Example 2 showed excellent acid resistance (Table 2) The salt rejection rate was so high that it was difficult to apply it to the mother liquor.

In addition, when Comparative Example 2 and Example 1 were compared, it was found that the addition of ethylenediamine decreased the rejection rate as the water permeation amount increased. In Examples 1 to 3, ethylenediamine was fixed at 0.2% by weight and the ratio of m-phenylenediamine and p-phenylenediamine was adjusted. As a result, the water permeation amount was increased while maintaining the rejection rate. In Examples 4 to 6, ethylenediamine was fixed at 0.2% by weight and the ratio of paraphenylenediamine to 1.3-diaminopropane was adjusted. As the amount of 1,3-diaminopropane was increased, the water removal rate was increased and the rejection rate was decreased.

From the above results, it has been found that when the basic membrane permeability is determined, the aromatic acid polyamide monomer shows excellent acid resistance. The minimum performance maintenance period was more than 3 weeks, and it was confirmed that the membrane had high water permeability and acid resistance as compared with the membrane made with the piperazine monomer (Comparative Example 1).

Claims (14)

A method for recovering polyvalent metal ions from a sulfuric acid-containing leach solution containing leached metal ions,
A porous polymeric support; And a polyamide coating layer formed by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound on the surface of the porous polymer scaffold and supplying a leaching solution containing a sulfuric acid into which a metal ion is leached, A first step of recovering ions,
Here, when the leach solution containing 2,000 ppm sulfuric acid in which metal ions are leached is supplied at a pressure of 15 kgf / cm 2 and a temperature of 25 ° C, the permeation flow rate of the composite membrane is 40 gallon / ft ² · day or more Way.
The method according to claim 1, wherein the sulfuric acid-containing leach solution containing leached metal ions is generated during wet non-ferrous smelting using a sulfide ore as a raw material.
The method of claim 1, wherein the porous polymeric support comprises polysulfone, polyethersulfone, cellulose acetate, polyamide, or a combination thereof.
The method of claim 1, wherein the weight ratio of aromatic polyamine: aliphatic polyamine in the mixture of aromatic polyamine and aliphatic polyamine is from 1: 1 to 1.9: 0.1.
The method of claim 1 wherein the weight ratio of aromatic polyamine: aliphatic polyamine in the mixture of aromatic polyamine and aliphatic polyamine is from 1.5: 0.5 to 1.8: 0.2.
The aromatic polyamine according to claim 1, wherein the aromatic polyvalent amine is selected from the group consisting of metaphenylenediamine, paraphenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6- Diamino benzene, phenylene diamine, 3-chloro-1,4-phenylenediamine, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol, xylenediamine, ≪ / RTI >
The process according to claim 1, wherein the aliphatic polyvalent amine is ethylenediamine, 1,3-diaminopropane, tris (2-aminoethyl) amine or a combination thereof.
The method of claim 1, wherein the polyfunctional acid halide compound is a polyfunctional acyl halide, a polyfunctional sulfonyl halide, a polyfunctional isocyanate, or a mixture thereof.
The method according to claim 1, wherein the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion.
The method according to claim 1, wherein the rejection rate of the polyvalent metal ion is 50% or more.
A porous polymeric support; And a polyamide coating layer formed on the surface of the porous polymer substrate by interfacial polymerization of a mixture of an aromatic polyamine and an aliphatic polyamine and a polyfunctional acid halide compound,
Characterized in that the permeate flow rate of the composite membrane is at least 40 gallon / ft ² · day when fed at a pressure of 15 kgf / cm 2 and at a temperature of 25 ° C, wherein the leachate containing 2,000 ppm sulfuric acid, And recovering the polyvalent metal ion from the leached sulfuric acid-containing leach solution.
12. The composite membrane according to claim 11, wherein the rejection rate of the polyvalent metal ion is higher than the rejection rate of the monovalent metal ion.
12. A water treatment apparatus comprising the composite membrane of claim 11.
14. The water treatment apparatus according to claim 13, characterized by being a smelting process water treatment apparatus.