CN114349143A - Complex coacervate phase system and preparation method and application thereof - Google Patents
Complex coacervate phase system and preparation method and application thereof Download PDFInfo
- Publication number
- CN114349143A CN114349143A CN202111592440.7A CN202111592440A CN114349143A CN 114349143 A CN114349143 A CN 114349143A CN 202111592440 A CN202111592440 A CN 202111592440A CN 114349143 A CN114349143 A CN 114349143A
- Authority
- CN
- China
- Prior art keywords
- phase system
- sodium
- quaternary ammonium
- complex
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the field of environmental pollution and surfactant science, and particularly relates to a complex condensed phase system which comprises an anionic surfactant and quaternary ammonium salt, wherein a condensed phase with low charge and high surface activity is obtained through electrostatic interaction between the anionic surfactant and the quaternary ammonium salt. The condensed phase of the present invention can adsorb and remove metal ions in the system with high efficiency.
Description
Technical Field
The invention belongs to the field of environmental pollution and surfactant science, and particularly relates to a complex condensed phase system and a preparation method and application thereof.
Background
With the acceleration of global industrialization process, the environmental pollution problem is becoming more serious and becomes one of the key problems threatening the survival and development of human society. Among the problems of environmental pollution, industrial wastewater containing metal ions such as heavy metals/rare earth elements discharged from mineral mining, metal smelting, electroplating and battery production is one of the key factors causing global water deterioration.
The current treatment methods for the industrial wastewater mainly comprise the following steps: chemical precipitation, ion exchange/adsorption, membrane separation, electrochemical methods, and the like. The chemical precipitation method has low decontamination factor, and the precipitation needs further concentration and solidification, and other methods are gradually replaced. The ion exchange method usually needs to carry out post-treatment on the used exchange resin in a combustion decomposition mode, and because the resin contains a large amount of ammonia nitrogen, toxic waste gas can be generated during combustion decomposition, so that the ion exchange method has great danger and is easy to cause secondary pollution. When the membrane separation method is used, because substances such as microorganisms and solid particles exist in the actual wastewater besides metal pollutants, the microorganisms and the solid particles can cause membrane pollution, membrane blockage and other problems, and the application of the membrane separation method in the actual engineering is limited. The electrochemical method is used for enriching heavy metal ions in the wastewater through oxidation-reduction reactions between a cathode and an anode under the electrochemical action, the electrochemical method comprises an internal electrolysis method and an electric flocculation method, the reaction speed of the internal electrolysis method is slow, and suspended matters are collected on the surface of an electrode after the internal electrolysis method is operated for a long time, so that the electrolytic capacity is reduced; whereas the electroflocculation process suffers from electrode passivation under long continuous operation.
In conclusion, the conventional methods for treating industrial wastewater have certain limitations, so that finding a new method for treating industrial wastewater containing metal ions such as heavy metals/rare earth elements has important practical significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a complex condensed phase system and a preparation method and application thereof.
The invention adopts the following technical scheme:
a complex condensed phase system comprises an anionic surfactant and quaternary ammonium salt, wherein the quaternary ammonium salt is a single-quaternary ammonium salt, the concentration of the anionic surfactant is 10 mM-40 mM, and the concentration of the quaternary ammonium salt is 20 mM-70 mM.
According to the embodiment of the invention, the anionic surfactant and the quaternary ammonium salt are subjected to electrostatic interaction to obtain the condensed phase with low charge and high surface activity, so that the occlusion performance and the enrichment capacity of the system are influenced, and the metal ion enrichment system with the metal ion enrichment capacity is obtained.
Specifically, a metal ion enrichment system with low charge and high surface activity can be obtained by utilizing the interaction between an anionic surfactant and quaternary ammonium salt with opposite charges. The quaternary ammonium salt can induce the anionic surfactant to form a condensed phase system, so that the occlusion performance and the enrichment capacity of the system are influenced, and the enrichment efficiency is increased.
According to an embodiment of the present invention, the complex coacervate phase system may further comprise a metal ion extractant, the metal ion extractant comprises at least one of tributyl phosphate (TBP), tri-N-octylphosphine oxide (TOPO), triisopentyl phosphate (TiBP), octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO), suberic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, 2-hydroxy-3-naphthoic acid, 2-naphthylacetic acid, biphenyl-4, 4-dicarboxylic acid, 4-hydroxymethylbiphenyl, 4' -dihydroxybiphenyl, 4-cyanobiphenyl, 4-phenylphenol, 2-naphthol, preferably octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO).
CMPO is a ligand with broad-spectrum complexing ability for heavy metals and lanthanide series and the like, but common CMPO extraction requires an organic solvent or an ionic liquid (such as [ C ]4mim][PF6]) The use of large amounts of organic solvents and ionic liquids as diluents not only increases the cost, but also raises a series of problems such as safety problems and volatile contaminants. In the coacervate system of the invention, CMPO can be concentrated in the droplets of the coacervate, which itself remains intact. In the invention, the coacervate phase has the function of enriching metal ions, and the CMPO can be coordinated with the metal ions, so that in the metal ion enrichment process, the coacervate phase firstly enriches the metal ions, and then the CMPO in the coacervate phase liquid drop is coordinated with the metal ions so as to firmly fix the metal ions to be stabilized in the coacervate phase, thereby realizing the long-term stability of the metal ions in the coacervate phaseAnd (5) performing quantitative enrichment.
According to an embodiment of the invention, the complex coacervate phase system further comprises water, such as deionized water.
According to an embodiment of the invention, the pH of the complex coacervate phase system is neutral, i.e. pH 7.
According to an embodiment of the invention, the concentration of anionic surfactant in the complex coacervate phase system is between 10mM and 40mM, preferably between 20mM and 30mM, e.g.10 mM, 20mM, 30mM, 40 mM.
According to an embodiment of the invention, the concentration of quaternary ammonium salt in the complex coacervate phase system is between 20mM and 70mM, preferably between 30mM and 60mM, e.g.20 mM, 30mM, 40mM, 50mM, 60mM, 70 mM.
According to an embodiment of the present invention, the concentration of the metal ion extractant in the complex condensed phase system is 0.1 to 5mM, preferably 0.2 to 4 mM.
According to an embodiment of the invention, the concentration of CMPO in the complex coacervate phase system is 0.1-5 mM, preferably 0.2-4 mM, 0.2-0.8 mM, 0.5-3.5 mM, 1-3 mM, e.g. 0.5mM, 1mM, 2mM, 3mM, 4 mM.
According to an embodiment of the invention, the molar ratio of the anionic surfactant to the quaternary ammonium salt in the complex condensed phase system is 1:5 to 5:1, preferably 2:5 to 5:2, such as 1:5, 2:5, 3:5, 4:5, 1: 1.
According to the embodiment of the invention, the mole ratio of the anionic surfactant to the metal ion extracting agent in the complex condensed phase system is 100: 1-10: 1.
Preferably, the molar ratio of the anionic surfactant to the CMPO in the complex condensed phase system is 100: 1-10: 1, preferably 80: 1-20: 1, 70: 1-20: 1, 60: 1-30: 1, 50: 1-40: 1, for example 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20: 1.
According to an embodiment of the present invention, the anionic surfactant may be anionic surfactants having different alkyl chain lengths, and may be at least one selected from the group consisting of a sodium sulfate salt having 8 to 20 carbon atoms, a sodium sulfonate salt having 8 to 20 carbon atoms, a sodium benzenesulfonate salt having 8 to 20 carbon atoms, and a polyethyleneated alkyl sulfate salt having 8 to 20 carbon atoms. The sodium sulfate salt having 8 to 20 carbon atoms includes, for example, sodium octyl sulfate, sodium decyl sulfate, sodium dodecyl sulfate or sodium tetradecyl sulfate; the sodium salt of a sulfonic acid having 8 to 20 carbon atoms includes, for example, sodium decyl sulfonate or sodium dodecyl sulfonate; the sodium salt of a benzenesulfonic acid having 8 to 20 carbon atoms includes, for example, sodium dodecylbenzenesulfonate or sodium tetradecylbenzenesulfonate; the polyethylene-substituted alkyl sulfate having 8 to 20 carbon atoms includes, for example, sodium lauryl ether sulfate, sodium tetradecyl ether sulfate, or sodium hexadecyl ether sulfate.
Quaternary ammonium salts are compounds formed by substituting four hydrogen atoms in an ammonium ion with a hydrocarbon group, and include mono-quaternary ammonium salts and di-quaternary ammonium salts. The monoquaternary ammonium salts are the most common quaternary ammonium salts in the art and have the formula R4NX, wherein R represents a hydrocarbon group, and X represents a halogen anion or an acid radical ion. The diquaternary ammonium salt is, for example, a quaternary ammonium salt having the formula wherein X is selected from the group consisting of positive integers of 8, 10, 12 or 14, Y is selected from the group consisting of positive integers of 3, 4, 6 or 8, and A is-May be selected from Cl-Or Br-And the like. Examples thereof include quaternary ammonium salts of Gemini type.
According to an embodiment of the invention, the quaternary ammonium salt is a mono-quaternary ammonium salt having the formula R4NX, wherein R may be the same or different from each other, are independently selected from C1-C8 alkyl, preferably C1-C6 alkyl, X is halogen anion selected from F-、Cl-、Br-Or I-。
Preferably, the quaternary ammonium salt is selected from at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetra-n-butylammonium chloride, tetrabutylammonium fluoride (TBAF).
According to an embodiment of the present invention, the structure of the coacervate phase is a liquid-liquid phase separation structure, and preferably the liquid-liquid phase separation structure is a coacervate phase in which droplets having a size of 1 to 20 μm are coacervated.
Liquid-liquid phase separation, also known as liquid-liquid coacervation, refers to the phenomenon or process whereby a homogeneous colloidal solution spontaneously separates into two incompatible liquid phases, one of which contains a high concentration of colloids, referred to as the coacervate or liquid-liquid coacervate, and is in equilibrium with the relatively dilute phase. The liquid-liquid condensed phase liquid drops can spontaneously condense and stratify in water to form a condensed phase with a clear phase interface with an equilibrium phase, namely the liquid-liquid condensed phase continuously condenses from condensed phase liquid drops with the initial size of 1-20 mu m and forms large liquid drops until the liquid drops are connected into a whole to form the condensed phase with the clear interface with the water.
According to an embodiment of the present invention, the condensed phase system of the present invention is capable of enriching metal ions, such as, for example, rare earth metal ions or heavy metal ions, preferably europium ions, neodymium ions, yttrium ions, ytterbium ions, lead ions.
The invention also provides a preparation method of the complex condensed phase system, which comprises the following steps: and mixing an anionic surfactant, quaternary ammonium salt and water to obtain the complex coacervate phase system.
According to an embodiment of the invention, the preparation method further comprises the steps of: a metal ion extractant, preferably CMPO, is added to the complex coacervate phase system. This step serves to achieve a more stable enrichment of the metal ions.
According to an embodiment of the invention, the preparation method further comprises the steps of: adding a metal ion extraction agent, preferably CMPO, to the complex coacervate phase system followed by addition of metal ions.
According to an embodiment of the present invention, after mixing the anionic surfactant, the quaternary ammonium salt and water, further comprising adjusting the pH to neutral using an acidic solution, for example, adjusting the pH to neutral using hydrochloric acid (HCl).
According to an embodiment of the invention, the anionic surfactant and the quaternary ammonium salt have the meaning as described above.
According to an embodiment of the invention, the concentration of anionic surfactant in the complex coacervate phase system is between 10mM and 40mM, preferably between 20mM and 30mM, e.g.10 mM, 20mM, 30mM, 40 mM.
According to an embodiment of the invention, the concentration of quaternary ammonium salt in the complex coacervate phase system is between 20mM and 70mM, preferably between 30mM and 60mM, e.g.20 mM, 30mM, 40mM, 50mM, 60 mM.
The invention also provides the application of the complex condensed phase system for enriching metal ions, such as the separation and enrichment of metal ions in industrial wastewater containing metal ions of heavy metals and/or rare earth metals.
According to an embodiment of the invention, in the use of the complex coacervate phase system for enrichment of metal ions, the concentration of the metal ions is between 50mg/L and 500 mg/L.
According to an embodiment of the invention, the metal ions are, for example, rare earth metal ions or heavy metal ions, preferably europium ions, neodymium ions, yttrium ions, ytterbium ions, lead ions.
The invention also provides an enrichment system of metal ions, which comprises the complex condensed phase system.
Advantageous effects
In the present invention, the anionic surfactant and the quaternary ammonium salt form a complex coacervate phase system of the surfactant and the quaternary ammonium salt by non-covalent bonding, and the coacervate phase can efficiently remove heavy metal ions from water when the pH is neutral. Compared with the existing heavy metal adsorbent, the complex condensed phase system has extremely high adsorption capacity and adsorption efficiency, can quickly realize adsorption within 5min, has the extraction rate of more than 60% on metal ions, and can reach more than 90% under the condition of adding the metal ion extractant.
In addition, the cohesive phase has high viscosity, the integral phase state is not damaged after the metal is adsorbed, and the cohesive phase is easy to settle after centrifugation and is convenient to separate.
Drawings
FIG. 1 is a graph showing the turbidity change of a system under the action of different concentrations of surfactant and quaternary ammonium salt.
FIG. 2 is an optical microscopic view and a macroscopic view of the condensed phase formed in example 1.
FIG. 3 is a cryo-transmission electron micrograph of the condensed phase formed in comparative example 1.
FIG. 4 is a graph showing the change of rheological parameters of TBAF/SDS coacervate phase.
FIG. 5 is a graph showing the analysis of the content of metal ions remaining in the supernatant after the condensed phase formed in example 2 was enriched with metals.
FIG. 6 is a graph showing the analysis of the content of metal ions remaining in the supernatant after the condensed phase formed in example 3 was enriched with metals.
FIG. 7 is a graph showing the analysis of the content of metal ions remaining in the supernatant after the condensed phase formed in example 10 was enriched with metals.
Fig. 8 is a graph showing analysis of the content of metal ions remaining in the supernatant after the aggregate formed in comparative example 4 was enriched with metal.
Fig. 9 is a graph showing analysis of the content of metal ions remaining in the supernatant after the aggregate formed in comparative example 5 was enriched with metal.
FIG. 10 is a graph showing the analysis of the content of metal ions remaining in the supernatant after the aggregate formed in example 11 was enriched with metal.
Fig. 11 is a macroscopic view of the condensed phase formed in example 10 after enrichment with metal.
Fig. 12 is a macroscopic view of the aggregate formed in comparative example 1.
Detailed Description
The condensed phase system of the present invention, its preparation method and application will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The instruments and models used:
a probe colorimeter with the model of Brinkman PC 920;
an inductively coupled plasma emission spectrometer (ICP-MS) with the model of Thermo Icap RQ;
optical microscopic imager: an optical microscope equipped with a digital camera, the model of the optical microscope being SP-8C (8 CA);
freezing transmission electron microscope: the model is JEOL JEM-2010 TEM;
a rheometer: TA Discovery-DHR-1 dynamic shear rheometer.
Example 1
Tetrabutylammonium fluoride (TBAF), Sodium Dodecyl Sulfate (SDS) and deionized water are compounded, stirred and dissolved according to the following proportion, and hydrochloric acid is used for adjusting the pH to 7.0, and the volume is 5 mL:
TBAF 60mM
SDS 40mM
comparative example 1
Tetrabutylammonium fluoride (TBAF), Sodium Dodecyl Sulfate (SDS) and deionized water are compounded, stirred and dissolved according to the following proportion, and hydrochloric acid is used for adjusting the pH to 7.0, and the volume is 5 mL:
TBAF 5mM
SDS 20mM
phase characterization and rheological testing of complex coacervate phase systems:
1. physical phase
And (3) phase diagram testing: turbidity was measured at 450nm using a probe colorimeter. The final turbidity value was recorded (. about.3 minutes) after the readings stabilized, and the turbidity was set to zero using triple distilled water as a standard sample.
And (3) adding SDS solution into TBAF solutions with different concentrations (0-80mM) dropwise, detecting the turbidity of the sample in real time, stopping stirring when the turbidity is reduced to a flat state, and standing the solution until the test is finished. Turbidity curves were plotted, the transition course of the aggregates was examined by turbidity titration, and the various turbidity curves were integrated to give the corresponding phase diagram (see FIG. 1).
As can be seen from figure 1, when the anionic surfactant concentration is below C1, the complexation of the quaternary ammonium salt with the anionic surfactant predominates, during which process the anionic surfactant molecules first electrostatically bind to the cationic charge of the quaternary ammonium salt, the solution remains clear, and then as the anionic surfactant concentration increases, the quaternary ammonium salt/anionic surfactant aggregates grow larger, increasing the turbidity rate until a plateau is reached.
Optical microscopic imaging: images of the liquid-liquid condensed phase were taken using an optical microscopy imager: as can be seen from FIG. 2, 20. mu.L of the solution of example 1 was dropped on a glass slide, and a liquid-liquid phase separation structure having a size of 1 to 20 μm was formed in the solution as observed through an objective lens.
And (3) imaging by a cryo-transmission electron microscope: the structure of the condensed phase was characterized by cryo-transmission electron microscopy: the solution of comparative example 1 was dropped on a copper mesh of a carbon-supported membrane, excess solution was sucked off using a filter paper, and then placed in liquid ethane to be rapidly frozen, and the frozen sample was imaged by a cryo-transmission electron microscope (operating voltage 120kV) in a low-temperature stage at-179 deg.C (see FIG. 3). As shown in FIG. 3, since the formed aggregates have a size of about 10nm, a spherical shape and a small number of sizes, the solution is transparent, and as shown in FIG. 12, the aggregates are macroscopically observed to be in a homogeneous state and have a large viscosity as a whole, and therefore, it can be seen from the results of macroscopic and cryo-transmission electron microscopy that the aggregates are not in a condensed phase, it is found that the condensed phase system can form a condensed phase only when the concentration range of the quaternary ammonium salt is 20mM to 70mM and the concentration of the anionic surfactant is 10mM to 40 mM.
2. Rheological Properties
A dynamic shear rheometer is adopted to research the rheological property of the mixed solution of the anionic surfactant and the quaternary ammonium salt at 25.0 +/-0.1 ℃. The linear viscoelastic region is determined by a strain sweep at a fixed frequency of 1.00Hz, and G' are measured by frequency sweep at a constant stress of 0.1 (linear viscoelastic range) over a frequency range of 0.05-100 Hz. At 25 ℃ the rheology was tested by fixing the ratio Y of TBAF to SDS to 2 and the concentration of TBAF to 40mM, 60mM, the results of which are shown in FIG. 4.
As shown in FIG. 4, the storage modulus (G ') and the dissipation modulus (G') both increased with the increase of the angular frequency (ω), and the dissipation modulus was larger than the storage modulus under the conditions of fixing the ratio Y of TBAF to SDS to be 2 and changing the concentration of TBAF to be 40mM and 60mM, indicating that the formed condensed phase system was a viscous soft substance rather than an elastic soft substance, and the condensed phase as a viscous soft substance could be rapidly separated from the dilute phase, facilitating the separation during the application process, for example, after adsorbing metal ions.
Comparative example 2
The Gemini type quaternary ammonium salt (12-3(OH) -12) with the structure shown in the formula I, Sodium Dodecyl Sulfate (SDS) and deionized water are compounded, stirred and dissolved according to the following proportion, and hydrochloric acid is used for adjusting the pH value to 7.0, and the volume is 5 mL:
gemini type quaternary ammonium salt (12-3(OH) -12) 60mM
SDS 40mM
Comparative example 3
Spermine, Sodium Dodecyl Sulfate (SDS) and deionized water are compounded, stirred and dissolved according to the following proportion, hydrochloric acid is used for adjusting the pH to 7.0, and the volume is 5 mL:
spermine 60mM
SDS 40mM
Example 2
In a condensed phase formed by 5mL of 60mM TBAF/40mM SDS having pH 7 formed in example 1 at 25 ℃, 300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) having a concentration of 10mM was added and mixed at 600-900rpm for half an hour to obtain an enrichment system for metal ions.
Meanwhile, 300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) having a concentration of 10mM was added to 5mL of an aqueous solution having a pH of 7 at 25 ℃ as a control system.
Respectively adding 1mL of europium nitrate with the concentration of 300mg/L into an enrichment system and a control system, respectively taking 200 mu L of uniformly mixed solution from the enrichment system and the control system when the enrichment system and the control system are encapsulated for 0, 5, 10, 20, 60 and 90 minutes, respectively, diluting ten times, centrifuging at the rotating speed of 8000rpm for 2 minutes, collecting supernatant, filtering by a filter membrane with the thickness of 0.22 mu m, and testing the mass concentration of metal ions in the supernatant by ICP-MS.
As shown in FIG. 5, in the case of using the condensed phase system formed of TBAF/SDS after 5 minutes, the metal ion concentration in the supernatant reached approximately 0.04. mu.g/mL, and the extraction rate reached 90%. Because the detection limit of the instrument is 0.02 mu g/mL, the metal ion concentration can be reduced to be less than 0.02 mu g/mL after 1.5 hours and cannot be detected, and the metal ion concentration in the control system is always higher than 45 mu g/mL, which shows that the enrichment system in the embodiment has good enrichment effect on europium.
Example 3
In a condensed phase formed by 5mL of 60mM TBAF/40mM SDS having pH 7 formed in example 1 at 25 ℃, 300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) having a concentration of 10mM was added and mixed at 600-900rpm for half an hour to obtain an enrichment system for metal ions.
Meanwhile, 300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) having a concentration of 10mM was added to 5mL of an aqueous solution having a pH of 7 at 25 ℃ as a control system.
Adding 1mL of neodymium nitrate with the concentration of 300mg/L into an enrichment system and a control system respectively, taking 200 mu L of uniformly mixed solution from the enrichment system and the control system respectively when the enrichment system and the control system are encapsulated for 0, 5, 10, 20, 60 and 90 minutes respectively, diluting ten times, centrifuging at the rotating speed of 8000rpm for 2 minutes, collecting supernatant, filtering by a filter membrane with the thickness of 0.22 mu m, and testing the mass concentration of metal ions in the supernatant by ICP-MS.
As shown in FIG. 6, in the case of using the gel phase system formed of TBAF/SDS after 5 minutes, the metal ion concentration in the supernatant reached approximately 0.04. mu.g/mL and the extraction rate reached 90%. Because the detection limit of the instrument is 0.02 mu g/mL, the metal ion concentration can be reduced to be less than 0.02 mu g/mL after 3 hours and cannot be detected, and the metal ion concentration in the control system is always higher than 45 mu g/mL, the enrichment system in the embodiment has better enrichment effect on neodymium.
Examples 4 to 9
The experimental procedures of examples 4-9 were the same as those of example 2, except for the following parameters, which are shown in Table 1:
TABLE 1
Example 10
300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) having a concentration of 10mM was added to 7 5mL of a condensed phase of 60mM TBAF/40mM SDS having a pH of 7 formed according to the protocol of example 1, respectively, at 25 ℃ and mixed at 900rpm for half an hour to obtain an enrichment system for metal ions.
Adding 1mL of neodymium nitrate with the concentration of 50, 70, 100, 200, 300, 400 and 500mg/L into the enrichment system respectively, encapsulating for 5 minutes, taking 200 mu L of the uniformly mixed solution, centrifuging at the rotation speed of 8000rpm for 2 minutes to separate (see figure 11), wherein the left figure in figure 11 is a macroscopic state diagram of standing for 10 seconds after reaction, and the solution is in a turbid state; and the right graph is a macroscopic state graph after 2 minutes of centrifugation, the liquid drops with darker colors on the bottle wall are condensed phases after metal ions are encapsulated, the condensed phases are easy to settle due to higher viscosity and are separated from the supernatant, the condensed phases are settled at the bottom, the supernatant is collected and filtered by a filter membrane with the diameter of 0.22 mu m, and the mass concentration of the metal ions in the supernatant is tested by ICP-MS.
As shown in FIG. 7, when the condensed phase system formed of TBAF/SDS was used, the extraction rate of the neodymium nitrate solution having an initial concentration of 50mg/L to 500mg/L could be 90% or more, indicating that the enrichment system of the present invention can achieve enrichment of metal ions at a concentration ranging from 50mg/L to 500 mg/L.
Comparative example 4
A comparative system was obtained by adding 300. mu.L of octyl (phenyl) -N, N-diisobutylcarbamoyl methylphosphine oxide (CMPO) having a concentration of 10mM to 7 5mL of a 60mM Gemini type quaternary ammonium salt (12-3(OH) -12) having a pH of 7/40 mM SDS system formed according to the scheme of comparative example 2 at 25 ℃ and mixing at 600-900rpm for half an hour.
Adding 1mL of neodymium nitrate with the concentration of 50, 70, 100, 200, 300, 400 and 500mg/L into the comparison system respectively, encapsulating for 5 minutes, taking 200 mu L of the uniformly mixed solution, centrifuging at the rotation speed of 8000rpm for 2 minutes, collecting supernatant, filtering by a filter membrane with the diameter of 0.22 mu m, and testing the mass concentration of metal ions in the supernatant by ICP-MS.
As shown in FIG. 8, when an aggregate system comprising Gemini type quaternary ammonium salt (12-3(OH) -12)/SDS was used, the extraction rate was only about 10% at the maximum for a neodymium nitrate solution having an initial concentration of 50mg/L to 500mg/L, indicating that the effect of enriching the aggregate was far less excellent than that of the condensed phase system of the present invention.
Comparative example 5
A comparative system was obtained by adding 300. mu.L of 10mM octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) to 7 5mL of 7 pH 60mM SDS system formed according to the scheme of comparative example 3 at 25 ℃ and mixing at 600-900rpm for half an hour.
Adding 1mL of neodymium nitrate with the concentration of 50, 70, 100, 200, 300, 400 and 500mg/L into the comparison system respectively, encapsulating for 5 minutes, taking 200 mu L of the uniformly mixed solution, centrifuging at the rotation speed of 8000rpm for 2 minutes, collecting supernatant, filtering by a filter membrane with the diameter of 0.22 mu m, and testing the mass concentration of metal ions in the supernatant by ICP-MS.
As shown in FIG. 9, in the case of using the system of aggregates formed by spermine/SDS, the extraction rate does not exceed 10% for the neodymium nitrate solution having the initial concentration of 50mg/L to 500mg/L, indicating that the effect of enriching the aggregates is far from being excellent as compared with the condensed phase system of the present invention.
Example 11
1mL of neodymium nitrate with the concentration of 50, 70, 100, 200, 300, 400 and 500mg/L was added to 7 5mL of 60mM TBAF and 40mM SDS coacervate phase system with pH 7 formed according to the protocol of example 1 at 25 ℃ respectively, and after 5 minutes of encapsulation, 200. mu.L of the well-mixed solution was taken, and after centrifugation at 8000rpm for 2 minutes, the supernatant was collected, filtered through a 0.22 μm filter and tested for the mass concentration of metal ions in the supernatant by ICP-MS.
As shown in FIG. 10, when a condensed phase system composed of TBAF/SDS was used, the extraction rate was about 60% for a neodymium nitrate solution having an initial concentration of 50mg/L to 500 mg/L.
As can be seen from a comparison between this example and the above examples, the complex condensed phase system of the present invention has a good effect of enriching metal ions. In addition, under the condition that the complex condensed phase system further comprises a metal ion extracting agent, the metal ion extracting agent plays an auxiliary role in the enrichment process of metal ions, and the extraction rate can be further improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The complex condensed phase system is characterized by comprising an anionic surfactant and quaternary ammonium salt, wherein the quaternary ammonium salt is a single-quaternary ammonium salt, the concentration of the anionic surfactant is 10 mM-40 mM, and the concentration of the quaternary ammonium salt is 20 mM-70 mM.
Preferably, the complex condensed phase system is a metal ion enrichment system having metal ion enrichment capacity.
2. The complex coacervate phase system of claim 1, wherein the complex coacervate phase system further comprises a metal ion extractant;
preferably, the metal ion extractant comprises at least one of tributyl phosphate (TBP), tri-N-octylphosphine oxide (TOPO), triisopentyl phosphate (TiBP), octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO), suberic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, 2-hydroxy-3-naphthoic acid, 2-naphthylacetic acid, biphenyl-4, 4-dicarboxylic acid, 4-hydroxymethylbiphenyl, 4' -dihydroxybiphenyl, 4-cyanobiphenyl, 4-phenylphenol, 2-naphthol;
for example, the metal ion extractant includes octyl (phenyl) -N, N-diisobutylcarbamoyl methyl phosphine oxide (CMPO);
preferably, the complex coacervate phase system further comprises water.
3. The complex coacervate phase system of claim 1 or 2, wherein the concentration of the metal ion extractant in the complex coacervate phase system is between 0.1 and 5 mM.
4. The complex coacervate phase system according to any of claims 1-3, wherein the molar ratio of anionic surfactant to quaternary ammonium salt in the complex coacervate phase system is 1: 5-5: 1.
Preferably, the molar ratio of the anionic surfactant to the metal ion extractant in the complex condensed phase system is 100: 1-10: 1;
for example, the molar ratio of the anionic surfactant to the CMPO is 100:1 to 10: 1.
5. A complex coacervate system according to any of the claims 1-4, wherein the anionic surfactant is selected from at least one of the group consisting of sodium sulfate with 8-20 carbon atoms, sodium sulfonate with 8-20 carbon atoms, sodium benzenesulfonate with 8-20 carbon atoms and polyethyleneated alkyl sulfate with 8-20 carbon atoms;
preferably, the sodium sulfate salt having 8 to 20 carbon atoms includes sodium octyl sulfate, sodium decyl sulfate, sodium dodecyl sulfate, or sodium tetradecyl sulfate; the sodium sulfonate with 8-20 carbon atoms comprises sodium decyl sulfonate or sodium dodecyl sulfonate; the sodium benzene sulfonate with 8-20 carbon atoms comprises sodium dodecyl benzene sulfonate or sodium tetradecyl benzene sulfonate; the polyethylene alkyl sulfate with 8-20 carbon atoms comprises sodium dodecyl ether sulfate, sodium tetradecyl ether sulfate or sodium hexadecyl ether sulfate.
6. The complex coacervate system of any of claims 1-5, wherein the quaternary ammonium salt has the formula R4NX, wherein R may be the same or different from each other, are independently selected from C1-C8 alkyl, preferably C1-C6 alkyl, X is halogen anion selected from F-、Cl-、Br-Or I-。
Preferably, the quaternary ammonium salt is selected from at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetra-n-butylammonium chloride, and tetrabutylammonium fluoride.
Preferably, the structure of the coacervate phase is a liquid-liquid phase separation structure, and the liquid-liquid phase separation structure is a coacervate phase formed by coacervating droplets with the size of 1-20 μm.
7. A method for preparing a complex coacervate phase system according to any of the claims 1 to 6, comprising the steps of: and mixing an anionic surfactant, quaternary ammonium salt and water to obtain the complex coacervate phase system.
Preferably, the preparation method further comprises the following steps: a metal ion extractant, preferably CMPO, is added to the complex coacervate phase system.
8. The method of claim 7, further comprising the steps of: adding a metal ion extraction agent, preferably CMPO, to the complex coacervate phase system followed by addition of metal ions.
Preferably, after mixing the anionic surfactant, the quaternary ammonium salt and the water, the following steps are further included: the pH is adjusted to neutral using an acidic solution, for example hydrochloric acid.
9. Use of the complex condensed phase system according to any one of claims 1 to 6 for metal ion enrichment, for example, for separation and enrichment of metal ions in industrial wastewater containing metal ions of heavy metals and/or rare earth metals, and the like.
Preferably, in the use of the complex coacervate phase system for enrichment of metal ions, the concentration of the metal ions is between 50mg/L and 500 mg/L.
Preferably, in the use of the complex condensed phase system for metal ion enrichment, the metal ions are, for example, rare earth metal ions or heavy metal ions, preferably europium ions, neodymium ions, yttrium ions, ytterbium ions or lead ions.
10. An enrichment system for metal ions comprising the complex coacervate phase system of any of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111592440.7A CN114349143B (en) | 2021-12-23 | 2021-12-23 | Complex coacervate phase system and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111592440.7A CN114349143B (en) | 2021-12-23 | 2021-12-23 | Complex coacervate phase system and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114349143A true CN114349143A (en) | 2022-04-15 |
| CN114349143B CN114349143B (en) | 2023-04-14 |
Family
ID=81101184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111592440.7A Active CN114349143B (en) | 2021-12-23 | 2021-12-23 | Complex coacervate phase system and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349143B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992432A (en) * | 1967-04-05 | 1976-11-16 | Continental Oil Company | Phase transfer catalysis of heterogeneous reactions by quaternary salts |
| EP0721194A2 (en) * | 1995-01-09 | 1996-07-10 | International Business Machines Corporation | Deaggregated electrically conductive polymers and precursors thereof |
| CN1342786A (en) * | 2001-09-19 | 2002-04-03 | 北京大学 | Process for preparing high-purity gold by electrolyzing extracted gold-contained organic phase |
| CN102430265A (en) * | 2011-09-26 | 2012-05-02 | 武汉大学 | Aqueous two-phase extraction system of mixed surfactant |
| CN102580682A (en) * | 2012-01-17 | 2012-07-18 | 湘潭大学 | Adsorbent for simultaneously removing heavy metals and phenol organics in mineral processing wastewater and preparation method thereof |
| CN103111263A (en) * | 2013-02-05 | 2013-05-22 | 中山大学 | Metallic-organic gel matrix solid-phase microextraction head with multiple levels of hole channels and preparation method thereof |
| CN103392018A (en) * | 2011-02-22 | 2013-11-13 | 独立行政法人物质·材料研究机构 | Method for extraction and separation of lanthanoid elements and actinoid elements, and means for extraction and separation of lanthanoid elements and actinoid elements |
| CN103468950A (en) * | 2013-08-23 | 2013-12-25 | 中国科学院过程工程研究所 | Method for removing metal ion purity of rare earth aqueous solution extraction |
| FR3001961A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | SOL-GEL PROCESS FOR SEPARATING METAL IONS FROM AQUEOUS SOLUTION |
| US20140251920A1 (en) * | 2013-03-08 | 2014-09-11 | Ecolab Usa Inc. | Enhanced foam removal of total suspended solids and multiply charged cations from aqueous or aqueous/oil mixed phase via increased viscoelasticity |
| CN104923079A (en) * | 2015-05-21 | 2015-09-23 | 浙江大学 | Preparation method and application of hyamine cationic polyelectrolyte-anionic surfactant compound |
| CN105861827A (en) * | 2016-04-08 | 2016-08-17 | 中南大学 | Acid-alkaline coupling extraction system used for extraction and separation of multi-metal solutions and application thereof |
| US20190002309A1 (en) * | 2017-06-30 | 2019-01-03 | The Regents Of The University Of California | Surfactant-assisted synthesis of surface-functionalized nanoparticle-polymer electrospun composites |
| CN109420565A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院化学研究所 | Surface activator composition, preparation method and its purposes for separation of metal ions flotation |
| CN113621835A (en) * | 2021-07-23 | 2021-11-09 | 福建金鑫钨业股份有限公司 | Method for efficiently removing molybdenum based on extraction-precipitation combination |
-
2021
- 2021-12-23 CN CN202111592440.7A patent/CN114349143B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992432A (en) * | 1967-04-05 | 1976-11-16 | Continental Oil Company | Phase transfer catalysis of heterogeneous reactions by quaternary salts |
| EP0721194A2 (en) * | 1995-01-09 | 1996-07-10 | International Business Machines Corporation | Deaggregated electrically conductive polymers and precursors thereof |
| CN1342786A (en) * | 2001-09-19 | 2002-04-03 | 北京大学 | Process for preparing high-purity gold by electrolyzing extracted gold-contained organic phase |
| CN103392018A (en) * | 2011-02-22 | 2013-11-13 | 独立行政法人物质·材料研究机构 | Method for extraction and separation of lanthanoid elements and actinoid elements, and means for extraction and separation of lanthanoid elements and actinoid elements |
| CN102430265A (en) * | 2011-09-26 | 2012-05-02 | 武汉大学 | Aqueous two-phase extraction system of mixed surfactant |
| CN102580682A (en) * | 2012-01-17 | 2012-07-18 | 湘潭大学 | Adsorbent for simultaneously removing heavy metals and phenol organics in mineral processing wastewater and preparation method thereof |
| CN103111263A (en) * | 2013-02-05 | 2013-05-22 | 中山大学 | Metallic-organic gel matrix solid-phase microextraction head with multiple levels of hole channels and preparation method thereof |
| FR3001961A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | SOL-GEL PROCESS FOR SEPARATING METAL IONS FROM AQUEOUS SOLUTION |
| WO2014124901A1 (en) * | 2013-02-13 | 2014-08-21 | Commissariat à l'énergie atomique et aux énergies alternatives | Sol-gel method for separating metal ions from an aqueous solution |
| US20140251920A1 (en) * | 2013-03-08 | 2014-09-11 | Ecolab Usa Inc. | Enhanced foam removal of total suspended solids and multiply charged cations from aqueous or aqueous/oil mixed phase via increased viscoelasticity |
| CN103468950A (en) * | 2013-08-23 | 2013-12-25 | 中国科学院过程工程研究所 | Method for removing metal ion purity of rare earth aqueous solution extraction |
| CN104923079A (en) * | 2015-05-21 | 2015-09-23 | 浙江大学 | Preparation method and application of hyamine cationic polyelectrolyte-anionic surfactant compound |
| CN105861827A (en) * | 2016-04-08 | 2016-08-17 | 中南大学 | Acid-alkaline coupling extraction system used for extraction and separation of multi-metal solutions and application thereof |
| US20190002309A1 (en) * | 2017-06-30 | 2019-01-03 | The Regents Of The University Of California | Surfactant-assisted synthesis of surface-functionalized nanoparticle-polymer electrospun composites |
| CN109420565A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院化学研究所 | Surface activator composition, preparation method and its purposes for separation of metal ions flotation |
| CN113621835A (en) * | 2021-07-23 | 2021-11-09 | 福建金鑫钨业股份有限公司 | Method for efficiently removing molybdenum based on extraction-precipitation combination |
Non-Patent Citations (6)
| Title |
|---|
| 乔富林等: "星状六聚阳离子表面活性剂与阴离子表面活性剂复配体系的聚集体转变及构象转变", 《中国化学会第十五届胶体与界面化学会议论文集（第一分会）》 * |
| 张永强;孙体昌;郭清;侯青霞;郭英超;卢铁强;燕春环;: "双水相体系萃取分离金属离子研究进展" * |
| 李继东等: "离子型表面活性剂自组装体系在化学中的应用", 《化学进展》 * |
| 牛明改等: "铑在氯化十六烷基吡啶-硫氰化钾-硫酸铵体系中的浮选分离和富集", 《理化检验(化学分册)》 * |
| 董修言等: "正负离子表面活性剂/离子液体双水相性质研究", 《化学通报》 * |
| 韩璐等: "表面活性剂与聚电解质界面扩张粘弹性研究", 《西华大学学报(自然科学版)》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114349143B (en) | 2023-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rasee et al. | Efficient separation, adsorption, and recovery of Samarium (III) ions using novel ligand-based composite adsorbent | |
| Deng et al. | Organic solvent-free cloud point extraction-like methodology using aggregation of graphene oxide | |
| WO2008085085A1 (en) | Sorbent for removing heavy metal ions from water | |
| Lee et al. | High electrochemical seawater desalination performance enabled by an iodide redox electrolyte paired with a sodium superionic conductor | |
| Joppien | Characterization of adsorbed polymers at the charged silica aqueous electrolyte interface | |
| Eisazadeh | Removal of mercury from water using polypyrrole and its composites | |
| JP2009161794A (en) | Method for recovering lithium, and lithium recovering apparatus using the method | |
| Li et al. | Efficient removal of fluoride by complexation extraction: mechanism and thermodynamics | |
| Ellis et al. | Anion exchange properties of b-FeOOH | |
| CN107282021A (en) | A kind of organo-mineral complexing bentonite clay material and its preparation method and application | |
| CN101880031A (en) | Micro-emulsion method for preparing nano-sulfur particles | |
| Howard et al. | Nanoscavenger based dispersion preconcentration; sub-micron particulate extractants for analyte collection and enrichment | |
| Oyarce et al. | Removal of lithium ions from aqueous solutions by an ultrafiltration membrane coupled to soluble functional polymer | |
| CN114349143B (en) | Complex coacervate phase system and preparation method and application thereof | |
| Myrvold | Interactions between lignosulphonates and the components of the lead-acid battery: Part 1. Adsorption isotherms | |
| Risser et al. | Spectroscopic study of surface redox reactions with manganese oxides | |
| Shibata et al. | Spectrophotometric determination of lanthanum with neo-thorone | |
| Dong et al. | Hydrophobic deep eutectic solvents as the green media for highly efficient extraction of Cr (VI) over a broad pH range and low oil-water ratio | |
| Majidi et al. | Separation and determination of trace level of gold from hydrochloric acid solutions using ultrasound-assisted cold-induced aggregation microextraction | |
| Wu et al. | Determination of chromium species in environmental water and human serum samples by FAAS after magnetic solid phase extraction | |
| CN110354798A (en) | A kind of cerium zirconium zinc metal composite adsorbent and the preparation method and application thereof | |
| Wang et al. | Molecular examination of ion-pair competition in alkaline aluminate solutions using in situ liquid SIMS | |
| WO2016054265A1 (en) | Processes for recovering rare earth elements | |
| WO2018227674A1 (en) | Method for removing radioactive thorium element in rare earth mineral | |
| CN1007839B (en) | Liquid ion-exchanger composite used as acetylcholine ion-selective microelectrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |