CN115246914B - Crown ether covalent organic framework material, preparation method and application of adsorption separation palladium - Google Patents

Crown ether covalent organic framework material, preparation method and application of adsorption separation palladium Download PDF

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CN115246914B
CN115246914B CN202210907161.3A CN202210907161A CN115246914B CN 115246914 B CN115246914 B CN 115246914B CN 202210907161 A CN202210907161 A CN 202210907161A CN 115246914 B CN115246914 B CN 115246914B
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余志扬
徐雷
张素芬
丁文雅
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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Abstract

The invention relates to the technical field of heavy metal adsorption separation, and discloses a crown ether covalent organic framework material, a preparation method and application of adsorption separation palladium, wherein the COF material has a structure shown in a formula I, raw materials are dissolved in a mixed solvent of o-dichlorobenzene and butanol, and acetic acid aqueous solution is added after ultrasonic treatment; vacuumizing the mixed solution, injecting inert gas, sealing to remove oxygen, performing reaction under electron beam irradiation, and performing post-treatment to obtain the crown ether covalent organic framework material. The material can specifically adsorb and separate palladium from an acidic aqueous phase containing 19 metal ions, the single-stage adsorption rate of palladium ions can be up to more than 94%, the selectivity is high, the operation is simple, the separation efficiency is high, and the material is particularly suitable for separating and recovering noble metal palladium in the nuclear industry.

Description

Crown ether covalent organic framework material, preparation method and application of adsorption separation palladium
Technical Field
The invention relates to the technical field of heavy metal adsorption separation, in particular to a crown ether covalent organic framework material, a preparation method and application of adsorption separation palladium.
Background
Palladium (Pd) is a noble metal element having a specific structure, which is specific to H 2 And O 2 Has excellent adsorption capacity and has an immovable shaking position in the industrial catalysis field. Besides good catalytic activity, palladium metal can keep chemical inertness in a wide temperature range, has the characteristics of high melting point, friction resistance, corrosion resistance, strong ductility, strong thermoelectric stability and the like, and has been widely applied to various fields of the national industry. However, the palladium resource reserves in China are quite limited, the yield is extremely low, and the requirements of the modern chemical industry can not be met. Currently, most of palladium metals used in the domestic chemical industry depend on import, and the lack of palladium resources has become an important bottleneck restricting the industrial development in China.
In the prior art, palladium metal sources are mainly realized through the paths of natural palladium-containing mineral resources, recovery of palladium metal in copper-nickel sulfide ore byproducts, secondary recovery and utilization of palladium-containing resources such as industrial waste palladium catalysts, and the like, the palladium resources obtained through the paths are extremely limited, and meanwhile, the palladium resources are difficult to use with the increase of loss. Therefore, developing a new material capable of efficiently separating noble metal palladium from waste liquid in metallurgical industry and spent fuel in nuclear industry is a necessary choice for solving the problem of shortage of palladium resources in China at present and promoting high-quality sustainable development of chemical industry in China.
The covalent organic frameworks (Covalent Organic Frameworks, COFs) are crystalline organic porous functional materials formed by connecting light elements (H, B, C, N, O, si and the like) through covalent bonds, and the materials have wide application prospects in the aspects of metal ion adsorption separation due to the advantages of stable chemical structures, large specific surface area, low framework density, high designability and the like. In recent years, studies have confirmed that COFs can be modified by a functional design, materials with different structures and properties can be obtained on the premise of not affecting the crystallinity and the porosity of the COFs, and the COFs are used for selective adsorption and separation of heavy metal ions, such as CN110975843a and reports in documents (Sun q., et al journal of the American Chemical Society,2017,139 (7), 2786-2793, etc.), CN110975843a discloses a preparation method and application of a covalent organic framework-based heavy metal ion adsorption separation membrane, and the preparation method and application of the covalent organic framework-based heavy metal ion adsorption separation membrane are characterized in that the polydopamine functional modification PDA-COFs-based heavy metal ion adsorption separation membrane is adopted, and the heavy metal ion adsorption and separation capability of the COFs can be further improved on the premise of retaining the advantage of large specific surface area of the COFs.
However, most of the methods are chemical methods, and the chemical reagents used have certain toxicity and complicated steps, so that the method is difficult to meet the requirement of mass production, and further the large-scale industrial application of the method is limited.
Disclosure of Invention
Aiming at the difficult problem that palladium ions are difficult to carry out high-selectivity adsorption separation from a high-acidity multi-metal ion aqueous solution in the prior art, the invention provides a crown ether covalent organic framework material capable of adsorbing heavy metal palladium ions, which can specifically adsorb and separate palladium from an acidic aqueous phase containing more than 19 metal ions, and the single-stage adsorption rate of palladium ions can be up to more than 94 percent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a crown ether covalent organic framework material having a structure according to formula I:
the palladium adsorption material has a porous two-dimensional infinite extension structure, and the triazine ring and the C=N double bond contained in the palladium adsorption material have strong selective complexing capacity on palladium ions. The principle is still under exploration, but according to the theory of Lewis soft and hard acid base, the N atom containing the lone pair electron is Lewis soft base which can coordinate with Lewis soft acid palladium ion to form stable chelate. In addition, the material has a unique 18-crown-6 structure, and the structure can form a coordination cavity with stronger electronegativity, so that the material can enhance the electrostatic adsorption effect between the material and positively charged palladium ions, and the selective adsorption capacity of the material on the palladium ions is strong.
The invention provides a preparation method of a crown ether covalent organic framework material, which comprises the following steps:
step 1, dissolving a compound shown as a formula II (1, 3, 5-tri (4-aminophenyl) benzene, TAPT) and a formula III in a mixed solvent of o-dichlorobenzene and n-butanol, and adding an acetic acid aqueous solution after ultrasonic treatment;
and 2, vacuumizing the mixed solution obtained in the step 1, injecting inert gas, sealing, performing polymerization reaction under electron beam irradiation, and performing post-treatment to obtain the crown ether covalent organic framework material.
The molar ratio of the compounds shown in the formula II to the formula III is 4:3-1:1.
In the step 1, the volume ratio of the o-dichlorobenzene to the butanol to the acetic acid aqueous solution is 5:5:1-10:10:1, and the concentration of the acetic acid aqueous solution is 4-8 mol/L.
In the step 2, the electron beam irradiation capacity is 1.5-10 MeV, the dose rate is 250-750 Gy/s, the absorbed dose is 50-150 kGy, and the crystallinity of the material is reduced by exceeding the dose, so that the yield of the material is reduced.
And step 1, carrying out ultrasonic treatment for 5-20min, wherein the irradiation time in step 2 is 180-240s.
The inert gas includes nitrogen, argon or other noble gases.
And washing the product for multiple times by adopting tetrahydrofuran, ethanol and the like to remove impurities, thereby obtaining the crown ether covalent organic framework material.
The invention also provides application of the crown ether covalent organic framework material in palladium adsorption, separation or recovery. The crown ether covalent organic framework material has the characteristics of high selectivity on palladium metal ions, capability of efficiently adsorbing the palladium ions from various ions, simplicity in operation, high separation efficiency and the like, and is particularly suitable for separating and recycling noble metal palladium from acidic multi-metal ion waste liquid in industry.
The application specifically includes: and mixing the crown ether covalent organic framework material or a carrier containing the crown ether covalent organic framework material with an acidic aqueous solution containing palladium ions, and adsorbing the palladium ions.
The using amount of the crown ether covalent organic framework material is determined according to the concentration of palladium ions in the waste liquid under actual conditions, and generally, when the concentration range of the palladium ions is 0.5-1.0 mmol/L, the adsorption separation effect is better according to the solid-liquid ratio of 10-100 mg/5.0-100 mL. Preferably, the minimum concentration of palladium ions in the acidic aqueous solution is 1.0ppm, such as 1.0 to 5.0ppm.
The acidic aqueous solution is a nitric acid aqueous solution, and the nitric acid concentration in the nitric acid aqueous solution is 0.4-6mol/L; mixing time is more than 30min, such as more than 60min, more than 70min, more than 80min, more than 100min, more than 120min, more than 140min, and more than 160 min. Preferably, the mixing time is 180min, and the adsorption rate of palladium ions under the conditions is more than 80%.
Preferably, the concentration of nitric acid in the nitric acid aqueous solution is 1-6mol/L; the adsorption rate of palladium ions is more than 80%; further preferably, the nitric acid concentration is 2.0 to 4.0mol/L, and the palladium ion adsorption rate is 90% or more.
The adsorption process temperature is at room temperature, the energy consumption is the lowest at the temperature, and the adsorption rate of palladium ions is reduced to a certain extent along with the increase of the temperature.
In some embodiments, the acidic aqueous solution further comprises other metal ions including alkali metals, alkaline earth metals, iron, cobalt, nickel, ruthenium, zirconium, molybdenum, and any one or more of all 16 rare earth metal ions other than palladium ions.
Such as one or more of Ni (II), li (I), na (I), K (I), rb (I), cs (I), ca (II), mg (II), sr (II), ba (II), nd (III), co (II), la (III), ru (III), yb (III), Y (III), fe (III), zr (IV), mo (VI) and the like. The crown ether covalent organic framework material can quickly and efficiently adsorb palladium ions from the crown ether covalent organic framework material in the presence of various ions, has high separation efficiency, has the adsorption rate of less than 10 percent on other metal ions except the palladium ions, and has excellent separation effect.
Wherein La (III), nd (III), yb (III) and Y (III) can represent all 16 rare earth metal ions.
In some embodiments, the mass concentration of the other metal ions may be 1000 times or less the concentration of palladium ions, and when the concentration of the other ions is higher than 1000 times, the adsorption efficiency of palladium ions is reduced. Preferably 100-1000 times.
Compared with the prior art, the invention has the following beneficial effects:
the invention designs and synthesizes the covalent organic framework material with the crown ether structure, which can efficiently adsorb, separate or recycle palladium ions from an acidic aqueous phase, has high selectivity and high separation efficiency, is particularly suitable for separating and recycling noble metal palladium industrially, and has simple and efficient synthesis process.
Drawings
FIG. 1 is a schematic diagram of the preparation process of a crown ether covalent organic framework material in an embodiment.
FIG. 2 is an XRD pattern of the crown ether covalent organic framework material BC-COF prepared in example 1.
FIG. 3 is a graph showing the adsorption rate of the BC-COF separated elemental palladium from an aqueous nitric acid solution as a function of nitric acid concentration in example 2;
FIG. 4 is a graph showing the partition coefficient of BC-COF in example 2 for separating elemental palladium from an aqueous nitric acid solution as a function of nitric acid concentration.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following specific embodiments are all purchased in the market, and the extraction rate is the percentage of the total amount of the extracted substances in the raw water phase, which is obtained by transferring the extracted substances from the water phase to the organic phase in the extraction process.
The partition coefficient refers to the ratio of partition ratio of the substance to be separated between two phases when extraction separation is performed under a certain condition, and the partition coefficient of palladium ions refers to the product of the ratio of the concentration of palladium ions adsorbed in the solid phase to the concentration of palladium ions in the liquid phase after adsorption and the ratio of the concentration of palladium ions to the ratio of palladium ions in the liquid phase after adsorption.
Example 1
The preparation process is shown in fig. 1, and comprises the following steps:
(1) TAPT (17.7 mg,0.05 mmol) and compound III (22.0 mg,0.05 mmol) are dissolved in a mixed solution of o-dichlorobenzene (0.25 mL) and n-butanol (0.25 mL) together, and after ultrasonic treatment for 40min, 6M aqueous acetic acid solution (0.05 mL) is added for uniform mixing;
(2) Pumping the reaction vessel filled with the mixed solution in the step (1) to 0After 098MPa, N is injected 2 Deoxidizing and sealing with PVDF film;
(3) The sealed reaction vessel is placed under the irradiation condition of 10MeV electron beam, the set dose rate is 500Gy/s, the irradiation is carried out for 200s for full reaction, and the absorbed dose of the electron beam irradiation is 100kGy.
(4) Washing the reaction precipitate with tetrahydrofuran for 2 times, washing with absolute ethyl alcohol for 2 times, and oven drying at 60deg.C for 24h to obtain BC-COF yellow powder with XRD shown in figure 2 and strong diffraction peak at 8-30deg.C and good crystallinity.
Example 2
(1) Alkali metal salt LiNO 3 、KNO 3 、RbNO 3 The method comprises the steps of carrying out a first treatment on the surface of the Alkaline earth metal salt Mg (NO) 3 ) 2 、Ca(NO 3 ) 2 、Sr(NO 3 ) 2 、Ba(NO 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Transition metal salt Fe (NO) 3 ) 3 、ZrO(NO 3 ) 2 、Co(NO 3 ) 2 、Ni(NO 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the Noble metal Pd (5% w/w) nitrate solution, ru nitrate solution; rare earth metal oxide Y 2 O 3 Rare earth metal nitrate La (NO) 3 ) 3 Nd (NO) 3 ) 3 Dissolving 16 metal salts in nitric acid solution, adding deionized water to obtain aqueous nitric acid solution containing multiple metal ions, wherein the concentration of each metal ion is 5.0X10 -4 M。
(2) Concentrated nitric acid and deionized water are added into the aqueous nitric acid solution, and the nitric acid concentration in the aqueous nitric acid solution is adjusted to be 0.4M, 1.0M, 2.0M, 3.0M, 4.0M, 5.0M and 6.0M respectively.
(3) The aqueous solutions containing 16 metal elements and having different nitric acid concentrations obtained in the step (2) are contacted and mixed with the BC-COF material prepared in the example 1, and the dosage ratio during mixing is as follows: 10.0mg of adsorbent is corresponding to each 5.0mL of nitric acid aqueous solution;
(4) And (3) carrying out adsorption experiments on the mixed solution obtained in the step (3) on a TAITECMM-10 type oscillator, operating at the oscillation speed of 150rpm and at the room temperature of 298K for 180 minutes to balance the adsorption, and measuring the content of each metal element in different nitric acid aqueous solutions before and after the adsorption.
The adsorption results are shown in fig. 3, 4 and table 1, and the abscissa in fig. 3 indicates the nitric acid concentration and the ordinate indicates the adsorption rate. The adsorption rate of palladium ions is shown in table 1, and K, which is the highest adsorption rate among other metal ions, is represented by lower adsorption rate of other metal ions. As can be seen from FIGS. 3-4 and Table 1, when the concentration of nitric acid is 3M, the effect of separating the elemental palladium is best, the adsorption rate of palladium is higher than 94%, and the adsorption rate of other 15 metal ions is lower than 15%, which shows that the BC-COF material provided by the invention has extremely high palladium selectivity, and is particularly suitable for efficiently separating and recovering palladium from strong acid aqueous phase solution containing multi-metal elements, and has extremely wide application range.
TABLE 1 adsorption test results of COF material BC-COF on Pd (II) and K (I)

Claims (10)

1. A crown ether covalent organic framework material characterized by having a structure according to formula I:
2. the method for preparing a crown ether covalent organic framework material according to claim 1, comprising:
step 1, dissolving a compound shown in a formula II and a formula III in a mixed solvent of o-dichlorobenzene and n-butanol, and adding an acetic acid aqueous solution after ultrasonic treatment;
and 2, vacuumizing the mixed solution obtained in the step 1, injecting inert gas, sealing, performing polymerization reaction under electron beam irradiation, and performing post-treatment to obtain the crown ether covalent organic framework material.
3. The method for preparing a crown ether covalent organic framework material according to claim 2, wherein the molar ratio of the compounds represented by formula II and formula III is 4:3-1:1.
4. The preparation method of the crown ether covalent organic framework material according to claim 2, wherein in the step 1, the volume ratio of the o-dichlorobenzene, the n-butanol and the aqueous solution of acetic acid is 5:5:1-10:10:1, and the concentration of the aqueous solution of acetic acid is 4-8 mol/L.
5. The method for preparing a crown ether covalent organic framework material according to claim 2, wherein the electron beam irradiation capacity in step 2 is 1.5MeV to 10MeV, the dose rate is 250 Gy/s to 750Gy/s, and the absorbed dose is 50kGy to 150kGy.
6. The use of a crown ether covalent organic framework material according to claim 1 in the field of adsorption, separation or recovery of palladium.
7. The use according to claim 6, wherein the crown ether covalent organic framework material or the support containing the crown ether covalent organic framework material is mixed with an acidic aqueous solution containing palladium ions for adsorption of palladium ions.
8. The use according to claim 7, wherein the concentration of palladium ions in the acidic aqueous solution ranges from 0.1mmol/L to 1.0mmol/L;
and/or the acidic aqueous solution is a nitric acid aqueous solution, and the concentration of nitric acid in the nitric acid aqueous solution is 0.4-6mol/L; mixing time is more than 30 min.
9. The use according to claim 7, wherein the acidic aqueous solution further comprises other metal ions including alkali metals, alkaline earth metals, iron, cobalt, nickel, ruthenium, zirconium, molybdenum and any one or more of all 16 rare earth metal ions other than palladium ions.
10. The use according to claim 9, wherein the other metal ion mass concentration is 1000 times or less the palladium ion mass concentration.
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CN114702635A (en) * 2022-03-28 2022-07-05 辽宁石油化工大学 Preparation method of Schiff base crown ether polymer and application of Schiff base crown ether polymer in anion exchange membrane

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Shuhao An et al.Constructing Catalytic Crown Ether-Based Covalent Organic Frameworks for Electroreduction of CO2.2021,第6卷(第10期),第3496-3502页. *

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