Synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system

Abstract

The invention discloses a synthesis of a cup-crown compound adsorbent material and a method for deeply selectively extracting indium from an acidic complex system, and belongs to the technical field of nonferrous metal metallurgy. The invention discloses a synthesis of a cup-crown compound adsorbent material and a method for deeply selectively extracting indium from an acidic complex system. Based on the pre-organization and complementary molecular design principles of host-guest chemistry, a 15-crown-5 ether subunit is introduced into a cup-crown [4] aromatic structure to form a cup-crown supramolecular compound, and the cup-crown compound is further loaded on the surface of SiO2 particles to form a stable adsorbent material, which can realize the deep selective separation and extraction of indium in an acidic complex system.

Description

Technical Field

[0001] The invention belongs to the technical field of nonferrous metallurgy, and more specifically, relates to a method for synthesizing a cup crown compound adsorption material and deeply selectively extracting indium from an acidic complex system. Background Art

[0002] With the rapid development of strategic emerging industries, a large amount of secondary resources containing indium are generated every year. After pretreatment, enrichment and other processes, they are mostly wet leached to produce a complex acidic solution system containing indium. Due to the low indium content, high content of impurity elements and large interference in this solution system, it is difficult to efficiently and selectively separate and extract indium. Therefore, it is crucial to develop efficient and selective indium adsorption materials. The application of Chinese patent application No. 201810562152.9 discloses an adsorption material for selectively separating indium and a preparation method thereof. By modifying the surface of the matrix with an amino functional monomer, an adsorption material for selectively separating indium is obtained, which can realize the adsorption and separation of indium in a low-concentration solution; the application of Chinese patent application No. 201711283603.7 discloses a method for recovering gallium and indium elements from waste slag containing gallium and indium elements. After adjusting the pH value of the solution to less than 4, more than 96% of gallium and indium in the slag can be separated; the application of Chinese patent application No. 201610249106.4 discloses a method for recovering indium from indium-containing smoke dust, which uses a polyvinylidene fluoride adsorption functional membrane to separate indium from the leaching solution. The indium in the smoke is adsorbed and enriched, realizing the efficient recovery of indium in the smoke; the application case with Chinese patent application number 202410792448.5 discloses a synthesis of an indium selective recognition adsorption material and a method for deep indium extraction. The synthesized adsorption material structure has good structural pre-organization, and the rich non-covalent interactions make the indium ions efficiently encapsulated in the macrocyclic molecular cavity, realizing the efficient selective adsorption of indium; the application case with Chinese patent application number 201911017802.2 discloses the synthesis of a P507 composite carbon fiber material and a method for adsorbing and separating indium in a liquid crystal panel. The synthesized P507 / C fiber composite material is used as an adsorbent, and the shaking table temperature is 25-45°C and 200-300 The recovery rate of indium is greater than 95% under the conditions of rpm speed and pH value of 0-3; Chinese patent application No. 201610421206.0 discloses a synthesis method and application of polysulfone microcapsules for adsorbing indium. Polysulfone is used as raw material, microcapsule technology is combined with extraction technology, and the extractant is coated by microencapsulation method. The prepared polysulfone microcapsule material achieves good indium adsorption effect; Chinese patent application No. 201210321309.1 discloses a method for recovering indium from waste liquid crystal panels by acid leaching-cation exchange resin adsorption process. A strong acid cation exchange resin column is used to countercurrently adsorb the waste liquid crystal panel leachate, thereby achieving effective separation of indium in the solution. Summary of the invention

[0003] 1. Problem to be solved

[0004] The purpose of the present invention is to overcome the problems of complex components, low indium content and large interference of impurity elements in the current indium-containing leaching system, and to solve the problems of low recovery depth and poor selectivity of traditional indium ion adsorbents. A method for synthesizing a calixcrown compound adsorbent and deeply selectively extracting indium from an acidic complex system is provided. Based on the pre-organization and complementary molecular design principles of host-guest chemistry, a 15-crown-5 ether subunit is introduced into a calix[4]arene structure to form a calixcrown supramolecular compound, which is further loaded on a SiO 2 A stable adsorption material is formed on the surface of the particles, which can realize the deep selective separation and extraction of indium in acidic complex systems.

[0005] 2. Technical solution

[0006] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0007] The present invention provides a method for the synthesis of a calixcrown compound adsorbent material and a method for deep selective extraction of indium from an acidic complex system. Based on the pre-organization and complementary molecular design principles of host-guest chemistry, a 15-crown-5 ether subunit is introduced into a calix[4]arene structure to form a calixcrown supramolecular compound, which is further loaded on a SiO 2 A stable adsorption material is formed on the surface of the particles, which can realize the deep selective separation and extraction of indium in acidic complex systems.

[0008] Furthermore, the specific process operation is:

[0009] (1) Add p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride in a certain proportion to anhydrous toluene and reflux for a period of time. After the reaction is completed, separate the toluene layer and vacuum evaporation to obtain a crude product, which is then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0010] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) is added into anhydrous chloroform in a certain proportion, and N,N-dimethylformamide (DMF) is added as an initiator to reflux for a period of time to obtain diethylene glycol dichloroethyl ester.

[0011] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI are added to acetone in a certain proportion and refluxed for a period of time. The reaction product is extracted with dichloromethane and vacuum rotary evaporation to obtain a crude product, which is then purified by column chromatography to obtain C5A.

[0012] (4) Dissolve C5A and silane coupling agent (KH560) in an organic solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution pH was adjusted with acid and reacted for a period of time to allow C5A to be grafted onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0013] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A is added to the indium-containing acidic leaching system and reacted at a constant temperature for a period of time to achieve deep selective separation and extraction of indium.

[0014] Furthermore, in the step (1), the molar ratio of p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride is in the range of (1-3):(8-12):(15-20), and the reflux reaction time is 1-8 h.

[0015] Furthermore, in step (2), tetraethylene glycol and thionyl chloride (SOCl 2 ) is in the range of 1:(15-30), and the reflux reaction time is 2-12 h.

[0016] Furthermore, in step (3), tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 The molar ratio of KI is in the range of (1-3):(2-6):(2-6):(0.1-0.3), and the reflux reaction time is 8-24 h.

[0017] Furthermore, the acid used in step (4) is one of acetic acid, hydrochloric acid and sulfuric acid, the pH value of the solution is adjusted to 3-6, and the reaction time is 2-12 h.

[0018] Furthermore, in step (5), the acidity range of the solution is 0.005-5 mol / L, the reaction temperature is 20-90° C., and the reaction time is 0.5-3 h.

[0019] 3. Beneficial effects

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The present invention provides a method for synthesizing a cup-crown compound adsorbent material and deeply selectively extracting indium from an acidic complex system. The size of the crown ether unit cavity on the cup-crown compound is highly matched with the indium ion, and the oxygen atoms on the ether ring form a highly negatively charged potential barrier through synergistic action, which has a strong coordination ability for the positively charged indium ion. Under the synergistic effect of size effect and electrostatic effect, the cup-crown compound can exhibit a highly efficient selective complexing ability for indium ions, thereby achieving unique matching and exclusive identification of indium ions in a complex system.

[0022] (2) The present invention provides a method for the synthesis of a cup-crown compound adsorbent material and a method for the deep selective extraction of indium from an acidic complex system. The cup-crown compound has a stable spatial structure of the cup-crown aromatic unit, and the bridging restricts the rotation of the phenol unit. After the crown ether is connected, a highly pre-organized macrocyclic supramolecular entity is formed. The energy loss caused by the conformational transition can be effectively reduced during the complexation with indium ions, which is conducive to the formation of a stable complex. In addition, the cup-crown aromatic unit is rich in π electrons, which can provide additional ion-dipole electrostatic force for the complexation process, further strengthening the complexation process.

[0023] (3) The present invention provides a method for the synthesis of a cup-crown compound adsorbent material and a method for the deep selective extraction of indium from an acidic complex system. The cup-crown compound has a rich modification site for the calixarene unit. Two of the four phenolic hydroxyl groups are used to form a crown ether ring, while the remaining two phenolic hydroxyl groups can be simultaneously grafted onto SiO 2 On the surface of the substrate, a stable combination of the cup-crown functional group and the substrate is achieved, thereby ensuring the excellent recycling performance of the cup-crown compound in the process of selectively adsorbing and extracting indium in the acidic leaching system. DETAILED DESCRIPTION

[0024] The present invention provides a method for the synthesis of a calixcrown compound adsorbent material and a method for deep selective extraction of indium from an acidic complex system. Based on the pre-organization and complementary molecular design principles of host-guest chemistry, a 15-crown-5 ether subunit is introduced into a calix[4]arene structure to form a calixcrown supramolecular compound, which is further loaded on a SiO 2 The surface of the particles forms a stable adsorption material, which can realize the deep selective separation and extraction of indium in the acidic complex system. The treatment process of the present invention specifically includes the following steps:

[0025] (1) Add p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride in an arbitrary molar ratio within the range of (1-3):(8-12):(15-20) to anhydrous toluene for reflux reaction for 1-8 h. After the reaction is completed, separate the toluene layer and vacuum rotary evaporate to obtain a crude product, which is then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0026] (2) Tetraethylene glycol and thionyl chloride (SOCl 2) is added to anhydrous chloroform in a molar ratio of 1:(15-30), and N,N-dimethylformamide (DMF) is added as an initiator to reflux for 2-12 h to obtain diethylene glycol dichloroethyl ester.

[0027] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI are added to acetone in any molar ratio within the range of (1-3):(2-6):(2-6):(0.1-0.3) and refluxed for 8-24 h. The reaction product is extracted with dichloromethane and vacuum evaporated to obtain a crude product, which is then purified by column chromatography to obtain C5A.

[0028] (4) Dissolve C5A and silane coupling agent (KH560) in THF or DMF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 3-6 with one of acetic acid, hydrochloric acid, and sulfuric acid for 2-12 h to graft C5A onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0029] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 0.005~5 mol / L and reacted at a constant temperature of 20~90℃ for 0.5~3 h to achieve deep selective separation and extraction of indium.

[0030] The present invention is further described below in conjunction with specific embodiments.

[0031] Example 1

[0032] The synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system in this embodiment specifically include the following steps:

[0033] (1) p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride were added to anhydrous toluene in a molar ratio of 1:8:15 and refluxed for 1 h. After the reaction, the toluene layer was separated and vacuum rotary evaporated to obtain a crude product, which was then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0034] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) was added into anhydrous chloroform at a molar ratio of 1:15, and N,N-dimethylformamide (DMF) was added as an initiator to reflux for 2 h to obtain diethylene glycol dichloroethyl ester.

[0035] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2CO 3 and KI were added to acetone at a molar ratio of 1:2:2:0.1 and refluxed for 8 h. The reaction product was extracted with dichloromethane and vacuum evaporated to obtain a crude product, which was then purified by column chromatography to obtain C5A.

[0036] (4) Dissolve C5A and silane coupling agent (KH560) in THF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 3 with acetic acid for 2 h to allow C5A to be grafted onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0037] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 0.005 mol / L and reacted at a constant temperature of 20°C for 0.5 h to achieve deep selective separation and extraction of indium, with an indium recovery rate of 99.33%.

[0038] Example 2

[0039] The synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system in this embodiment specifically include the following steps:

[0040] (1) p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride were added to anhydrous toluene in a molar ratio of 3:12:20 and refluxed for 8 h. After the reaction, the toluene layer was separated and vacuum rotary evaporated to obtain a crude product, which was then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0041] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) was added into anhydrous chloroform at a molar ratio of 1:30, and N,N-dimethylformamide (DMF) was added as an initiator to reflux for 12 h to obtain diethylene glycol dichloroethyl ester.

[0042] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI were added to acetone at a molar ratio of 3:6:6:0.3 and refluxed for 24 h. The reaction product was extracted with dichloromethane and vacuum evaporated to obtain a crude product, which was then purified by column chromatography to obtain C5A.

[0043] (4) Dissolve C5A and silane coupling agent (KH560) in DMF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 6 with hydrochloric acid for 12 h to allow C5A to be grafted onto SiO 2Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0044] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 5 mol / L and reacted at a constant temperature of 90°C for 3 h to achieve deep selective separation and extraction of indium, with an indium recovery rate of 99.17%.

[0045] Example 3

[0046] The synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system in this embodiment specifically include the following steps:

[0047] (1) p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride were added to anhydrous toluene in a molar ratio of 2:9:17 and refluxed for 3 h. After the reaction, the toluene layer was separated and vacuum rotary evaporated to obtain a crude product, which was then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0048] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) was added into anhydrous chloroform at a molar ratio of 1:20, and N,N-dimethylformamide (DMF) was added as an initiator and refluxed for 4 h to obtain diethylene glycol dichloroethyl ester.

[0049] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI were added to acetone at a molar ratio of 2:3:3:0.2 and refluxed for 12 h. The reaction product was extracted with dichloromethane and vacuum evaporated to obtain a crude product, which was then purified by column chromatography to obtain C5A.

[0050] (4) Dissolve C5A and silane coupling agent (KH560) in DMF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 4 with sulfuric acid for 4 h to allow C5A to be grafted onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0051] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 0.1 mol / L and reacted at a constant temperature of 40°C for 1 h to achieve deep selective separation and extraction of indium, with an indium recovery rate of 99.28%.

[0052] Example 4

[0053] The synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system in this embodiment specifically include the following steps:

[0054] (1) p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride were added to anhydrous toluene in a molar ratio of 2:10:16 and refluxed for 5 h. After the reaction, the toluene layer was separated and vacuum rotary evaporated to obtain a crude product, which was then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0055] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) was added into anhydrous chloroform at a molar ratio of 1:25, and N,N-dimethylformamide (DMF) was added as an initiator to reflux for 8 h to obtain diethylene glycol dichloroethyl ester.

[0056] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI were added to acetone at a molar ratio of 3:5:5:0.3 and refluxed for 16 h. The reaction product was extracted with dichloromethane and vacuum evaporated to obtain a crude product, which was then purified by column chromatography to obtain C5A.

[0057] (4) Dissolve C5A and silane coupling agent (KH560) in THF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 5 with acetic acid for 8 h to allow C5A to be grafted onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0058] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 1 mol / L and reacted at a constant temperature of 60°C for 2 h to achieve deep selective separation and extraction of indium, with an indium recovery rate of 99.07%.

[0059] Example 5

[0060] The synthesis of a cup crown compound adsorption material and a method for deep selective extraction of indium from an acidic complex system in this embodiment specifically include the following steps:

[0061] (1) p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride were added to anhydrous toluene at a molar ratio of 3:11:18 and refluxed for 6 h. After the reaction, the toluene layer was separated and vacuum rotary evaporated to obtain a crude product, which was then recrystallized from acetone to obtain de-tert-butylcalix[4]arene.

[0062] (2) Tetraethylene glycol and thionyl chloride (SOCl 2 ) was added into anhydrous chloroform at a molar ratio of 1:28, and N,N-dimethylformamide (DMF) was added as an initiator to reflux for 10 h to obtain diethylene glycol dichloroethyl ester.

[0063] (3) Remove tert-butyl calix[4]arene, diethylene glycol dichloroethyl ester, K 2 CO 3 and KI were added to acetone at a molar ratio of 2:4:4:0.2 and refluxed for 20 h. The reaction product was extracted with dichloromethane and vacuum evaporated to obtain a crude product, which was then purified by column chromatography to obtain C5A.

[0064] (4) Dissolve C5A and silane coupling agent (KH560) in DMF solvent, then add ethanol and hydroxyl-loaded SiO 2 The solution was then adjusted to pH 4.5 with hydrochloric acid for 10 h to allow C5A to be grafted onto SiO 2 Granular microspheres, the target product cup crown compound adsorption material SiO 2 @C5A.

[0065] (5) The synthesized cup-crown compound adsorbs the material SiO 2 @C5A was added to an indium-containing leaching system with an acidity of 3 mol / L and reacted at a constant temperature of 70°C for 2.5 h to achieve deep selective separation and extraction of indium, with an indium recovery rate of 99.41%.

Claims

1. A method for synthesizing a calix crown compound adsorption material, characterized in that: The 15-crown-5 ether subunit was introduced into the calix[4]arene structure to form a calix-crown supramolecular compound, which was then loaded onto the surface of SiO2 particles to form a stable adsorption material, thus achieving deep selective separation and extraction of indium in acidic complex systems. The specific synthesis method is: (1) adding p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride in proportion to anhydrous toluene for reflux reaction; after the reaction is completed, separating the toluene layer, vacuum rotary evaporation to obtain a crude product, and then recrystallizing from acetone to obtain de-tert-butylcalix[4]arene; (2) adding tetraethylene glycol and thionyl chloride in proportion to anhydrous chloroform, and adding N,N-dimethylformamide as an initiator to reflux the reaction to obtain diethylene glycol dichloroethyl ester; (3) Adding de-tert-butylcalix[4]arene, diethylene glycol bis(chloroethyl) ester, K2CO3 and KI to acetone in proportion for reflux reaction; extracting the reaction product with dichloromethane and vacuum rotary evaporation to obtain a crude product, which is then purified by column chromatography to obtain C5A; wherein the molar ratio of de-tert-butylcalix[4]arene, diethylene glycol bis(chloroethyl) ester, K2CO3 and KI is in the range of (1-3):(2-6):(2-6):(0.1-0.3), and the reflux reaction time is 8-24 h; (4) C5A and a silane coupling agent are dissolved in an organic solvent, and then ethanol and hydroxyl-loaded SiO2 microspheres are added. The pH of the solution is adjusted with an acid and reacted to graft C5A onto the SiO2 microspheres to obtain the target product, the cup-crown compound adsorption material SiO2@C5A.

2. The method for synthesizing a calix crown compound adsorption material according to claim 1, characterized in that: In the step (1), the molar ratio of p-tert-butylcalix[4]arene, phenol and anhydrous aluminum chloride is in the range of (1-3):(8-12):(15-20), and the reflux reaction time is 1-8 h.

3. The method for synthesizing a calix crown compound adsorption material according to claim 1, characterized in that: In the step (2), the molar ratio of tetraethylene glycol to thionyl chloride is in the range of 1:(15-30), and the reflux reaction time is 2-12 h.

4. The method for synthesizing a calix crown compound adsorption material according to claim 1, characterized in that: The acid used in step (4) is one of acetic acid, hydrochloric acid and sulfuric acid, the pH value of the solution is adjusted to 3-6, and the reaction time is 2-12 h.

5. A method for deep selective extraction of indium in an acidic complex system using a cup crown compound adsorption material synthesized by any of claims 1 to 4, characterized in that: The synthesized cup-crown compound adsorption material SiO2@C5A is added to the indium-containing acidic leaching system for constant temperature reaction to achieve deep selective separation and extraction of indium.

6. The method for deep selective extraction of indium in an acidic complex system according to claim 5, characterized in that: The acidity range of the solution is The reaction temperature is , the reaction time is .