A nickel-containing liquid iron removal adsorption material and preparation method thereof

Abstract

The invention discloses a nickel-containing liquid iron removal adsorption material and a preparation method thereof, the method comprising the following steps: (a) preparation of amine balls: mixing a chlorine ball with a first solvent for swelling, then adding an amine compound, heating and refluxing; (b) purification: recovering the solvent of the composite material obtained in step (a) to obtain an amine ball; (c) preparation of a functional monomer: mixing kojic acid, an aldehyde compound, and an ammonium salt, adding a second solvent, stirring evenly, and heating to react; (d) grafting reaction: adding the amine ball obtained in step (b) to the monomer prepared in step (c), controlling the speed of the stirrer, and heating the system to perform a reflux reaction; (e) purification: recovering the solvent of the material obtained in step (d) to obtain an adsorption material for removing iron from a nickel-containing liquid. The adsorption material synthesized by the present invention has excellent performance in selectively adsorbing iron ions, and is suitable for selective adsorption and separation of iron ions in a complex multi-component heavy metal ion environment.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorption materials, and in particular relates to an adsorption material for removing iron from a nickel-containing liquid and a preparation method thereof. Background Art

[0002] The acceleration of industrialization has driven the development of the metal industry. Alloys or batteries are widely used in the fields of medicine, automobiles, aviation, etc. After the alloys or batteries are discarded, the heavy metal elements of cobalt and nickel in them need to be recycled and reused. Because they are also mixed with other metal ions such as iron, they are similar in nature and are all transition metals, which are difficult to separate.

[0003] At present, there are many methods for separating iron and nickel. A Chinese invention patent (CN101125687 A) discloses a method for removing iron from nickel chloride leaching solution. Chlorine is introduced into the leaching solution to control the redox potential of Fe 2+ Oxidized to Fe 3 + , by adding nickel carbonate to form iron hydroxide precipitation to remove iron. Chinese invention patent (CN103224259 A) discloses a method for refining and recovering valuable metals from crude nickel sulfate, wherein iron salts are removed by adding a fluoride salt precipitant and adjusting the pH with alkaline solution. Chinese invention patent (CN110872107 A) discloses a method for recovering iron from alloy impregnation solutions in the cobalt-nickel industry, using diammonium hydrogen phosphate and hydrogen peroxide to synthesize iron phosphate to remove iron. However, when the above methods are used to remove iron from nickel, there are characteristics that the reagents are difficult to recover, are highly toxic, and pose safety risks to production personnel.

[0004] In the prior art, the more mature iron removal technology includes precipitation method, solvent extraction method, ion exchange method, liquid membrane separation method, etc. Precipitation method and solvent extraction method are more commonly used in industrial production, and are filtered through a quartz sand pool, but the sedimentation method is difficult to handle and difficult to recycle, and the solvent extraction method will produce a large amount of waste liquid, causing environmental pollution. Adsorption separation method can effectively solve the above problems, and will not cause environmental pollution due to excessive use of medicaments. Many researchers have studied the iron removal by adsorption separation method: such as mineral modification, microbial colonies, ion imprinting materials, chelating resins, etc. Among them, chelating resins are widely used because of their wide range of use, higher efficiency, and environmental protection, but most chelating resins cannot effectively separate iron and nickel, and will cause a certain amount of nickel loss. Therefore, it is necessary to develop a chelating resin that can effectively separate iron and nickel. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the present invention provides a method for preparing an adsorbent material for removing iron from a nickel-containing liquid that can be used for industrial production.

[0006] The technical solution of the present invention is:

[0007] The present invention relates to an adsorption material for removing iron from nickel-containing liquid, comprising a compound having the following structure:

[0008]

[0009] The present invention also relates to a method for preparing a nickel-containing liquid iron removal adsorption material, comprising the following steps:

[0010] (a) Preparation of amine balls: mixing chlorine balls with a first solvent to swell, then adding an amine compound, and heating and refluxing;

[0011] (b) purification: recovering the solvent from the composite material obtained in step (a) to obtain amine balls;

[0012] (c) Preparation of functional monomers: kojic acid, aldehyde compound and ammonium salt are mixed in proportion, a second solvent is added, stirred evenly, and the temperature is raised for reaction;

[0013] (d) Grafting reaction: adding the amine balls obtained in step (b) to the monomer prepared in step (c), controlling the speed of the stirrer, and heating the system to perform a reflux reaction;

[0014] (e) Purification: The material obtained in step (d) is subjected to solvent recovery to obtain an adsorption material for removing iron from the nickel-containing liquid.

[0015] Preferably, in step (a), swelling is carried out at 20-50°C for 2-6 hours, the reaction temperature is 50-110°C, and reflux is carried out for 10-20 hours; the mass ratio of the chlorine balls, the first solvent and the amine compound added in step (a) is 1:(1-4):(1-4).

[0016] Preferably, in step (c), the mass ratio of kojic acid, aldehyde compound and ammonium salt is 1: (0.5-1.5): (1.5-2.5); the mass ratio of the second solvent added in step (c) to kojic acid is 1: (2-5); the reaction temperature is 40-60° C., and the reaction is carried out for 16-26 hours.

[0017] Kojic acid is a substance produced by the metabolism of various Aspergillus species and Aspergillus oryzae, and is widely used in food processing and cosmetics industries. In the agricultural field, kojic acid is also often used as an analytical reagent for iron, and has a strong effect on iron, making it an ideal monomer for chelating iron.

[0018] Preferably, in step (d), the mass ratio of the added amine balls to the monomer prepared in step (c) is 1:(2-4); the agitator speed is 180-300 rpm, the temperature is controlled at 50-70° C., and the reflux reaction is carried out for 12-24 hours.

[0019] Preferably, in step (b), the composite material obtained in step (a) is washed with ethanol and pure water or the solvent is recovered by distillation;

[0020] In step (e), the material obtained in step (d) is washed with ethanol and pure water or the solvent is recovered by distillation.

[0021] Preferably, in step (b), the distillation temperature is 50-110°C; in step (e), the distillation temperature is 50-110°C.

[0022] Preferably, in step (a), the first solvent is a mixture of one or more of methanol, ethanol, ethylene dichloride, and toluene;

[0023] The amine compound is a mixture of one or more of ethylenediamine, diethylenetriamine and tetraethylenepentamine.

[0024] Preferably, in step (c), the aldehyde compound is a mixture of one or more of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde;

[0025] The ammonium salt is a mixture of one or more of ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium carbonate;

[0026] The second solvent is a mixture of one or more of methanol, ethanol, isopropanol and n-butanol.

[0027] The beneficial effects of the present invention are:

[0028] 1) The nickel-containing liquid iron removal adsorption material synthesized by the present invention has excellent performance in selectively adsorbing iron ions. The functional groups contained in the material utilize the chelation effect of their coordinating atoms to adsorb iron ions and can form bidentate or even tridentate complexes, which are suitable for selective adsorption and separation of iron ions in a complex multi-component heavy metal ion environment;

[0029] 2) The synthesis of the nickel-containing liquid iron removal adsorption material in the present invention is more environmentally friendly and uses cheap fungal metabolites for synthesis, thus reducing the use of toxic reagents and dangerous surface treatment methods;

[0030] 3) The synthesis of the nickel-containing liquid iron removal adsorption material of the present invention is simple to operate, the reagent cost is low, and the reaction conditions are mild. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The present invention will be further described below in conjunction with the accompanying drawings and embodiments:

[0032] Figure 1 This is a before and after comparison diagram of the adsorption effect test of product A in Example 1;

[0033] Figure 2 It is the infrared spectra of the product obtained in Example 1 and the base ball (chlorine ball). DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0035] Example 1

[0036] (a) Preparation of amine balls: Chlorine balls were mixed with toluene, swelled at 40°C for 4 hours, ethylenediamine was added, the temperature was raised to 110°C, and refluxed for 16 hours; the mass ratio of the added chlorine balls, toluene and ethylenediamine was 1:3:2, and the chlorine balls were purchased from Shanghai Resin Factory.

[0037] (b) Purification: The composite material obtained in step (a) is washed with ethanol and pure water to obtain amine spheres.

[0038] (c) Preparation of functional monomers: kojic acid, formaldehyde and ammonium chloride were mixed in a ratio of 1:1:2, ethanol solvent was added and stirred evenly, the temperature was raised to 50°C, and the reaction was carried out for 24 hours; the mass of the added ethanol accounted for 20% of the mass of the kojic acid.

[0039] (d) Grafting reaction: Add amine balls to the monomer prepared in step (c) for reaction. The mass ratio of the added amine balls to the monomer prepared in step (c) is 1:4. The stirrer speed is controlled at 300 rpm, and the system is heated to 50°C for reflux reaction for 24 hours.

[0040] (e) Purification: The composite material obtained in step (c) is washed with ethanol and pure water to obtain an adsorption material for removing iron from a nickel-containing liquid, which is recorded as product A.

[0041] Figure 2 The infrared spectra of the product obtained in Example 1 and the base ball (chlorine ball) are compared. The hydroxyl group (3300cm -1 ), carbonyl (1665-1685cm -1 ), indicating that a composite material containing hydroxyl and carbonyl groups was successfully obtained after the reaction.

[0042] Example 2

[0043] (a) Preparation of amine balls: Chlorine balls were mixed with toluene, swelled at 40°C for 4 hours, ethylenediamine was added, the temperature was raised to 110°C, and refluxed for 16 hours. The mass ratio of the added chlorine balls, toluene and ethylenediamine was 1:2:2; the chlorine balls were purchased from Shanghai Resin Factory.

[0044] (b) Purification: The composite material obtained in step (a) is washed with ethanol and pure water to obtain amine spheres.

[0045] (c) Preparation of functional monomers: kojic acid, formaldehyde and ammonium chloride were mixed in a ratio of 1:0.75:2, ethanol solvent was added and stirred evenly, the temperature was raised to 50°C, and the reaction was carried out for 24 hours; the mass of the added ethanol accounted for 20% of the mass of the kojic acid.

[0046] (d) Grafting reaction: Add amine balls to the monomer prepared in step (c) for reaction. The mass ratio of the added amine balls to the monomer prepared in step (c) is 1:4. The stirrer speed is controlled at 300 rpm, and the system is heated to 50°C for reflux reaction for 24 hours.

[0047] (e) Purification: The composite material obtained in step (c) is washed with ethanol and pure water to obtain an adsorption material for removing iron from a nickel-containing liquid, which is recorded as product B.

[0048] Example 3

[0049] (a) Preparation of amine balls: Chlorine balls were mixed with toluene, swelled at 40°C for 4 hours, ethylenediamine was added, the temperature was raised to 110°C, and refluxed for 16 hours; the mass ratio of the added chlorine balls, toluene and ethylenediamine was 1:2:3; the chlorine balls were purchased from Shanghai Resin Factory.

[0050] (b) Purification: The composite material obtained in step (a) is washed with ethanol and pure water to obtain amine spheres.

[0051] (c) Preparation of functional monomers: kojic acid, formaldehyde and ammonium chloride were mixed in a ratio of 1:1.5:2, ethanol solvent was added and stirred evenly, the temperature was raised to 50°C, and the reaction was carried out for 24 hours; the mass of the added ethanol accounted for 20% of the mass of the kojic acid.

[0052] (d) Grafting reaction: Add amine balls to the monomer prepared in step (c) for reaction. The mass ratio of the added amine balls to the monomer prepared in step (c) is 1:4. The stirrer speed is controlled at 300 rpm, and the system is heated to 50°C for reflux reaction for 24 hours.

[0053] (e) Purification: The composite material obtained in step (c) is washed with ethanol and pure water to obtain an adsorption material for removing iron from a nickel-containing liquid, which is recorded as product C.

[0054] The performance test of the products prepared in Examples 1-3 was carried out as follows: (1) 5-20 g of the nickel-containing liquid iron removal adsorption material synthesized in Examples 1, 2, and 3 was added to the prepared wastewater containing 100 ppm of multi-metals (Fe, Cu, Ni, Co, Al, Li); (2) The liquid in step (1) was placed in a 100-500 mL conical flask and oscillated in a constant temperature oscillator for 12-18 hours, and then passed through a 0.45 micron membrane to measure the metal ion content. The results are shown in Table 1. The photos of the sample corresponding to Example 1 before and after adsorption are shown in Table 1. Figure 1 shown.

[0055] Table 1 Effect of adsorption materials for iron removal from nickel-containing liquid on adsorption of multiple heavy metals

[0056]

[0057] It can be seen from Table 1 that in the presence of multiple metals, the adsorption material synthesized by the present invention has excellent performance in selectively adsorbing iron ions, and is suitable for selective adsorption and separation of iron ions in a complex multiple heavy metal ion environment.

[0058] It should be understood that the above specific embodiments of the present invention are only used to illustrate or explain the principles of the present invention, and do not constitute a limitation of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. In addition, the appended claims of the present invention are intended to cover all changes and modifications that fall within the scope and boundaries of the appended claims, or the equivalent forms of such scope and boundaries.

Claims

1. A method for preparing an adsorbent material for removing iron from a nickel-containing liquid, characterized in that: The following steps are involved: (a) Preparation of amine balls: mixing chlorine balls with a first solvent to swell, then adding an amine compound, heating and refluxing to react; wherein the amine compound is a mixture of one or more of ethylenediamine, diethylenetriamine, and tetraethylenepentamine; (b) Purification: The composite material obtained in step (a) is washed with ethanol and pure water or the solvent is recovered by distillation to obtain amine spheres; (c) Preparation of functional monomers: kojic acid, aldehyde compounds and ammonium salts are mixed in a proportion such that the mass ratio of kojic acid, aldehyde compounds and ammonium salts is 1: (0.5-1.5): (1.5-2.5), a second solvent is added and stirred evenly, the temperature is raised to a reaction temperature of 40-60° C., and the reaction time is 16-26 h; (d) Grafting reaction: adding the amine balls obtained in step (b) to the monomer prepared in step (c), controlling the speed of the stirrer, and heating the system to perform a reflux reaction; (e) Purification: The material obtained in step (d) is washed with ethanol and pure water or the solvent is recovered by distillation to obtain an adsorption material for removing iron from the nickel-containing liquid.

2. The preparation method according to claim 1, characterized in that: In step (a), swelling is carried out at 20-50° C. for 2-6 hours, the reaction temperature is 50-110° C., and the reflux time is 10-20 hours; the mass ratio of the chlorine balls, the first solvent and the amine compound added in step (a) is 1:(1-4):(1-4).

3. The preparation method according to claim 1, characterized in that: The mass ratio of the second solvent added in step (c) to kojic acid is 1:(2-5).

4. The preparation method according to claim 1, characterized in that: In step (d), the mass ratio of the added amine balls to the monomer prepared in step (c) is 1:(2-4); the agitator speed is 180-300 rpm, the reflux reaction temperature is controlled at 50-70° C., and the reflux reaction time is 12-24 h.

5. The preparation method according to claim 1, characterized in that: In step (b), the distillation temperature is 50-110°C; in step (e), the distillation temperature is 50-110°C.

6. The preparation method according to claim 1, characterized in that: In step (a), the first solvent is a mixture of one or more of methanol, ethanol, ethylene dichloride and toluene.

7. The preparation method according to claim 1, characterized in that: In step (c), the aldehyde compound is a mixture of one or more of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; The ammonium salt is a mixture of one or more of ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium carbonate; The second solvent is a mixture of one or more of methanol, ethanol, isopropanol and n-butanol.

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