CN113121758B - Nano-iron oxyhydroxide gel composite material and preparation method and application thereof - Google Patents

Nano-iron oxyhydroxide gel composite material and preparation method and application thereof Download PDF

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CN113121758B
CN113121758B CN201911411243.3A CN201911411243A CN113121758B CN 113121758 B CN113121758 B CN 113121758B CN 201911411243 A CN201911411243 A CN 201911411243A CN 113121758 B CN113121758 B CN 113121758B
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composite material
iron oxyhydroxide
gel composite
nano iron
drying
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CN113121758A (en
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李永涛
姚波
刘永林
张玉龙
柯美国
林学明
徐会娟
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Guangzhou Qin'an Agricultural Technology Co ltd
South China Agricultural University
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Guangzhou Qin'an Agricultural Technology Co ltd
South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4837—Lignin
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a nano iron oxyhydroxide gel composite material and a preparation method and application thereof. The invention uses the paper-making black liquor of alkaline pulping, acrylamide, maleic anhydride, cross-linking agent and initiator to prepare the gel composite material with cross-linked interpenetrating network macromolecules and high permeability, and generates nano iron oxyhydroxide in the gel composite material by an in-situ synthesis method. The nano iron oxyhydroxide in the composite material obtained by the invention is uniformly distributed, the interpenetrating network structure of the composite material effectively prevents the nano iron oxyhydroxide from gathering and falling off, a proper place is provided for the dispersion and fixation of the nano iron oxyhydroxide, the adsorption and removal effect on heavy metals is obvious, and the composite material has a wide application prospect in the field of removing heavy metals.

Description

Nano-iron oxyhydroxide gel composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a nano iron oxyhydroxide gel composite material and a preparation method and application thereof.
Background
Pb is widely existed in nature, but Pb pollution in soil and water body environment mainly comes from various industrial activities and transportation of human beings. Pb and compounds thereof become one of 68 priority-controlled pollutants in China due to the characteristic of non-degradable toxic pollution, and in addition, Pb can further harm human health through various ways such as food chains, rivers, underground water and the like.
At present, the methods for researching and widely applying Pb in the environment mainly comprise: one is a biochemical method using plants, microorganisms, and the like. The heavy metal Pb in the environment is reduced through the absorption, accumulation and flocculation of plants or microorganisms, so that the pollution remediation effect is achieved. The method has the advantages of high treatment efficiency, low cost, high selectivity and the like, but also has the defects of difficult control of microbial adsorption activity, difficult storage, long implementation period of phytoremediation treatment, limited concentration of heavy metal Pb, and the like. And the other is a physical-chemical method for removing heavy metal ions by means of adsorption, membrane separation, extraction and the like without changing the chemical form of the heavy metal. The common method is an adsorption method, and has the advantages of simple operation, good selectivity, high removal efficiency, capability of treating the lead-containing wastewater with low concentration and the like, but the common adsorbent such as activated carbon has the defects of short service life and the like. Therefore, the selection of a suitable material for adsorption becomes a key factor for treating heavy metals.
With the rapid development of environmental molecular science, in the research of polluted environment remediation, the nano remediation agent becomes a new research hotspot, and precipitation-coprecipitation is formed through the adsorption effect on heavy metal ions, so that the conversion, migration and bioavailability of heavy metals in the environment are reduced. The nano material is different from common materials in the aspects of physical properties such as light, magnetism, heat and the like, has novel characteristics of absorption, radiation, catalysis, adsorption and the like, and in addition, the nano repairing agent contains a large number of micro interfaces and microporosity and can be used for strengthening the reaction on various interfaces. The iron oxyhydroxide has stronger reaction activity, catalytic performance and larger ion exchange capacity, thereby having wide application range. The surface of the iron oxyhydroxide has a large number of hydroxyl groups similar to carboxymethyl cellulose, has certain surface group ion exchange adsorption capacity while having pore adsorption capacity, and is suitable for adsorption of heavy metal ions. However, iron oxyhydroxide nanoparticles are difficult to separate and particles are easy to agglomerate due to the size of the nanometer size, thereby reducing the adsorption performance. Therefore, the stable adsorption of the iron oxyhydroxide nanoparticles by selecting a proper material to disperse the iron oxyhydroxide nanoparticles becomes a key means for solving the adsorption and recovery of lead.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a preparation method of a nano iron oxyhydroxide gel composite material; and (3) loading nanoscale iron oxyhydroxide (beta-FeOOH) on the lignin hydrogel. By combining the hydrogel and the nano material, the problems that the heavy metal adsorption nano material is easy to agglomerate and difficult to recover in the prior art are solved, and a novel composite material is provided for heavy metal restoration. The preparation method comprises the steps of utilizing the papermaking black liquor of alkaline pulping, acrylamide, maleic anhydride and a cross-linking agent (such as N, N-methylene bisacrylamide), introducing an initiator (such as potassium persulfate) to prepare the gel composite material with cross-linked interpenetrating network macromolecules and high permeability, and generating the nano iron oxyhydroxide in the gel composite material by an in-situ synthesis method, wherein the interpenetrating network structure of the composite material prevents the nano iron oxyhydroxide from aggregating and falling off.
Another object of the present invention is to provide a nano iron oxyhydroxide gel composite material, which disperses and fixes nano iron oxyhydroxide, and realizes adsorption of Pb by using the reaction of a large number of hydroxyl groups on the surface of the iron oxyhydroxide with Pb and the adsorption performance of the nano particles; the composite material has high strength and high penetrating water absorption, and can be recycled to achieve the aim of thoroughly removing lead.
The invention also aims to provide application of the nano iron oxyhydroxide gel composite material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nanometer iron oxyhydroxide gel composite material comprises the following steps:
(1) adding a solvent to uniformly mix Acrylamide (AM), alkaline pulping papermaking black liquor, Maleic Anhydride (MAH) and a cross-linking agent, and then adding soluble ferrite to uniformly mix;
(2) adding an initiator into the mixture obtained in the step (1), fully dissolving the initiator, standing until gel is generated, cleaning and drying;
(3) and (3) soaking the xerogel obtained in the step (2) in an alkali solution, and then drying the xerogel in an oxygen-containing atmosphere to obtain the nano iron oxyhydroxide gel composite material.
The alkaline pulping and papermaking black liquor in the step (1) is a mixture and contains a large amount of alkali lignin and macromolecular organic matters, wherein the macromolecular organic matters are favorable for dispersion and crosslinking, and can play a better role in dispersing iron ions; molecular weight is more than 10000, and the product has alkalinity and can promote the generation of iron oxyhydroxide.
The alkaline pulping papermaking black liquor, the acrylamide and the maleic anhydride in the step (1) are preferably mixed according to the mass ratio of (5-10) to (3-5) to (1-2).
The cross-linking agent in the step (1) is preferably N, N-methylene bisacrylamide (NMBA); the dosage of the N, N-methylene bisacrylamide is preferably mixed according to the mass ratio of the N, N-methylene bisacrylamide to the alkaline pulping papermaking black liquor of (0.01-0.02) to (5-10).
In the step (1), Acrylamide (AM), alkaline pulping papermaking black liquor, Maleic Anhydride (MAH) and a cross-linking agent are completely dissolved and uniformly mixed by stirring, and the stirring is preferably mechanical stirring.
The final concentration of the soluble ferrous salt solution in the step (1) is preferably0.03～0.17mol·L-1。
The amount of the soluble ferrous salt penetrating into the composite material and the loading amount of the nano particles are controlled by limiting the concentration of the soluble ferrous salt so as to achieve the purpose of use, the gel forming is influenced too much, and the adsorption amount is reduced too little.
The soluble ferrous salt in the step (1) is preferably FeSO4.7Η2O。
The soluble ferrous salt in the step (1) can be prepared into a solution firstly and then added; the solvent is preferably water.
Said sufficient dissolution in step (2) is preferably achieved by stirring; the stirring time is preferably 1-2 h.
The initiator in the step (2) is preferably potassium persulfate (KPS); the dosage of the potassium persulfate is preferably mixed according to the mass ratio of the potassium persulfate to the alkaline pulping papermaking black liquor of (0.05-0.1) to (5-10).
The drying in the step (2) is preferably freeze drying; the freeze drying time is preferably 6-18 h.
The soaking time in the step (3) is preferably 2-4 h.
The alkali solution in the step (3) is preferably a weak alkali solution; further preferably a carbonate solution; more preferably NaHCO3And (3) solution.
The concentration of the alkali solution in the step (3) is preferably 1-2 mol.L-1。
The soaking in the step (3) is preferably continuously stirred and soaked; the stirring is preferably mechanical stirring.
The drying under an oxygen-containing atmosphere described in the step (3) may be drying in air or drying by introducing oxygen.
The water in the steps (1), (2) and (3) is preferably deionized water, distilled water or ultrapure water.
All reagents used in the above steps were purchased from alatin.
A nanometer iron oxyhydroxide gel composite material is prepared by the preparation method.
The application of the nanometer iron oxyhydroxide gel composite material in the field of heavy metal removal.
The nano iron oxyhydroxide gel composite material can be applied to removing heavy metals in the environment (water environment or soil environment), and the heavy metals in the soil environment are removed by adding the material into the soil in a flooding environment to remove the heavy metals.
The nano iron oxyhydroxide gel composite material is also suitable for the water environment polluted by heavy metal; the lead removal effect is particularly remarkable.
The invention utilizes the crosslinking polymerization of the papermaking black liquor (containing a large amount of alkali lignin) and acrylamide prepared by an alkaline method to realize interpenetrating network macromolecules; ferrous ions are uniformly dispersed in the nano iron oxide powder, and the nano iron oxide powder is slowly oxidized in situ to obtain the nano iron oxyhydroxide. In the nano iron oxyhydroxide gel composite material prepared by the invention, nano iron oxyhydroxide is uniformly distributed on the composite material, abundant hydroxyl on the surface of the iron oxyhydroxide is utilized to react with heavy metal lead in the environment and/or lead (Pb) is adsorbed by depending on the larger specific surface area of nano particles; recovery with gel after adsorption is complete.
Compared with the prior art, the invention has the following advantages and effects:
(1) the raw material of the invention is the black liquor of alkaline pulping paper making, which is derived from the waste liquor of paper making factories, belongs to resource recycling, saves cost and reduces environmental pollution.
(2) The alkaline pulping and papermaking black liquor (mainly alkali lignin) has strong dispersibility, various active groups exist on the organization structure of the alkaline pulping and papermaking black liquor, and the polymerization and dielectric behavior is displayed in a water body environment, so that the exchange effect of metal ions is facilitated, and the effect of removing heavy metals is further achieved.
(3) The obtained iron oxyhydroxide gel composite material has stronger permeability after freeze drying and is beneficial to the permeation and adsorption of heavy metal solution.
(4) The composite material prepared by the invention only needs simple mixing and soaking processes, and is simple and easy to operate.
(5) The nano particles prepared by the in-situ synthesis method are uniform and firm on the gel, and compared with other methods, the method is easier to control the nano particle size and is more convenient to operate.
(6) The cross-linking agent (such as N, N-methylene bisacrylamide) and the acrylamide are initiated to polymerize to form the cross-linking agent, so that the aggregation and falling-off of the nano iron oxyhydroxide can be well prevented, and a proper place is provided for the dispersion and fixation of the nano iron oxyhydroxide.
(7) The composite material has obvious effect of adsorbing and removing heavy metals.
Drawings
FIG. 1 is a photograph showing a real object of the nano iron oxyhydroxide gel composite obtained in example 1.
FIG. 2 is an XRD pattern of β -FeOOH in the nano iron oxyhydroxide gel composite obtained in example 1.
FIG. 3 is a scanning electron micrograph (magnification 1500) of the nano iron oxyhydroxide gel composite obtained in example 1.
FIG. 4 is a Largmuir fitting graph of Pb adsorption of the nano iron oxyhydroxide gel composite obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The alkaline pulping and papermaking black liquor used in the embodiment is waste water generated by a conventional alkaline pulping process in the papermaking industry, and the alkaline pulping and papermaking black liquor is liquid and contains a large amount of alkaline lignin; the black liquor from the alkaline pulping process used in the following examples was from Guangzhou paper making group, Inc.
Example 1
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (derived from Guangzhou paper making group Co., Ltd., alkali-containing lignin LS), 1.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L- 1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 6 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in the air (or introducing oxygen for drying) for 2 hours to obtain the nano iron oxyhydroxide gel composite material.
The appearance of the nano iron oxyhydroxide gel composite material is shown in figure 1.
XRD analysis of the obtained nano iron oxyhydroxide gel composite material was performed by an X-ray diffractometer (model D/max2200, Rigaku corporation, Tokyo, Japan), and the result is shown in FIG. 2.
The morphology of the nano iron oxyhydroxide gel composite material was measured by a scanning electron microscope (model number QUANTA 200, FEI corporation, oregon, usa), and the result is shown in fig. 3.
Example 2
(1) Weighing 4.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 12 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 3
(1) Weighing 5.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH), and N, N-methylene bisacrylamide serving as a crosslinking agent(NMBA)0.01g, adding 20mL deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 18 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in the air (or introducing oxygen for drying) for 3 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 4
(1) Weighing 3.00g of Acrylamide (AM), 8.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 6 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 5
(1) Weighing 3.00g of Acrylamide (AM), 10.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 12 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 6
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 2.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 18 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 7
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 6 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3The solution is dried in air (or aerated with oxygen) for 4hDrying) to obtain the nano iron oxyhydroxide gel composite material.
Example 8
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.01g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.3 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 12 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 9
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.5 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 18 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 10
(1) Weighing Acrylamide (AM)3.00g, alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.) 5.00g, Maleic Anhydride (MAH)100g of cross-linking agent N, N-methylene bisacrylamide (NMBA)0.02g, 20mL of deionized water is added, the mixture is mechanically stirred until all the raw materials are completely dissolved, the raw materials are uniformly mixed, and then the raw materials are mixed by 0.1 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.075g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 6 hours;
(3) soaking the xerogel obtained in the step (2) in 1 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 11
(1) Weighing 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.5 mol.L-1FeSO4.7Η2O solution 10 mL.
(2) Adding 0.1g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 1 hour in the step (1), uniformly stirring, standing until gel is generated after the mixture is fully dissolved, fully cleaning, and freeze-drying for 12 hours;
(3) soaking the xerogel obtained in the step (2) in 2 mol. L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
Example 12 comparative experiment
To further demonstrate the advantages of the composite, a blank was prepared for comparison:
(1) weighing 3.00g of Acrylamide (AM), 0.3g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.5g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, and mechanically stirring until all the raw materials are completely dissolved;
(2) adding 0.05g of initiator potassium persulfate (KPS) into the mixture uniformly stirred for 2 hours in the step (1), continuously cleaning, and freeze-drying for 18 hours; a blank hydrogel was obtained.
Example 13
To highlight the feasibility and significance of the raw materials, experimental sequences and experimental conditions, comparisons were made by the following experiments.
(1) Taking 3.00g of Acrylamide (AM), 5.00g of alkali lignin (chemical purity, purchased from Aladdin), 1.00g of Maleic Anhydride (MAH) and 0.02g of cross-linking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.5 mol.L-1FeSO4.7Η2O solution 10 mL. 0.05g of initiator potassium persulfate (KPS) is added into the mixture after being uniformly stirred for 1 hour, the mixture is uniformly stirred, after the mixture is fully dissolved, the strength of gel generated after standing is low, and the gel is easy to break and cannot be subjected to the next reaction.
(2) Taking 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all raw materials are completely dissolved, adding 0.05g of initiator potassium persulfate (KPS) into the mixture after uniformly stirring for 1h, uniformly stirring, standing after fully dissolving, and generating gel. Freeze drying the gel, and soaking in 10mL of 0.5 mol/L-1FeSO4.7Η2O solution for 2 hours, and then washing and freeze-drying. The obtained xerogel is soaked in 2 mol.L-1NaHCO3And drying the solution in air (or drying by introducing oxygen) for 4 hours to obtain the nano iron oxyhydroxide gel composite material.
(3) Taking 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 1 mol.L-1FeSO4.7Η2O solution 10 mL. After stirring for 1h, the mixture was added with the initiator potassium persulfate (K)PS)0.05g, uniformly stirring, fully dissolving, standing to generate gel with low strength, and being easy to break, so that the next reaction can not be carried out. The preparation method exposes more FeSO4.7Η2O, iron ions tend to deactivate the initiator or react rapidly and do not polymerize the gel better.
(4) Taking 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.01 mol.L-1FeSO4.7Η2O solution 10 mL. 0.05g of initiator potassium persulfate (KPS) is added into the mixture after being uniformly stirred for 1 hour, the mixture is uniformly stirred, after the mixture is fully dissolved, the strength of gel generated after standing is low, and the gel is easy to break and cannot be subjected to the next reaction.
(5) Taking 3.00g of Acrylamide (AM), 5.00g of alkaline pulping papermaking black liquor (from Guangzhou paper making group Co., Ltd.), 1.00g of Maleic Anhydride (MAH) and 0.02g of crosslinking agent N, N-methylene bisacrylamide (NMBA), adding 20mL of deionized water, mechanically stirring until all the raw materials are completely dissolved, uniformly mixing, and then mixing 0.1 mol.L-1FeSO4.7Η2O solution 10 mL. And adding 0.05g of initiator potassium persulfate (KPS) into the mixture after uniformly stirring for 1h, uniformly stirring, standing to generate gel after fully dissolving, cleaning and freeze-drying. The obtained xerogel is soaked in 2 mol.L-1NaHCO3The solution is dried under nitrogen protection or vacuum freeze-dried for 4 h. XRD analysis is carried out on the finally obtained product, no beta-FeOOH diffraction peak is found, and the fact that the scheme cannot generate the beta-FeOOH is proved, so that the importance of oxygen is shown.
Example 14
The beneficial effects of the present invention are further illustrated by the relevant experimental data below.
The nano composite material prepared by the embodiment of the invention is used for adsorbing heavy metal Pb2+And (3) measuring the heavy metal content of the wastewater solution, comparing before and after adsorption, and determining the adsorption effect.
0.05g of the nanocomposite obtained in example 1 was added to 40mL of a 100mg/L aqueous solution of Pb, and the mixture was placed in a shaker 100r/min, and then, 5, 10, 15, 20, 25, 30, 60, 90, 120, 180, 240, 300, 360, 480, and 1440min were respectively adsorbed and sampled (at room temperature without pH adjustment), and the absorbance of the adsorption equilibrium solution was measured by an atomic absorption spectrometer, whereby the concentration of Pb was calculated, and the Pb (II) adsorption was calculated according to the following equation:
Figure BDA0002350021240000111
Figure BDA0002350021240000112
wherein q ise(mg/g) represents the amount of adsorption at adsorption equilibrium, C0(mg/L) represents the initial concentration of Pb (II), Ce(mg/L) represents Pb (II) adsorption concentration when adsorption reaches equilibrium, m (g) represents mass of the composite material, V (L) represents volume of Pb (II) solution, q (II) represents volume of the composite material, andt(mg/g) represents the amount of adsorption of the material after a certain period of adsorption, Ct(mg/L) represents the concentration of the Pb (II) solution after adsorption for a certain period of time.
The adsorption capacity at the adsorption equilibrium is calculated to be 89.4mg/g and the maximum adsorption capacity is 400mg/g according to the formula (shown in figure 4).
0.05g of the nanocomposite obtained in example 1 was added to 40mL of a 100mg/L aqueous solution of Pb, and the mixture was placed in a shaker at 50r/min for adsorption for various periods of time, and then absorbance of the adsorption equilibrium solution was measured by an atomic absorption spectrometer, whereby the concentration of Pb and the adsorption efficiency were calculated. The adsorption rate at the adsorption equilibrium reaches 86.9mg/g, and the result is not obviously different from the above result.
According to the above conditions, the materials prepared in examples 2 to 11 adsorbed Pb solutions in the same manner (0.025 g each was added to 40mL of a 100mg/L aqueous Pb solution and placed in a shaker at 100r/min), and the equilibrium adsorption rates were 90.3mg/g, 88.6mg/g, 86mg/g, 89mg/g, 89.1mg/g, 87.7mg/g, 87.9mg/g, 86.4mg/g, 89.7mg/g, and 88.8mg/g, respectively.
0.05g of the blank obtained in example 12 was added to 40mL of a 100mg/L aqueous solution of Pb, and the mixture was placed in a shaker 100r/min, and after adsorption for 300min, samples were taken, and the absorbance of the adsorption equilibrium solution was measured by an atomic absorption spectrometer, whereby the concentration of Pb and the adsorption amount were calculated. The absorption capacity of the obtained blank material is 19.5mg/g when the absorption balance is realized, and the difference with the nano composite material is obvious.
0.05g of the material obtained in example 13(2) was added to 40mL of a 100mg/L aqueous solution of Pb, and the mixture was placed in a shaker 100r/min, and after adsorption for 300min, samples were taken, and the absorbance of the adsorption equilibrium solution was measured by an atomic absorption spectrometer, whereby the concentration of Pb and the adsorption amount were calculated. The adsorption capacity of the material is 27.3mg/g when the adsorption equilibrium is obtained, and FeSO is changed4.7Η2The addition sequence of O has obvious influence on the adsorption, and the good dispersion of iron ions at the early stage is crucial to the adsorption.
0.05g of the material obtained in example 13(4) was added to 40mL of a 100mg/L aqueous solution of Pb, and the mixture was placed in a shaker 100r/min, and after adsorption for 300min, samples were taken, and the absorbance of the adsorption equilibrium solution was measured by an atomic absorption spectrometer, whereby the concentration of Pb and the adsorption amount were calculated. The adsorption capacity of the material is 12.1mg/g when the adsorption balance is obtained, and FeSO is reduced4.7Η2The amount of O, the amount of adsorption is significantly reduced.
The composite material prepared by the invention can be used for removing Pb in a polluted paddy field, and can be placed in overlying water of the paddy field to adsorb Pb in water firstly and then to adsorb Pb in soil resolved into water, so that the aim of removing Pb in soil is fulfilled repeatedly. After the rice grows for one period, the rice can be fished out by a screen or filtered out when water is drained, so that the aim of recovery is achieved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a nanometer iron oxyhydroxide gel composite material is characterized by comprising the following steps:
(1) adding solvent to uniformly mix acrylamide, alkaline pulping papermaking black liquor, maleic anhydride and cross-linking agent, and then adding soluble ferrous salt to uniformly mix;
(2) adding an initiator into the mixture obtained in the step (1), fully dissolving the initiator, standing until gel is generated, cleaning and drying;
(3) and (3) soaking the xerogel obtained in the step (2) in an alkali solution, and then drying the xerogel in an oxygen-containing atmosphere to obtain the nano iron oxyhydroxide gel composite material.
2. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 1, characterized in that:
the final concentration of the soluble ferrous salt solution in the step (1) is 0.03-0.17 mol.L-1。
3. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 1, characterized in that:
the cross-linking agent in the step (1) is N, N-methylene bisacrylamide;
the initiator in the step (2) is potassium persulfate;
the concentration of the alkali solution in the step (3) is 1-2 mol.L-1。
4. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 3, characterized in that:
the dosage of the N, N-methylene bisacrylamide is proportioned according to the mass ratio of the N, N-methylene bisacrylamide to the alkaline pulping papermaking black liquor of (0.01-0.02) to (5-10);
the amount of the potassium persulfate is proportioned according to the mass ratio of the potassium persulfate to the alkaline pulping and papermaking black liquor of (0.05-0.1) to (5-10).
5. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 1, characterized in that:
the alkaline pulping papermaking black liquor, the acrylamide and the maleic anhydride in the step (1) are mixed according to the mass ratio of (5-10) to (3-5) to (1-2);
the drying in the step (2) is freeze drying;
the alkali solution in the step (3) is a weak alkali solution.
6. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 5, characterized in that:
the freeze drying time is 6-18 h;
the alkali solution in the step (3) is a carbonate solution;
the drying in the oxygen-containing atmosphere in the step (3) is drying in air or drying by introducing oxygen.
7. The method for preparing a nano iron oxyhydroxide gel composite material according to claim 1, characterized in that:
the soluble ferrous salt in the step (1) is FeSO4.7Η2O；
The alkali solution in the step (3) is NaHCO3A solution;
and (4) soaking for 2-4 h.
8. A nanometer iron oxyhydroxide gel composite material is characterized in that:
the nano iron oxyhydroxide gel composite material is prepared by the preparation method of any one of claims 1 to 7.
9. Use of the nano iron oxyhydroxide gel composite according to claim 8 in the field of heavy metal removal.
10. Use of the nano iron oxyhydroxide gel composite according to claim 9 in the field of heavy metal removal, characterized in that:
the heavy metal comprises heavy metal in water or soil;
the heavy metal is lead.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101119934A (en) * 2005-02-16 2008-02-06 独立行政法人科学技术振兴机构 Method for producing iron oxyhydroxide and adsorbing material comprising iron oxyhydroxide
CN102504109A (en) * 2011-11-15 2012-06-20 西南石油大学 Cyclodextrin supported hydrogel and preparation method thereof
JP2013166090A (en) * 2012-02-14 2013-08-29 Nippon Filcon Co Ltd Gel-like metal adsorbing material and gel-like metal adsorbing material supported adsorbent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101119934A (en) * 2005-02-16 2008-02-06 独立行政法人科学技术振兴机构 Method for producing iron oxyhydroxide and adsorbing material comprising iron oxyhydroxide
CN102504109A (en) * 2011-11-15 2012-06-20 西南石油大学 Cyclodextrin supported hydrogel and preparation method thereof
JP2013166090A (en) * 2012-02-14 2013-08-29 Nippon Filcon Co Ltd Gel-like metal adsorbing material and gel-like metal adsorbing material supported adsorbent

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