CN109046292B - Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof - Google Patents

Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof Download PDF

Info

Publication number
CN109046292B
CN109046292B CN201811092532.7A CN201811092532A CN109046292B CN 109046292 B CN109046292 B CN 109046292B CN 201811092532 A CN201811092532 A CN 201811092532A CN 109046292 B CN109046292 B CN 109046292B
Authority
CN
China
Prior art keywords
organic
adsorbent
inorganic hybrid
exchange resin
ion exchange
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811092532.7A
Other languages
Chinese (zh)
Other versions
CN109046292A (en
Inventor
孙奇娜
崔悦
张庆瑞
陈龑斐
刘欣超
贾清川
韩梦星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yanshan University
Original Assignee
Yanshan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yanshan University filed Critical Yanshan University
Priority to CN201811092532.7A priority Critical patent/CN109046292B/en
Publication of CN109046292A publication Critical patent/CN109046292A/en
Application granted granted Critical
Publication of CN109046292B publication Critical patent/CN109046292B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • 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
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic 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
    • C02F1/285—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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to organic-inorganic hybrid adsorbents with hierarchical structures, a preparation method and application thereof.A preparation method comprises the steps of adding ion exchange resin, dopamine, copper sulfate and hydrogen peroxide into a Tris-HCl buffer solution, separating the ion exchange resin with the adhesive polydopamine on the surface by a dark reaction at room temperature, adding the resin into a ferrous salt solution, reacting at room temperature, separating the ion exchange resin with iron, then adding thiol protease and the ion exchange resin with iron into a PBS buffer solution, reacting at room temperature, separating solid materials, and naturally drying to obtain the organic-inorganic hybrid adsorbents with hierarchical structures.

Description

Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of heavy metal sewage treatment, and particularly relates to organic-inorganic hybrid adsorbents with hierarchical structures and a preparation method thereof.
Background
Along with the rapid growth of the economy of China, particularly the centralized development of the industries such as mining and metallurgy, machinery, electroplating, printing and dyeing and the like within hours, the problem of heavy metal pollution in the environment, particularly in water bodies, is increasingly emphasized, because mercury, lead, cadmium and other heavy metals have stronger biotoxicity, the heavy metal pollution in the water bodies can cause great harm to the ecological environment of the water bodies, the physical and chemical properties of heavy metal ions are similar to iron, calcium, potassium, sodium and other ions in the organisms, the heavy metal ions are easy to accumulate in the bodies and finally enter human bodies through food chains to cause serious diseases and even threaten human life, and in order to control the heavy metal pollution of water bodies, 10 emission limit values of the heavy metal pollutants are regulated in 13 pollutants in the comprehensive sewage emission standard of China.
Among the heavy metal pollution treatment methods for various water bodies, the adsorption method is conventional treatment methods, which have the advantages of simple treatment process, high treatment efficiency, easy modularization of equipment and industrial scale application as early as decades ago(-1～0)The traditional adsorbent is applied to fields in a water treatment process, has low cost and high chemical property and mechanical property stability, is easy to separate from treated effluent in equipment, has small specific surface area and adsorption capacity, and has large influence on the adsorption effect of target heavy metal pollutants by coexisting ions of sodium, calcium, magnesium and the like in a water body[1-4]。
In the nano adsorbent, inorganic materials such as metal oxide/hydroxide/salt and the like show better adsorption performance than the traditional commercial adsorbent, particularly, in nano iron material which is a research hotspot in recent years, taking the treatment of typical heavy metal lead ions Pb (II) as an example, the adsorption capacity of the magnetic Fe/Mn nano adsorbent can reach 118.06mg/g, the removal rate can reach 70 percent, and Fe can reach 70 percent3O4The highest removal rate of the nano adsorbent is 90 percent, and the removal rate of the nano iron FeNPs is 91 percent[5-7]. The nano iron adsorbent has huge specific surface area and good adsorption capacity to heavy metal ions in water, and because iron is the original constant in human bodies and other numerous organisms, the biological safety of the element in the preparation and application process is better than that of other metal elements such as cerium, zirconium, copper, manganese and the like.
In addition, in recent years, the synthesis of organic-inorganic hybrid nano materials with special morphology by inducing protein has appeared in the field of nano material preparation, and the hybrid materials generally have the biological activity of organic components and the stability of inorganic components, and can greatly improve the stability of organic components and the activity of the materials, so that the hybrid materials are attracted by in the fields of biology, food and medicine, and the corresponding nano flower-shaped powder materials can be prepared by using copper, manganese, nickel and cobalt as inorganic components, sericin, bovine serum albumin, ovalbumin and numerous enzymes as organic templates, and the application of the hybrid materials comprises biosensors, biocatalysis, pharmacy and the like[8-12]。
However, the nano adsorbent is powder, so that the nano adsorbent is easy to agglomerate in a water phase to lose the unique performance of a nano material, has poor settleability, is easy to run off along with water, is difficult to separate from a treated water body, and is difficult to directly load in an adsorption column for use.
Reference to the literature
[1] Wangbaozhen, heavy metal wastewater treatment technology and development trend [ J ] environmental science, 1979(01):62-68+38.
[2] Research on the adsorption performance of the sodium sulfide modified activated carbon on Pb (II) is carried out on Zhu Xiaotao, Mao Lei, Yang Bao Zi, Li Shuang Chang, Tongshitang, 2016,32(3):222-233.
[3] Xujia 40719New developments of ion exchange resins [ J ] chemical world, 1958(02):19-22.
[4] Li yan, laboratory research on multi-stage ion exchange treatment technology of high-concentration special heavy metal wastewater [ D ]. tianjin university, 2014.
[5] Zhao Shi Wei, He Zi and He Jie Liu Jie, and removing lead ion from water with the new magnetic Fe/Mn nano composite material [ J ]. proceedings of Harbin university 2012(08):27-30.
[6] Bana research on Fe3O 4/aspergillus niger composites for removal of heavy metal ions in water [ D ] gilin university, 2014.
[7] The green synthesized nano iron can remove Pb (II) and Cd (II) J in water body at the same time, and environmental science reports 2015,35(11) 3538 and 3544.
[8]Ge Jun,Lei Jiandu,Zare Richard N.Protein-inorganic hybridnanoflowers[J].Nature nanotechnology.2012(06):428-432.
[9]Linghao He,Shuai Zhang,et al.Protein-templated cobaltous phosphatenanocomposites for the highly sensitive and selective detection of platelet-derived growth factor[J].Biosensors and Bioelectronics.2015(10):553-560.
[10] Huecuite, protein-controlled synthetic copper nanoclusters were used to mimic enzyme research [ D ] university of gilin, 2017.
[11] Preparation and application of manganese phosphate-based nanoflower hybrid materials in a garden plant [ D ]. Zheng Zhou Qing Industrial academy 2015.
[12] Preparation and application research of novel protein-inorganic salt hybrid nanocomposite material [ D ]. Fuzhou university, 2016.
Disclosure of Invention
Based on the above, it is necessary to provide kinds of organic-inorganic hybrid adsorbents with hierarchical structures, and a preparation method and applications thereof, aiming at the problems that the existing powder nano adsorbent is easy to agglomerate and run off when treating heavy metal-containing wastewater and is difficult to separate from a treated water body.
kinds of organic-inorganic hybrid adsorbents with a hierarchical structure are prepared by the following steps:
(1) adding ion exchange resin, dopamine, copper sulfate and hydrogen peroxide into a Tris-HCl buffer solution, carrying out a dark reaction at room temperature for 30-40 minutes, and separating the ion exchange resin with the adhesive polydopamine on the surface;
(2) adding ion exchange resin with adhesive polydopamine on the surface into a ferrous salt solution, reacting for 2-4 hours at room temperature, and separating out the ion exchange resin with iron;
(3) adding thiol protease and ion exchange resin with iron into PBS buffer solution, reacting for 4-6 hours at room temperature, separating solid material, and naturally drying to obtain the organic-inorganic hybrid adsorbent with a hierarchical structure.
The adsorbent prepared by the preparation method of the organic-inorganic hybrid adsorbent with the hierarchical structure has a sub-10 nm flower-shaped hierarchical structure of the surface nano-iron component, can efficiently adsorb lead ions in water, solves the problems that the existing powdery nano-adsorbent is easy to agglomerate and run off and is difficult to separate from a treated water body when treating lead-containing wastewater, and is suitable for treating heavy metal sewage.
In examples, the pH of the Tris-HCl buffer solution in the step (1) is 8.0-9.0.
In examples, the ion exchange resin, dopamine, copper sulfate and hydrogen peroxide in step (1) are added in an amount of 5-15 g and 2-3 g (HO) per 1L of Tris-HCl buffer solution2C6H3CH2CH2NH2·HCl、1～2g CuSO4·5H2O, 2.5-4.0 mL of 30% by mass of H2O2And (3) solution.
In examples, the ion exchange resin in step (1) was a macroporous cation exchange resin.
In examples, the concentration of Fe in the ferrous salt solution in the step (2) is 0.02-0.2 mol/L.
In examples, the ferrous salt in the step (2) is any ferrous sulfate or ferrous chloride.
In examples, the concentration of thiol protease in the PBS buffer solution in step (3) is 0.5-5 g/L, and the pH of the solution is 7.2-7.6.
In of the embodiments, the thiol protease in step (3) is a cysteine protease.
The invention also relates to organic-inorganic hybrid adsorbents with hierarchical structures, which are prepared by the preparation method of any .
The invention also relates to application of the organic-inorganic hybrid adsorbent with the hierarchical structure in removal of heavy metal pollution of a water body.
In of the examples, the organic-inorganic hybrid adsorbent with a hierarchical structure of the present invention is suitable for removing lead ions in a water body.
In examples, the specific method for removing lead ions in water body by using the organic-inorganic hybrid adsorbent with hierarchical structure of the invention can be as follows:
(1) fully mixing the adsorbent with a lead-containing water body;
(2) and separating the adsorbent after treatment to obtain water after lead removal.
In of the examples, the mixing method of the adsorbent and water includes, but is not limited to, one or more of mechanical agitation, aeration, and water passage through the adsorbent in a fluidized state ;
in examples, the separation method of the adsorbent from water includes, but is not limited to, or more of filtration interception, standing sedimentation and centrifugal separation.
In examples, 0.3-1.0 g of adsorbent is used per 1L of water, the pH range is 3-7, and the lead ion concentration is 1-200 mg/L.
Of these, examples used 0.5g of adsorbent per 1L of water.
In of these examples, the use temperature may be 20 ℃ to 60 ℃.
Drawings
FIG. 1 is an electron microscope image of a sub-10 nm flower-like hierarchical structure morphology of a nano-iron component on the surface of the adsorbent.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The preparation method of the organic-inorganic hybrid adsorbent with the hierarchical structure comprises the following steps:
(1) adding ion exchange resin, dopamine, copper sulfate and hydrogen peroxide into a Tris-HCl buffer solution, carrying out a dark reaction at room temperature for 30-40 minutes, and separating the ion exchange resin with the adhesive polydopamine on the surface;
(2) adding ion exchange resin with adhesive polydopamine on the surface into a ferrous salt solution, reacting for 2-4 hours at room temperature, and separating out the ion exchange resin with iron;
(3) adding thiol protease and ion exchange resin with iron into PBS buffer solution, reacting for 4-6 hours at room temperature, separating solid material, and naturally drying to obtain the organic-inorganic hybrid adsorbent with a hierarchical structure.
Preferably, the pH of the Tris-HCl buffer solution in the step (1) is 8.0-9.0.
Preferably, the dosage of the ion exchange resin, dopamine, copper sulfate and hydrogen peroxide in the step (1) is as follows: adding 5-15 g of ion exchange resin and 2-3 g of (HO) into 1LTris-HCl buffer solution2C6H3CH2CH2NH2·HCl、1～2gCuSO4·5H2O, 2.5-4.0 mL of 30% by mass of H2O2And (3) solution.
Preferably, the ion exchange resin in step (1) is a macroporous cation exchange resin.
Preferably, the concentration of Fe in the ferrous salt solution in the step (2) is 0.02-0.2 mol/L.
Preferably, the ferrous salt in the step (2) is any kinds of ferrous sulfate or ferrous chloride.
Preferably, the concentration of the thiol protease in the PBS buffer solution in the step (3) is 0.5-5 g/L, and the pH of the solution is 7.2-7.6.
Preferably, the thiol protease in step (3) is a cysteine protease.
The organic-inorganic hybrid adsorbent with the hierarchical structure is prepared by the preparation method.
The organic-inorganic hybrid adsorbent with the hierarchical structure takes ion exchange resin as a framework, polydopamine as an adhesive, thiol protease as a guiding agent and iron as an inorganic nano-component, the macroscopic appearance of the adsorbent is spherical, the diameter of the adsorbent is millimeter, the inorganic nano-component forms a flower-shaped hierarchical structure on the surface of the framework, and the scale of the adsorbent is sub-10 nm.
The organic-inorganic hybrid adsorbent with the hierarchical structure has a good application prospect in removing heavy metal pollution of a water body.
In particular, the organic-inorganic hybrid adsorbent with a hierarchical structure is suitable for removing lead ions in a water body.
The specific method for removing the lead ions in the water body by applying the organic-inorganic hybrid adsorbent with the hierarchical structure can be as follows:
(1) fully mixing the adsorbent with a lead-containing water body;
(2) and separating the adsorbent after treatment to obtain water after lead removal.
Wherein the mixing method of the adsorbent and the water comprises but is not limited to or more of mechanical stirring, aeration and water passing through the adsorbent in a fluidized state;
wherein, the separation method of the adsorbent and the water comprises or more of filtration interception, standing sedimentation and centrifugal separation.
Preferably, 0.3-1.0 g of adsorbent is used per 1L of water, the pH range is 3-7, and the lead ion concentration is 1-200 mg/L.
More preferably, 0.5g of adsorbent is used per 1L of water, and the removal rate of lead ions can reach more than 90%.
For water containing sodium ions and the concentration of the sodium ions is 0-64 times (molar ratio) of that of the lead ions, the removal rate of the lead ions by the adsorbent can reach more than 95% of that of water without coexisting sodium ions.
The lead ion removing method can be used at the temperature of 20-60 ℃.
The lead ion removal rate of the invention refers to the percentage of the reduction of the lead ion concentration in water in the lead ion concentration in the raw water after the treatment is finished.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the organic-inorganic hybrid adsorbent with the hierarchical structure adopts new rapid and mild methods, is easy for large-scale production, the preparation process is completely carried out in normal-temperature aqueous phase, the finally prepared adsorbent is naturally aired at normal temperature to obtain the flower-shaped hierarchical morphology of the nano-components, heating and drying are not needed, the conditions are mild, under the combined action of all the components, the preparation process of the adsorbent only needs about 6.5-10.7 hours, the preparation time of similar load hybrid materials is greatly shortened, a small amount of copper sulfate and hydrogen peroxide are used for promoting the polymerization reaction of dopamine in a buffer solution, the required concentration of the dopamine is only 2-3 g/L, and the preparation cost is greatly reduced;
2. the preparation method of the organic-inorganic hybrid adsorbent with the hierarchical structure realizes the stable growth of the nano-iron with the flower-like hierarchical morphology of sub-10 nm on a macroscopic skeleton, which jointly realizes the adhesion of the nano-components and the macroscopic skeleton by means of catechol functional groups and terminal amino functional groups of polydopamine generated in a buffer solution and intermolecular force provided by chain link active centers on macroporous resin, greatly increases the stability of the nano-components, enables ferrous salt to be dispersed on the surface of the skeleton under the action of resin functional group sulfonic acid groups, relieves the problem of surface nano-component agglomeration in the hybrid material synthesis process, combines the guiding action of protease, finally enables the inorganic nano-components to form uniform flower-like hierarchical morphology on the surface of the adsorbent, can lead the flower-like hierarchical morphology, contains cysteine protease residues, contains only sulfydryl in amino acid, and can be in an ionized state without depending on a substrate, thereby promoting the dimension of the nano-iron components to be reduced to sub-10 nm level, and plays an indispensable key role;
3. the organic-inorganic hybrid adsorbent with the hierarchical structure realizes the efficient and rapid selective adsorption of the adsorbent on the lead ions in water through the synergistic effect of the components: the adsorption sites of the adsorbent for lead are positioned on the surface, so that the adsorption rate is greatly improved compared with the adsorption sites of the pore channels; the electrostatic effect of sulfonic acid groups on the surface of the skeleton on lead ions can increase the concentration of the lead ions in a water phase near the surface of the adsorbent, so that a concentration gradient from a water phase main body to the water phase on the surface of the adsorbent is generated, the mass transfer of the lead ions is promoted, the capacity of treating low-concentration lead is improved, and the treatment depth of the adsorbent is increased; the amino and hydroxyl of the adhesive can chelate lead ions, and the sulfhydryl of the guiding agent and the lead ions can form strong coordination, so that effective adsorption sites on the surface of the adsorbent are increased, and the adsorption capacity and the processing capacity of the adsorbent to the lead are improved; the scale of the inorganic component reaches sub-10 nm level, so that more Fe-O bonds are exposed on the surface of the inorganic component and become active sites, stronger ion exchange effect and flocculation effect are provided, the specific selective adsorption of the adsorbent to lead is realized, and the selective adsorption is obviously enhanced under the action of sulfonic acid groups, amino groups, hydroxyl groups and sulfydryl on the surface of the adsorbent;
4. the organic-inorganic hybrid adsorbent with the hierarchical structure can meet the practical application of water treatment: the adsorbent takes commercial resin as a framework, is in a spherical shape with a diameter of millimeter on a macroscopic scale, can be very easily separated from treated water, and solves the practical application problem of the powder nano adsorbent.
Example 1
To 0.1L Tris-HCl buffer solution was added 1.0g of macroporous cation exchange resin, 0.2g of (HO)2C6H3CH2CH2NH2HCl, 0.1g of CuSO4·5H2O and 0.25mL of 30% by mass of H2O2Reacting for 40 minutes at room temperature in a dark place, and filtering out solid-phase particles A; adding A to FeSO4Reacting in the solution for 4 hours at room temperature, and filtering out solid-phase particles B; adding the B into PBS buffer solution containing cysteine protease, reacting for 6 hours at room temperature, and preparing to obtain an adsorbent;
wherein the pH of the Tris-HCl buffer solution is 9, and the pH value is FeSO4The solution concentration was 0.2mol/L, the pH of the PBS buffer solution was 7.2, and the concentration of cysteine protease was 1 g/L.
The lead concentration in the lead-containing water body is 200 mg/L;
putting 0.5L of the water containing lead into a beaker, adding 0.5g of adsorbent, stirring for reaction for 6 hours, filtering to separate the adsorbent, and measuring the lead concentration in the treated water to be 10.2mg/L and the lead ion removal rate to be 94.9%;
wherein the reaction temperature is 40 ℃, and the initial pH of the water body is 5.
Example 2
To 0.1L Tris-HCl buffer solution was added 0.5g of macroporous cation exchange resin, 0.3g of (HO)2C6H3CH2CH2NH2HCl, 0.2g of CuSO4·5H2O and 0.4mL of 30% by mass of H2O2Reacting for 30 minutes at room temperature in a dark place, and filtering out solid-phase particles A; adding A to FeCl2Reacting in the solution at room temperature for 2 hours, and filtering out solid-phase particles B; adding the B into a PBS buffer solution containing cysteine protease, reacting for 4 hours at room temperature, and preparing to obtain an adsorbent;
wherein the pH value of the Tris-HCl buffer solution is 8, and the FeCl2The solution concentration was 0.02mol/L, the pH of the PBS buffer solution was 7.6, and the cysteine protease concentration was 5 g/L.
The lead concentration in the lead-containing water body is 1 mg/L;
adding 0.06g of adsorbent into a glass tube with the diameter of 8mm, introducing 0.2L of the lead-containing water from the bottom of the glass tube, allowing the lead-containing water to flow out from the top of the glass tube, performing circulating treatment for 4 hours, and performing centrifugal separation to obtain the adsorbent, wherein the lead concentration in the treated water is 0.09mg/L, and the lead ion removal rate is 91.0%;
wherein the reaction temperature is 20 ℃, and the initial pH of the water body is 7.
Example 3
To 0.1L Tris-HCl buffer solution was added 1.5g of macroporous cation exchange resin, 0.25g of (HO)2C6H3CH2CH2NH2HCl, 0.15g of CuSO4·5H2O and 0.3mL of 30% by mass of H2O2Reacting for 38 minutes at room temperature in a dark place, and filtering out solid-phase particles A; adding A to FeSO4Reacting in the solution at room temperature for 3.5 hours, and filtering out solid-phase particles B; adding B intoReacting in PBS buffer solution with cysteine protease at room temperature for 5 hours to prepare an adsorbent;
wherein the pH of the Tris-HCl buffer solution is 8.6, and the pH value is FeSO4The solution concentration was 0.16mol/L, the pH of the PBS buffer solution was 7.4, and the concentration of cysteine protease was 0.5 g/L.
The lead concentration in the lead-containing water body is 50 mg/L;
putting 0.2L of the water containing lead into a beaker, adding 0.1g of adsorbent, introducing air for aeration for 2 hours, filtering and separating the adsorbent, and measuring the lead concentration in the treated water to be 4.3mg/L and the lead ion removal rate to be 91.4%;
wherein the reaction temperature is 60 ℃, and the initial pH of the water body is 3.
Example 4
To 0.1L Tris-HCl buffer solution was added 0.5g of macroporous cation exchange resin, 0.25g of (HO)2C6H3CH2CH2NH2HCl, 0.15g of CuSO4·5H2O and 0.3mL of 30% by mass of H2O2Reacting for 40 minutes at room temperature in a dark place, and filtering out solid-phase particles A; adding A to FeSO4Reacting in the solution for 4 hours at room temperature, and filtering out solid-phase particles B; adding the B into PBS buffer solution containing cysteine protease, reacting for 6 hours at room temperature, and preparing to obtain an adsorbent;
wherein the pH of the Tris-HCl buffer solution is 8.8, and the pH value is FeSO4The solution concentration was 0.16mol/L, the pH of the PBS buffer solution was 7.6, and the cysteine protease concentration was 3 g/L.
The lead concentration in the lead-containing water body is 100 mg/L;
putting 0.5L of the water containing lead into a beaker, adding 0.25g of adsorbent, stirring for reaction for 6 hours, filtering to separate the adsorbent, and measuring the lead concentration in the treated water to be 2.2mg/L and the lead ion removal rate to be 97.8%;
wherein the reaction temperature is 25 ℃, and the initial pH of the water body is 6.
The lead concentration in the lead-containing water body is 100mg/L, the sodium ion concentration is 711mg/L, and the sodium ion concentration is 64 times (molar ratio) of the lead ion concentration;
putting 0.5L of the water containing lead into a beaker, adding 0.25g of adsorbent, stirring for reaction for 6 hours, and filtering to separate the adsorbent, wherein the lead concentration in the treated water is measured to be 7.1mg/L, the lead ion removal rate is 92.9 percent, and the lead ion removal rate is 95 percent of that in the case of not containing sodium ions under the same conditions;
wherein the reaction temperature is 25 ℃, and the initial pH of the water body is 6.
The lead concentration in the lead-containing water body is 100mg/L, the sodium ion concentration is 356mg/L, and the sodium ion concentration is 32 times (molar ratio) of the lead ion concentration;
putting 0.5L of the water containing lead into a beaker, adding 0.25g of adsorbent, stirring for reaction for 6 hours, and filtering to separate the adsorbent, wherein the lead concentration in the treated water is measured to be 5.8mg/L, the lead ion removal rate is 94.2%, and the lead ion removal rate is 96.3% of that when the water does not contain sodium ions under the same conditions;
wherein the reaction temperature is 25 ℃, and the initial pH of the water body is 6.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

  1. The preparation method of kinds of organic-inorganic hybrid adsorbents with hierarchical structures is characterized by comprising the following steps:
    (1) adding ion exchange resin, dopamine, copper sulfate and hydrogen peroxide into a Tris-HCl buffer solution, carrying out a dark reaction at room temperature for 30-40 minutes, and separating the ion exchange resin with the adhesive polydopamine on the surface;
    (2) adding ion exchange resin with adhesive polydopamine on the surface into a ferrous salt solution, reacting for 2-4 hours at room temperature, and separating out the ion exchange resin with iron;
    (3) adding thiol protease and ion exchange resin with iron into PBS buffer solution, reacting for 4-6 hours at room temperature, separating solid material, and naturally drying to obtain the organic-inorganic hybrid adsorbent with a hierarchical structure.
  2. 2. The method for preparing an organic-inorganic hybrid adsorbent having a hierarchical structure according to claim 1, wherein the pH of the Tris-HCl buffer solution in the step (1) is 8.0-9.0.
  3. 3. The method for preparing the organic-inorganic hybrid adsorbent with hierarchical structure according to claim 1, wherein the amounts of the ion exchange resin, dopamine, copper sulfate and hydrogen peroxide in step (1) are as follows: adding 5-15 g of ion exchange resin and 2-3 g of (HO) into 1L of Tris-HCl buffer solution2C6H3CH2CH2NH2·HCl、1～2g CuSO4·5H2O, 2.5-4.0 mL of 30% by mass of H2O2And (3) solution.
  4. 4. The method for preparing an organic-inorganic hybrid adsorbent having a hierarchical structure according to claim 1, wherein the ion exchange resin in the step (1) is a macroporous cation exchange resin.
  5. 5. The method for preparing the organic-inorganic hybrid adsorbent with the hierarchical structure according to claim 1, wherein the concentration of Fe in the ferrous salt solution in the step (2) is 0.02-0.2 mol/L.
  6. 6. The method for preparing an organic-inorganic hybrid adsorbent with a hierarchical structure according to claim 1, wherein the ferrous salt in the step (2) is any kinds of ferrous sulfate or ferrous chloride.
  7. 7. The method for preparing the organic-inorganic hybrid adsorbent with the hierarchical structure according to claim 1, wherein the concentration of the thiol protease in the PBS buffer solution of step (3) is 0.5-5 g/L, and the pH of the solution is 7.2-7.6.
  8. 8. The method for preparing an organic-inorganic hybrid adsorbent having a hierarchical structure according to claim 1, wherein the thiol protease in the step (3) is cysteine protease.
  9. 9, kinds of organic-inorganic hybrid adsorbents with hierarchical structures, which are characterized by being prepared by the preparation method of any of claims 1-8.
  10. 10. The organic-inorganic hybrid adsorbent having a hierarchical structure according to claim 9 is used for removing heavy metal pollution in a water body.
CN201811092532.7A 2018-09-19 2018-09-19 Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof Active CN109046292B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811092532.7A CN109046292B (en) 2018-09-19 2018-09-19 Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811092532.7A CN109046292B (en) 2018-09-19 2018-09-19 Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109046292A CN109046292A (en) 2018-12-21
CN109046292B true CN109046292B (en) 2020-01-31

Family

ID=64762945

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811092532.7A Active CN109046292B (en) 2018-09-19 2018-09-19 Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109046292B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112892486A (en) * 2021-01-19 2021-06-04 西南科技大学 Preparation method of inorganic heavy metal waste liquid adsorption material, adsorption material and application
CN113680331A (en) * 2021-08-27 2021-11-23 燕山大学 Sub-10 nm zirconium oxide coating composite resin for efficiently removing complex copper and preparation method and application thereof
CN114452980B (en) * 2021-12-30 2023-04-11 浙江微通催化新材料有限公司 Preparation method of platinum-supported Ni/Mg/Fe hydrotalcite catalyst and application of catalyst in preparation of aniline

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105478074A (en) * 2015-12-23 2016-04-13 中国科学院烟台海岸带研究所 Preparation method and application of heavy metal ion remover
CN105642256B (en) * 2016-01-29 2017-12-26 江苏科技大学 A kind of hydrophobic resin oiliness sorbing material and preparation method
CN105771933A (en) * 2016-04-28 2016-07-20 深圳大学 Heavy metal absorbing material for water, method for preparing heavy metal absorbing material and application thereof
CN106832163A (en) * 2017-01-25 2017-06-13 河北大学 A kind of preparation method of hydrophilic molecules trace entirety resin
CN107096513B (en) * 2017-05-05 2019-09-10 燕山大学 A kind of method that resin base cupric phosphate nano flower profile depth removes heavy metal in water removal
CN107486254A (en) * 2017-08-24 2017-12-19 江苏亚峰科技集团有限公司 A kind of sewage disposal spent ion exchange resin
CN107282023B (en) * 2017-08-25 2020-05-19 益阳医学高等专科学校 Nano adsorbent for chemical waste liquid treatment and preparation method thereof

Also Published As

Publication number Publication date
CN109046292A (en) 2018-12-21

Similar Documents

Publication Publication Date Title
Brião et al. Removal of toxic metals from water using chitosan-based magnetic adsorbents. A review
Choudhary et al. Surface functionalized biomass for adsorption and recovery of gold from electronic scrap and refinery wastewater
Liu et al. Fast and robust lead (II) removal from water by bioinspired amyloid lysozyme fibrils conjugated with polyethyleneimine (PEI)
Liu et al. Modification of calcium-rich biochar by loading Si/Mn binary oxide after NaOH activation and its adsorption mechanisms for removal of Cu (II) from aqueous solution
Liu et al. Improved Pb (II) removal in aqueous solution by sulfide@ biochar and polysaccharose-FeS@ biochar composites: efficiencies and mechanisms
Yu et al. Enhanced and selective adsorption of Pb2+ and Cu2+ by EDTAD-modified biomass of baker’s yeast
CN109046292B (en) Organic-inorganic hybrid adsorbent with hierarchical structure and preparation method and application thereof
Tian et al. Enhanced elimination of Cr (VI) from aqueous media by polyethyleneimine modified corn straw biochar supported sulfide nanoscale zero valent iron: Performance and mechanism
Zhang et al. Preparation of chitosan/lignosulfonate for effectively removing Pb (II) in water
WO2017088216A1 (en) Magnetic solid polyamine adsorbent particle material, preparation method and application thereof
WO2016124047A1 (en) Granular material of magnetic solid-organosulfur adsorbent containing organosulfur adsorption group and preparation method thereof
Cai et al. Advanced treatment of piggery tail water by dual coagulation with Na+ zeolite and Mg/Fe chloride and resource utilization of the coagulation sludge for efficient decontamination of Cd2+
CN112316906B (en) Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of ferromagnetic amino-modified lanthanide metal organic framework material in adsorption dephosphorization
CN105664884A (en) Magnetic adsorbent for removing heavy metal in water and method for preparing magnetic adsorbent
Saikia et al. Adsorptive removal of gallium from aqueous solution onto biogenic elemental tellurium nanoparticles
Li et al. Potentiality of phosphorus− accumulating organisms biomasses in biosorption of Cd (II), Pb (II), Cu (II) and Zn (II) from aqueous solutions: Behaviors and mechanisms
Liu et al. Fabrication of novel magnetic core-shell chelating adsorbent for rapid and highly efficient adsorption of heavy metal ions from aqueous solution
CN108059301B (en) Method for recovering heavy metals in heavy metal sewage by using activated sludge
Pfeifer et al. A review: a comparison of different adsorbents for removal of Cr (VI), Cd (II) and Ni (II)
CN110801814A (en) Preparation method of magnetic amino walnut shell biochar novel adsorbent
CN104826600A (en) Preparation method of magnetic kaolin
CN114425305B (en) Mercury adsorption material, preparation method thereof and application thereof in flue gas or solution mercury removal
CN101386438B (en) Method for processing heavy metal ion in water using amidocyanogen modified Fe3O4@SiO2 composite microparticle
Onyancha et al. Influence of magnetism-mediated potentialities of recyclable adsorbents for heavy metal ions removal from aqueous solutions–an organized review
CN114515567B (en) Biological magnetic nanocomposite material, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant