CN113042014B - Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof - Google Patents

Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof Download PDF

Info

Publication number
CN113042014B
CN113042014B CN202110341095.3A CN202110341095A CN113042014B CN 113042014 B CN113042014 B CN 113042014B CN 202110341095 A CN202110341095 A CN 202110341095A CN 113042014 B CN113042014 B CN 113042014B
Authority
CN
China
Prior art keywords
graphene oxide
modified graphene
oxide composite
heavy metal
composite aerogel
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
CN202110341095.3A
Other languages
Chinese (zh)
Other versions
CN113042014A (en
Inventor
吕生华
吴磊
李泽雄
刘雷鹏
刘相
高党国
左鹏军
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202110341095.3A priority Critical patent/CN113042014B/en
Publication of CN113042014A publication Critical patent/CN113042014A/en
Application granted granted Critical
Publication of CN113042014B publication Critical patent/CN113042014B/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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • 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
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • 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
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to a modified graphene oxide composite aerogel type heavy metal ion adsorbent and a preparation method and application thereof. The aerogel type adsorbent prepared by the invention has a stable structure, good strength and water-resistant stability, can be repeatedly used for a plurality of times, and has a regeneration time of more than 50 times. Has the advantages of high adsorption rate, high adsorption capacity, convenient recycling and environmental protection in the aspect of adsorption performance.

Description

Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof
Technical Field
The invention relates to a modified graphene oxide composite aerogel type heavy metal ion adsorbent, and a preparation method and application thereof, and belongs to the field of functional materials.
Background
The waste water polluted by heavy metal ions mainly refers to waste water containing toxic heavy metal ions such as chromium, nickel, copper, zinc, mercury, manganese, cadmium, vanadium, lead, tin and the like. The sources of the wastewater containing the heavy metal ions are wide, and a large amount of wastewater containing the heavy metal ions is generated in the production process of industries such as metal mines, nonferrous smelting, electronic industry, mechanical industry, chemical industry, garbage incineration, leather making and the like. The waste water containing heavy metal ions which does not meet the standard is not treated or is discharged in large quantity, so that the waste water containing heavy metal ions is harmful to human bodies and ecological environment, and according to data statistics, the annual discharge amount of the waste water containing heavy metal ions in China is over 50 hundred million tons.
The treatment method of the wastewater containing the heavy metal ions comprises a chemical precipitation method, an electrolysis method, a chemical method, an ion exchange method, an adsorption method and the like, and the treatment method of the wastewater containing the heavy metal ions not only meets the discharge requirements of the state and related departments, but also considers the economy, the applicability and the simple and convenient treatment process. For example, the chemical precipitation method is a method which is proved and commonly used at home and abroad, but in practical application, a certain amount of alkaline agent is added according to the type, concentration and the like of heavy metal ions in wastewater to increase the pH value, so that various metal ions and hydroxyl (OH-) react to generate metal hydroxide for co-precipitation. When the waste water contains various metal ions, different pH values are controlled according to specific conditions. The problems that easily occur are: at a certain pH value, a heavy metal ion forms a precipitate, and a heavy metal ion which forms the precipitate is dissolved reversely. The precipitation method has simple process flow and convenient operation, but is suitable for waste water with larger metal ion content. The wastewater after precipitation treatment can only be discharged up to the standard, the treatment effect is not satisfactory, the wastewater cannot adapt to increasingly strict environmental regulations, the water reuse is difficult to realize, precipitates are easy to form secondary pollution, a chemical method is easy to cause secondary pollution, and an electrolysis method and an ion exchange method are low in efficiency and high in energy consumption.
At present, the adsorption method is considered to be the most extensive method for removing pollutants due to its advantages of low cost, simple operation, high removal rate, reusability, and the like. Activated carbon, mineral zeolites, bio-based materials, polymer-based composite materials, carbon-based materials, and the like have been widely used in the research of adsorbents. Among the adsorbents, particularly, the graphene oxide nanosheet layer is used as a novel carbon material, the surface of the graphene oxide nanosheet layer is rich in oxygen-containing functional groups such as carboxyl, hydroxyl and epoxy groups, and the graphene oxide nanosheet layer has the advantages of high specific surface area, good chemical stability, environmental friendliness and the like, and is an effective adsorbent for removing water body pollution. Although the graphene oxide single-sheet layer has excellent adsorption performance, because the sheet layer size is small and the aggregation and condensation phenomenon is easy to occur between the sheet layers, the single-sheet layer and few-sheet layer dispersion state required by optimal adsorption is difficult to form, in order to overcome the defects of the graphene oxide in the adsorption aspect, the common method can assemble the graphene oxide nano-sheet layer in the form of the single-sheet layer or few-sheet layer to form the graphene oxide aerogel with certain strength and a three-dimensional structure, so that the graphene oxide aerogel has volume stability, and can be conveniently recycled, regenerated and reutilized after re-adsorption, thereby solving the application problem of the two-dimensional graphene oxide nano-sheet layer as an adsorption material, and the three-dimensional porous structure has high porosity and specific surface area, and can improve the contact area and acting force between the graphene oxide nano-sheet layer and metal ions, improving the ability of adsorbing ions.
Disclosure of Invention
The invention aims to provide a modified graphene oxide composite aerogel type heavy metal ion adsorbent and a preparation method and application thereof. The prepared aerogel adsorbent has the characteristics of stable structure, high specific surface area, high porosity, high adsorbability and the like, and the prepared modified graphene composite aerogel type heavy metal ion adsorbent has the performances of high adsorption rate, high adsorption capacity and convenience in recycling. The density of the aerogel is 0.05-0.07 g/cm 3 The specific surface area is 345m 2 /g~370 m 2 Per g, for daughter Pb 2+ 、Cd 2+ 、Cr 3+ 、Cu 2+ And the adsorption removal rate of the metal ions is more than 99.5 percent. Meanwhile, the preparation process and the process route are scientific and reasonable, the process operation is simple, the catalyst can be regenerated and repeatedly utilized, and the catalyst has the advantages of high-efficiency adsorption on metal ions and the like.
In order to achieve the above purpose, the invention provides a preparation method of a modified graphene oxide composite aerogel type heavy metal ion adsorbent, which comprises the following steps:
step one, preparation of modified graphene oxide composite hydrosol
Adding 4-6 parts of octa-armed polyethylene glycol acrylate and 6-8 parts of polyether macromonomer into 390-420 parts of graphene oxide dispersion liquid, uniformly stirring, heating to 70-85 ℃, adding a mixed solution of 18-22 parts of acrylic acid, 5-7 parts of cationic monomer, 0.5-1 part of ammonium persulfate and 50-80 parts of water in a dropping manner for 1.5-2 hours, and carrying out heat preservation reaction for 2-3 hours after the addition is finished to obtain the modified graphene oxide intercalation composite hydrosol.
Step two, preparation of modified graphene oxide composite hydrogel
Maintaining the temperature of the modified graphene oxide intercalation composite hydrosol prepared in the first step at 60-70 ℃, sequentially adding 6-8 parts of eight-arm polyethylene glycol carboxyl and 5-7 parts of polyether amine while stirring, continuously stirring to form a uniform graphene oxide hydrosol after the addition is finished, stopping stirring, heating to 90-95 ℃, keeping the temperature for 3-4 hours, and cooling to obtain the modified graphene oxide composite hydrogel.
Step three, preparing the modified graphene oxide composite aerogel
And D, freezing the modified graphene oxide composite hydrogel obtained in the step two, and freeze-drying for 24-26 hours to obtain the modified graphene oxide composite aerogel.
Step four, preparing the modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparing the same
And (3) soaking the modified graphene oxide composite aerogel obtained in the third step in a graphene oxide lamellar mixed solution for 30-40 minutes, draining, keeping at 150-180 ℃ for 2-3 hours, performing high-temperature activation treatment, and cooling to obtain the modified graphene oxide composite aerogel type heavy metal ion adsorbent.
The graphene oxide dispersion liquid is an aqueous graphene oxide nanosheet layer dispersion liquid prepared by an improved Hummers method, wherein the content of graphene oxide is 0.05%, the diameter size of a graphene oxide nanosheet layer in the dispersion liquid is 150-530 nm, the thickness of the graphene oxide nanosheet layer is 1.3-3.5 nm, the pH value of the dispersion liquid is 4-6, the oxygen content of graphene oxide is 39.6-43.7%, the epoxy group content is 28.5-32.6%, the carboxyl group content is 38.3-42.4%, and the hydroxyl group content is 25.2-29.1%.
The average annual molecular weight of the eight-arm polyethylene glycol acrylate is 10000, and the purity is more than 95%.
The polyether macromonomer is one of allyl alcohol polyoxyethylene ether, methyl allyl alcohol polyoxyethylene ether and isoamyl alcohol polyoxyethylene ether, the purity is more than 99%, the molecular weight is 2100-2600, the water content is 1%, the hydroxyl value is 21-22 mgKOH/g, the unsaturation degree is 0.3-0.35 mol/kg, and the pH value of a 1% aqueous solution is 5.0-7.0.
The acrylic acid purity was 99%.
The cationic monomer is one or a mixture of more of acryloyloxyethyl dimethyl benzyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, N-dimethylaminoethyl methacrylate and dimethyl diallyl ammonium chloride, and the purity is 99%.
The eight-arm polyethylene glycol carboxyl is white viscous liquid, the relative molecular mass is 550-1000, and the purity is more than 98%.
The polyether amine is colorless or light yellow liquid in appearance, the purity is more than 99%, the relative molecular weight is 1300-2000, the density is 0.997g/mL, the amine value is 220-273 mg KOH/g, and the viscosity is 15-30 mPa.s.
The temperature of the freeze drying is-50 to-58 ℃, and the vacuum degree is less than 50 Pa.
The modified graphene oxide composite aerogel type heavy metal ion adsorbent is prepared by the preparation method.
The modified graphene oxide composite aerogel type heavy metal ion adsorbent prepared by the preparation method is used for adsorbing metal ions Pb in industrial wastewater 2+ 、Cd 2+ 、Cr 3+ 、Cu 2+ 。
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the modified graphene oxide composite aerogel type heavy metal ion adsorbent is prepared by selecting the graphene oxide nanosheet layer, the eight-arm polyethylene glycol acrylate, the polyether macromonomer, the acrylic acid, the cationic monomer, the eight-arm polyethylene glycol carboxyl group and the polyether amine as main materials through copolymerization, crosslinking and heat treatment, and the structure of the modified graphene oxide composite aerogel type heavy metal ion adsorbent is rich in carboxyl, amino, hydroxyl, a ring structure and the like, and has strong adsorption capacity on heavy metal ions.
(2) Monomer eight-arm polyethylene glycol acrylate with multiple functionality and cross-linking agent eight-arm polyethylene glycol carboxyl are selected to form a net structure, so that the structural stability and strength of the aerogel are improved, the porosity of the aerogel is high, the specific surface area is large, and the density of the aerogel is 0.05-0.07 g/cm 3 Specific surface area of 345m 2 /g~370 m 2 Per g, for daughter Pb 2+ 、Cd 2+ 、Cr 3 + 、Cu 2+ And the adsorption removal rate of the metal ions is more than 99.5 percent. Has the advantages of high adsorption rate, high adsorption capacity, convenient recycling and environmental protection in the aspect of adsorption performance.
(3) The preparation process is scientific and reasonable, the preparation method is simple, and the obtained aerogel has good practicability.
Drawings
FIG. 1 is an SEM image of a modified graphene oxide composite aerogel type heavy metal ion adsorbent
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Step one, preparing a modified graphene oxide composite hydrosol: adding 4 parts of eight-arm polyethylene glycol acrylate and 6 parts of polyether macromonomer into 390 parts of graphene oxide dispersion liquid, uniformly stirring, heating to 70 ℃, adding a mixed solution of 18 parts of acrylic acid, 5 parts of cationic monomer, 0.5 part of ammonium persulfate and 50 parts of water in a dropping manner, wherein the dropping time is 1.5 hours, and carrying out heat preservation reaction for 2 hours after the addition is finished to obtain the modified graphene oxide intercalation composite hydrosol.
Step two, preparing the modified graphene oxide composite hydrogel: and (3) maintaining the modified graphene oxide intercalation composite hydrosol prepared in the first step at 60 ℃, sequentially adding 6-eight-arm polyethylene glycol carboxyl and 5 parts of polyether amine while stirring, continuously stirring to form uniform graphene oxide hydrosol after adding, stopping stirring, heating to 90 ℃, preserving heat for 3 hours, and cooling to obtain the modified graphene oxide composite hydrogel.
Step three, preparing the modified graphene oxide composite aerogel: and D, freezing the modified graphene oxide composite hydrogel obtained in the step two, and freeze-drying for 24 hours to obtain the modified graphene oxide composite aerogel.
Step four, preparing the modified graphene oxide composite aerogel type heavy metal ion adsorbent: and (3) soaking the modified graphene oxide composite aerogel obtained in the third step in the graphene oxide lamellar mixed solution for 30 minutes, draining, keeping at 150 ℃ for 2 hours, performing high-temperature activation treatment, and cooling to obtain the modified graphene oxide composite aerogel type heavy metal ion adsorbent.
Example 2
Step one, preparing a modified graphene oxide composite hydrosol: adding 6 parts of eight-arm polyethylene glycol acrylate and 8 parts of polyether macromonomer into 420 parts of graphene oxide dispersion liquid, uniformly stirring, heating to 85 ℃, adding a mixed solution of 22 parts of acrylic acid, 7 parts of cationic monomer, 1 part of ammonium persulfate and 80 parts of water in a dropping manner, wherein the dropping time is 2 hours, and carrying out heat preservation reaction for 3 hours after the addition is finished to obtain the modified graphene oxide intercalation composite hydrosol.
Step two, preparing the modified graphene oxide composite hydrogel: and (3) maintaining the modified graphene oxide intercalation composite hydrosol prepared in the first step at 70 ℃, sequentially adding 8 parts of eight-arm polyethylene glycol carboxyl and 7 parts of polyether amine while stirring, continuously stirring to form uniform graphene oxide hydrosol after the addition is finished, stopping stirring, heating to 95 ℃, keeping the temperature for 4 hours, and cooling to obtain the modified graphene oxide composite hydrogel.
Step three, preparing the modified graphene oxide composite aerogel: and D, freezing the modified graphene oxide composite hydrogel obtained in the step two, and freeze-drying for 26 hours to obtain the modified graphene oxide composite aerogel.
Step four, preparing the modified graphene oxide composite aerogel type heavy metal ion adsorbent: and (3) soaking the modified graphene oxide composite aerogel obtained in the third step in the graphene oxide lamellar mixed solution for 40 minutes, draining, keeping at 180 ℃ for 3 hours for high-temperature activation treatment, and cooling to obtain the modified graphene oxide composite aerogel type heavy metal ion adsorbent.
Example 3
Step one, preparing a modified graphene oxide composite hydrosol: adding 6 parts of eight-arm polyethylene glycol acrylate and 8 parts of polyether macromonomer into 390 parts of graphene oxide dispersion liquid, uniformly stirring, heating to 85 ℃, adding a mixed solution of 18 parts of acrylic acid, 5 parts of cationic monomer, 0.5 part of ammonium persulfate and 50 parts of water in a dropping manner, wherein the dropping time is 1.5 hours, and carrying out heat preservation reaction for 2 hours after the addition is finished to obtain the modified graphene oxide intercalation composite hydrosol.
Step two, preparing the modified graphene oxide composite hydrogel: and (3) maintaining the modified graphene oxide intercalation composite hydrosol prepared in the first step at 60 ℃, sequentially adding 6 parts of eight-arm polyethylene glycol carboxyl and 5 parts of polyether amine while stirring, continuously stirring to form uniform graphene oxide hydrosol after the addition is finished, stopping stirring, heating to 90 ℃, preserving heat for 3 hours, and cooling to obtain the modified graphene oxide composite hydrogel.
Step three, preparing the modified graphene oxide composite aerogel: and D, freezing the modified graphene oxide composite hydrogel obtained in the step two, and freeze-drying for 24 hours to obtain the modified graphene oxide composite aerogel.
Step four, preparing the modified graphene oxide composite aerogel type heavy metal ion adsorbent: and (3) soaking the modified graphene oxide composite aerogel obtained in the third step in the graphene oxide lamellar mixed solution for 30 minutes, draining, keeping at 150 ℃ for 2 hours, performing high-temperature activation treatment, and cooling to obtain the modified graphene oxide composite aerogel type heavy metal ion adsorbent.
Comparative example
Chinese invention patent CN106140114B discloses a modified graphene oxide composite aerogel type heavy metal ion adsorbent and a preparation method thereof, and the adsorption capacity of the products of examples 1-3 to metal ions is shown in Table 1.
Research examples 1-3 respectively research the metal ions Cd 2+ 、Pb 2+ 、Cr 3+ 、Cu 2+ The adsorption performance of (3). Respectively weighing the 20mg composite aerogel, respectively placing the 20mg composite aerogel into a 250mL conical flask, and sequentially adding 50mL Pb with the concentration of 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L and 70mg/L into the conical flask 2+ 、Cd 2+ 、Cr 3+ 、Cu 2+ And (3) solution. Placing the conical flask in a 30 ℃ constant temperature shaking table for full adsorption for 12h, measuring the concentration after adsorption by adopting an atomic absorption method, and calculating to obtain the composite aerogel for different initial concentrations of metal Cd 2+ 、Pb 2+ 、Cr 3+ 、Cu 2+ The maximum adsorption amount and adsorption performance of (2) are shown in Table 1.
TABLE 1 adsorption Properties of the products prepared
Figure 903668DEST_PATH_IMAGE002
As can be seen from the data of the test junctions in table 1: comparing the comparative example and the example, it can be seen that the adsorption amount of the heavy metal ions in the example is significantly improved.
The invention is not limited to the embodiments, and any equivalent changes of the technical solutions of the invention by those skilled in the art through reading the description of the invention are covered by the claims of the invention.

Claims (6)

1. A preparation method of a modified graphene oxide composite aerogel type heavy metal ion adsorbent is characterized by comprising the following steps:
the method comprises the following steps:
step one, preparing a modified graphene oxide composite hydrosol:
adding 4-6 parts of octa-armed polyethylene glycol acrylate and 6-8 parts of polyether macromonomer into 390-420 parts of graphene oxide dispersion liquid, uniformly stirring, heating to 70-85 ℃, adding a mixed solution of 18-22 parts of acrylic acid, 5-7 parts of cationic monomer, 0.5-1 part of ammonium persulfate and 50-80 parts of water in a dropping manner for 1.5-2 hours, and carrying out heat preservation reaction for 2-3 hours after the addition is finished to obtain a modified graphene oxide intercalation composite hydrosol;
step two, preparing the modified graphene oxide composite hydrogel:
maintaining the temperature of the modified graphene oxide intercalation composite hydrosol prepared in the first step at 60-70 ℃, sequentially adding 6-8 parts of eight-arm polyethylene glycol carboxyl and 5-7 parts of polyether amine while stirring, continuously stirring to form a uniform graphene oxide hydrosol after the addition is finished, stopping stirring, heating to 90-95 ℃, preserving heat for 3-4 hours, and cooling to obtain a modified graphene oxide composite hydrogel;
step three, preparing the modified graphene oxide composite aerogel:
freezing the modified graphene oxide composite hydrogel obtained in the step two, and carrying out freeze drying for 24-26 hours to obtain modified graphene oxide composite aerogel;
step four, preparing a modified graphene oxide composite aerogel type heavy metal ion adsorbent:
dipping the modified graphene oxide composite aerogel obtained in the third step in a graphene oxide lamellar mixed solution for 30-40 minutes, draining, keeping at 150-180 ℃ for 2-3 hours, performing high-temperature activation treatment, and cooling to obtain a modified graphene oxide composite aerogel type heavy metal ion adsorbent;
in the first step, the graphene oxide dispersion liquid is an aqueous dispersion liquid of graphene oxide nanosheet layers prepared by an improved Hummers method, wherein the mass fraction of graphene oxide is 0.05%, the diameter size of the graphene oxide nanosheet layers in the dispersion liquid is 150 nm-530 nm, the thickness of the graphene oxide nanosheet layers is 1.3-3.5 nm, the pH value of the dispersion liquid is 4-6, the oxygen content of graphene oxide is 39.6% -43.7%, the epoxy group content is 28.5-32.6%, the carboxyl group content is 38.3-42.4%, and the hydroxyl group content is 25.2-29.1%;
the average molecular weight of the eight-arm polyethylene glycol acrylate is 10000, and the purity is more than 95%;
the polyether macromonomer is one of allyl alcohol polyoxyethylene ether, methyl allyl alcohol polyoxyethylene ether and isoamylene alcohol polyoxyethylene ether, the purity is more than 99%, the molecular weight is 2100-2600, the moisture content is 1%, the hydroxyl value is 21-22 mgKOH/g, the unsaturation degree is 0.3-0.35 mol/kg, and the pH value of a 1% aqueous solution is 5.0-7.0;
in the first step, the cationic monomer is one or a mixture of more of acryloyloxyethyl dimethyl benzyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, N-dimethylaminoethyl methacrylate and dimethyl diallyl ammonium chloride, and the purity is 99%.
2. The preparation method of the modified graphene oxide composite aerogel type heavy metal ion adsorbent according to claim 1, characterized in that:
in the second step, the eight-arm polyethylene glycol carboxyl is white viscous liquid, the relative molecular mass is 550-1000, and the purity is more than 98%.
3. The preparation method of the modified graphene oxide composite aerogel type heavy metal ion adsorbent according to claim 1, characterized in that:
in the second step, the polyether amine is colorless to light yellow liquid, the purity is higher than 99%, the relative molecular weight is 1300-2000, the density is 0.997g/mL, the amine value is 220-273 mg KOH/g, and the viscosity is 15-30 mPa.s.
4. The preparation method of the modified graphene oxide composite aerogel type heavy metal ion adsorbent according to claim 1, characterized in that:
in the third step, the temperature of the freeze drying is-50 to-58 ℃, and the vacuum degree is less than 50 Pa.
5. The modified graphene oxide composite aerogel type heavy metal ion adsorbent prepared according to the preparation method of claim 1.
6. The modified graphene oxide composite aerogel type heavy metal ion adsorbent prepared by the preparation method according to claim 1 is used for adsorbing metal ions Pb in industrial wastewater 2+ 、Cd 2+ 、Cr 3+ 、Cu 2+ The use of (1).
CN202110341095.3A 2021-03-30 2021-03-30 Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof Active CN113042014B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110341095.3A CN113042014B (en) 2021-03-30 2021-03-30 Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110341095.3A CN113042014B (en) 2021-03-30 2021-03-30 Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113042014A CN113042014A (en) 2021-06-29
CN113042014B true CN113042014B (en) 2022-08-12

Family

ID=76516906

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110341095.3A Active CN113042014B (en) 2021-03-30 2021-03-30 Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113042014B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910568A (en) * 2015-01-28 2015-09-16 云南中烟工业有限责任公司 Graphene-polymer composite aerogel filter perfume rod and preparation method thereof
WO2018076462A1 (en) * 2016-10-26 2018-05-03 苏州蓝锐纳米科技有限公司 Preparation method for reduced graphene oxide/aspergillus niger cellulose aerogel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9725601B2 (en) * 2011-04-04 2017-08-08 Carnegie Mellon University Carbon nanotube aerogels, composites including the same, and devices formed therefrom
CN104707579B (en) * 2015-01-10 2016-04-20 济南大学 A kind of preparations and applicatio of the hyperbranched polyetheramine grafting GO adsorbent for heavy metal and Dye Adsorption
CN104558998B (en) * 2015-01-28 2016-08-17 云南中烟工业有限责任公司 A kind of filter tip efficient absorption rod of graphene-polymer composite aerogel and preparation method thereof
CN105601850A (en) * 2015-12-24 2016-05-25 吉首大学 Preparation method of graphene oxide composite gel applicable to heavy metal adsorption
CN107570121B (en) * 2017-09-26 2021-01-08 盐城工学院 Amphoteric polysaccharide/cross-linked graphene oxide double-network composite hydrogel adsorption material and preparation method thereof
CN107913674B (en) * 2017-10-27 2020-08-04 苏州大学 MOF-loaded 3D ruthenium/graphene aerogel composite material, preparation method thereof and application thereof in continuous CO treatment
CN108940140B (en) * 2018-07-20 2020-06-30 北京欧美中科学技术研究院 Method for preparing graphene carbon aerogel composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910568A (en) * 2015-01-28 2015-09-16 云南中烟工业有限责任公司 Graphene-polymer composite aerogel filter perfume rod and preparation method thereof
WO2018076462A1 (en) * 2016-10-26 2018-05-03 苏州蓝锐纳米科技有限公司 Preparation method for reduced graphene oxide/aspergillus niger cellulose aerogel

Also Published As

Publication number Publication date
CN113042014A (en) 2021-06-29

Similar Documents

Publication Publication Date Title
Allahkarami et al. Removal of cerium from different aqueous solutions using different adsorbents: A review
CN109942874B (en) Composite sponge for heavy metal sewage treatment and preparation method thereof
CN112791714B (en) Magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, preparation method and application
CN108246269B (en) Lithium ion adsorbent and preparation method and application thereof
CN110898802B (en) Sludge-based biochar and preparation method and application thereof, acetic acid modified sludge-based biochar and preparation method and application thereof
CN113083238A (en) Thiosemicarbazide functionalized graphene oxide/chitosan composite adsorbent and preparation method and application thereof
CN112473630A (en) Composite graphene chitosan aerogel and preparation method and application thereof
CN113042014B (en) Modified graphene oxide composite aerogel type heavy metal ion adsorbent and preparation method and application thereof
CN111514861B (en) Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN114213140A (en) Coal gangue-based ceramsite for phosphorus adsorption, preparation method thereof and water treatment equipment
Wang et al. Biosorption of Sr (II) from aqueous solutions using aerobic granules: equilibrium and mechanisms
CN107175069B (en) Modified diatomite water purifying agent and preparation method thereof
CN114146694B (en) Preparation method, product and application of sodium alginate/polyvinyl alcohol/polyacrylamide/kaolin adsorption material
CN116037074A (en) Sewage treatment agent for heavy metal treatment and preparation method thereof
Klimiuk et al. The effect of poly (vinyl alcohol) on cadmium adsorption and desorption from alginate adsorbents
CN106279548B (en) A kind of polyvinyl alcohol hydrogel and preparation method thereof for handling heavy metal ion-containing waste water
CN100525887C (en) Reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and production method thereof
Wang et al. Synchronously construction of hierarchical porous channels and cationic surface charge on lanthanum-hydrogel for rapid phosphorus removal
CN114539562A (en) Green synthesis method of antibacterial super-large porous hydrogel, product thereof and application of antibacterial super-large porous hydrogel in degradation of various pollutants in wastewater treatment
CN110734127A (en) carbon composite nano zero-valent metal porous functional material, preparation method and application thereof
CN105399906A (en) Humidifying adsorption composite porous chelate resin
CN114832773B (en) Composite hollow carbon sphere ion adsorption material and preparation method and application thereof
CN110787780A (en) Regeneration method of composite adsorbent for adsorbing cations
CN114653338B (en) Simultaneously removing CS in natural gas 2 Nitrogen-doped metal ion loaded adsorbent with Hg and preparation method thereof
CN114768768A (en) Renewable desulfurizer

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