CN112569905A - Chitosan grafted triethylene tetramine dithiocarbamate adsorbing material - Google Patents
Chitosan grafted triethylene tetramine dithiocarbamate adsorbing material Download PDFInfo
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- CN112569905A CN112569905A CN202011219537.9A CN202011219537A CN112569905A CN 112569905 A CN112569905 A CN 112569905A CN 202011219537 A CN202011219537 A CN 202011219537A CN 112569905 A CN112569905 A CN 112569905A
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- triethylene tetramine
- heavy metal
- dithiocarbamate
- chitosan
- ions
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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The development of science and technology brings great convenience and a great deal of economic benefits to people and promotes the development of human social civilization and economy; meanwhile, the pollution problem is brought to people and natural environment. Among them, heavy metal pollution is considered as an important factor to human health and ecological environment due to its biotoxicity and irreversibility. Heavy metals and compounds thereof have very stable chemical properties, are extremely difficult to degrade in natural environment, have enrichment property and are easy to form large-area heavy metal pollution. The application discloses a high-molecular functional material capable of adsorbing heavy metal ions in wastewater is synthesized by using biomass chitosan and triethylene tetramine. The preparation process of the adsorbing material is as follows: firstly, taking 1% acetic acid solution as a solvent, reacting chitosan with glutaraldehyde 1:1 to obtain an intermediate product, reacting with triethylene tetramine to obtain an imine intermediate, reducing C ═ N double bonds with sodium borohydride, and reacting carbon disulfide with amine groups to obtain the solid heavy metal ion adsorbing material. The material can effectively adsorb heavy metal ions in water to clean wastewater polluted by the heavy metal ions.
Description
Technical Field
The patent relates to the research field of environmental management materials, in particular to a chitosan grafted triethylene tetramine dithiocarbamate adsorbing material which is synthesized and used for adsorbing heavy metal ions such as cadmium, copper, lead and the like.
Background
Heavy metal ions may harm animals and plants as well as human beings, and the harmfulness thereof has been recognized to a large extent. Various heavy metal ion treatment methods have been developed, and one effective treatment method is adsorption. There are many reports on adsorption methods of cadmium, copper and lead ions, such as: method for treating Cd in water by using wheat straw biochar2+The study on the adsorption characteristics of (1) (China environmental science, 2017, volume 2, page 551-559); biological carbon to Cu2+The adsorption characteristics and the influence factors thereof (Anhui agricultural science, 2014, volume 5, page 1467-; core-shell structure Fe3O4/MnO2Preparation and characterization of magnetic adsorbent and research on lead adsorption removal (journal of environmental science, 2013, volume 10, 2730-2736).
There are also various kinds of adsorption materials for heavy metal ions. The dithiocarbamate adsorbent has good heavy metal adsorption performance. There are many reports that organic small molecules and macromolecules of dithiocarbamates have very high coordination stability to many heavy metal ions, such as mercury (Hg), lead (Pb), cadmium (Cd), manganese (Mn), chromium (Cr), copper (Cu), nickel (Ni), zinc (Zn), and other cations (Engineering edition), zheng zhou university, book 2013, volume 6, pages 44-47, Chemical Engineering Journal 2012, volume 209, page 547-.
Crosslinked polyethyleneimine dithiocarbamate heavy metal ion adsorption materials have been reported in patents and literature to have a large adsorption capacity (patent No. ZL 201810122779.2; Environmental Science and Pollution Research,2020,27, 2444-. However, for such an adsorbent material, there may be some functional groups that are not capable of adsorbing, but are wrapped inside the polymer material, and the polyethyleneimine of high molecular weight is expensive, thereby wasting resources.
Chitosan is a product obtained by deacetylation of chitin in nature, and has been widely used in sewage treatment due to its biological functionality, microbial biodegradability and safety. One of the main disadvantages of chitosan is poor porosity of the polymer, resulting in slow mass transfer, and the chitosan modified product is generally used for adsorbing heavy metals.
The chitosan grafted triethylene tetramine dithiocarbamate adsorbing material which has high adsorption capacity to various heavy metal ions, is insoluble in water and easy to separate is obtained by adopting cheap and easily available biomass chitosan, linking a polyamino compound, namely triethylene tetramine, with a short amino grafted chain and a definite structure on the chitosan grafted triethylene tetramine and finally linking heavy metal ion adsorption functional groups on the chitosan grafted triethylene tetramine.
The chitosan is grafted with the dithiocarbamate adsorbing material of triethylene tetramine through the longer-chain glutaraldehyde, so that the adsorption of functional group dithiocarbamate deep into the aqueous solution is facilitated, and the heavy metal ions in the aqueous solution are captured.
Disclosure of Invention
The invention discloses a chitosan grafted triethylene tetramine dithiocarbamate heavy metal ion adsorption material, namely chitosan is dissolved in acetic acid and then condensed with one end of glutaraldehyde, the other end of glutaraldehyde reacts with triethylene tetramine, then, the formed imine structure is reduced by sodium borohydride to obtain a graft polymer of chitosan grafted triethylene tetramine, and finally, the graft polymer reacts with carbon disulfide, a dithioamino-functional group capable of adsorbing various heavy metal ions is introduced, the chelating capacity of the adsorption material for heavy metals is increased, and the dithiocarbamate heavy metal ion adsorption material of chitosan grafted triethylene tetramine is obtained; and the heavy metal ions of cadmium, copper and lead in the wastewater are adsorbed by the adsorption material.
The synthesis experiment procedure of the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material comprises the following steps: weighing a certain amount of chitosan powder, putting the chitosan powder into a reaction container, adding a certain amount of 1% acetic acid solution, heating and stirring the mixture at a proper temperature, adding a certain amount of glutaraldehyde after the mixture is dissolved uniformly, and continuing to react for a period of time. Meanwhile, a certain amount of triethylene tetramine and a certain amount of cosolvent absolute ethyl alcohol are uniformly stirred, and then the mixture is poured into the chitosan solution to continue to react for a period of time. Then, in the process of heating and stirring, a certain amount of reducing agent sodium borohydride is added for multiple times. Then, after the reaction is cooled to room temperature, a certain amount of carbon disulfide is added, stirring is continued for a period of time, the obtained reaction mixed solution is transferred into a container, ultrasonic treatment is carried out in ultrasonic waves for a period of time, then suction filtration is carried out, and the high polymer adsorbing material is washed for 3 times by 95% ethanol. And finally, drying the obtained modified polymer in a drying oven at a proper temperature for a period of time to obtain the chitosan grafted triethylene tetramine dithiocarbamate heavy metal ion adsorbing material.
The experimental operation procedure of adsorbing heavy metal ions by the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is as follows: weighing a certain amount of macromolecular adsorption material into a container, respectively transferring a certain amount of cadmium (II), copper (II) and lead (II) ion stock solutions with determined concentrations into the container, sealing a bottle opening with a plastic film, and vibrating for a certain time. And centrifuging the liquid after adsorption for a period of time at a certain rotating speed, taking the supernatant, detecting by ICP-OES (inductively coupled plasma-optical emission spectrometry), respectively obtaining the residual concentrations of cadmium (II), copper (II) and lead (II) in the solution after adsorption, and further calculating the adsorption capacity of the adsorption material.
The present invention is illustrated in more detail by the following examples, which are not to be construed as limiting the scope of the invention.
Detailed Description
Example one
The operation procedure of the synthesis experiment of the chitosan grafted triethylene tetramine dithiocarbamate heavy metal ion adsorbing material comprises the following steps: 0.1g of chitosan powder is weighed and put into a reaction container, 25mL of 1% acetic acid solution is added, the mixture is put into a 60 ℃ water bath kettle to be heated and stirred, 0.3g of glutaraldehyde is added after the uniform dissolution, and the reaction is continued for a period of time. Meanwhile, 0.4g of triethylene tetramine is weighed and added into a 100 ml round-bottom flask, 15 ml of absolute ethyl alcohol is added, the mixture is placed into a preheated oil bath kettle at the temperature of 60 ℃ to be stirred, and the mixture is added into a chitosan solution to continue to react for 3 to 4 hours after being dissolved uniformly. During this time, 0.2g of sodium borohydride, a reducing agent, was added in portions. The reaction was then allowed to cool to room temperature, 0.4g of carbon disulfide was added, and the resulting product was transferred to an erlenmeyer flask, sonicated for 30 minutes in ultrasound, then transferred to a buchner funnel, filtered with suction, and washed 3 times with 95% ethanol. And finally, drying the obtained modified polymer in an oven at 60 ℃ for 24 hours to obtain 2.32 g of chitosan grafted triethylene tetramine dithiocarbamate adsorbing material.
Example two
The experimental operation procedure of adsorbing cadmium ions by the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is as follows: 0.025 g of the adsorbing material was weighed into a 100 ml Erlenmeyer flask, 25ml of a cadmium (II) ion stock solution (200 mg/L of cadmium (II) ion) was pipetted into the Erlenmeyer flask, sealed, and shaken for 60 minutes. The liquid after completion of the adsorption was then centrifuged at 4000 rpm for 30 minutes to obtain a supernatant, which was measured by ICP-OES to calculate the adsorption amount of cadmium (II) ions on the adsorbent to be 182 mg/g.
EXAMPLE III
The experimental operation procedure of adsorbing cadmium ions by the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is as follows: 0.025 g of the adsorbent was weighed into a 100 ml Erlenmeyer flask, 25ml of a stock solution of copper (II) ions (200 mg/l copper (II) ions) was pipetted into the Erlenmeyer flask, sealed and shaken for 60 minutes. The liquid after completion of the adsorption was then centrifuged at 4000 rpm for 30 minutes to obtain a supernatant, which was measured by ICP-OES and calculated to have an adsorbed amount of copper (II) ions of 164 mg/g.
Example four
The experimental operation procedure of adsorbing the lead ions by the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is as follows: 0.025 g of the adsorbing material was weighed into a 100 ml Erlenmeyer flask, 25ml of a stock solution of lead (II) ions (200 mg/l of lead (II) ions) was pipetted into the Erlenmeyer flask, sealed and shaken for 60 minutes. The liquid after completion of the adsorption was then centrifuged at 4000 rpm for 90 minutes to obtain a supernatant, which was measured by ICP-OES and calculated to have an adsorption amount of 352 mg/g of lead (II) ions.
Claims (2)
1. A chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is characterized in that a synthesis method of the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material is that chitosan and glutaraldehyde are condensed to obtain a high-molecular single-ended imine intermediate, the intermediate is condensed with triethylene tetramine through aldehyde group at the other end of the glutaraldehyde to form a high-molecular double-ended imine intermediate of chitosan grafted triethylene tetramine, then sodium borohydride is used for reducing all carbon-nitrogen double bonds, and then the high-molecular double-ended imine intermediate reacts with carbon disulfide to generate the chitosan grafted triethylene tetramine dithiocarbamate adsorbing material which is insoluble in water and easy to separate.
2. The chitosan grafted triethylene tetramine dithiocarbamate adsorbent material of claim 1, wherein the chitosan grafted triethylene tetramine dithiocarbamate adsorbent material can be used for adsorbing cadmium ions, copper ions and lead ions in water, and has adsorption capacities of 182 mg, 164 mg/g and 352 mg/g for solutions with concentrations of 200 mg/L, 200 mg/L and 500 mg/L of cadmium (II) ions, copper (II) ions and lead (II) ions respectively.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368832A (en) * | 2021-06-25 | 2021-09-10 | 吉林大学 | Adsorbent material and preparation method and application thereof |
| CN113861310A (en) * | 2021-09-09 | 2021-12-31 | 广州振清环保技术有限公司 | Reactive polyamide chitosan thiocarbamate and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113368832A (en) * | 2021-06-25 | 2021-09-10 | 吉林大学 | Adsorbent material and preparation method and application thereof |
| CN113368832B (en) * | 2021-06-25 | 2022-11-18 | 吉林大学 | Adsorbent material and preparation method and application thereof |
| CN113861310A (en) * | 2021-09-09 | 2021-12-31 | 广州振清环保技术有限公司 | Reactive polyamide chitosan thiocarbamate and application thereof |
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