CN106824085B - Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent - Google Patents

Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent Download PDF

Info

Publication number
CN106824085B
CN106824085B CN201710166921.9A CN201710166921A CN106824085B CN 106824085 B CN106824085 B CN 106824085B CN 201710166921 A CN201710166921 A CN 201710166921A CN 106824085 B CN106824085 B CN 106824085B
Authority
CN
China
Prior art keywords
peanut shell
carbon material
adsorbent
deionized water
peanut
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.)
Expired - Fee Related
Application number
CN201710166921.9A
Other languages
Chinese (zh)
Other versions
CN106824085A (en
Inventor
蔡卫权
魏家豪
赵亚真
李忠磊
刘莹
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.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
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 Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201710166921.9A priority Critical patent/CN106824085B/en
Publication of CN106824085A publication Critical patent/CN106824085A/en
Application granted granted Critical
Publication of CN106824085B publication Critical patent/CN106824085B/en
Expired - Fee Related 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
    • 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
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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

Abstract

The invention provides a preparation method of an amino functionalized peanut shell carbon material heavy metal adsorbent, which adopts a one-step hydrothermal method to prepare the adsorbent. The method has the remarkable advantages of simple and convenient preparation process, cheap and easily-obtained raw materials, excellent adsorption performance of the prepared carbon material and the like, and the product is prepared by a one-step hydrothermal method, so that the energy consumption is low and the preparation efficiency is high; under certain conditions, when the peanut shell concentration is 120g/L and hexamethylenediamine is a nitrogen source, the adsorption quantity of the prepared carbon material to Cr (VI) reaches 49.34mg/g, the removal rate reaches 98.7 percent, and the removal rate can still reach more than 80.0 percent after 3 times of circulation; when the peanut shell concentration is 120g/L, DMF and is a nitrogen source, the residual concentration of Cr (VI) in the water body can be reduced to 0.39mg/L after the prepared carbon material adsorbs Cr (VI), and the discharge standard of the Cr (VI) content in the industrial sewage specified by the state can be reached.

Description

Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent
Technical Field
The invention relates to the technical field of preparation and application of carbon-based composite adsorption materials, in particular to a preparation method for preparing an amino-functionalized carbon material adsorbent by a one-step hydrothermal method by taking peanut shells as raw materials, wherein the adsorbent is used for adsorbing highly toxic pollutants Cr (VI) in a water body.
Background
Chromium pollution is mainly from tanned leather, mining, steel and alloy, dye and pigment manufacturing and other production industries. Chromium in the water body exists mainly as Cr (VI), Cr (VI) has strong toxicity, the concentration of Cr (VI) in the industrial wastewater is generally 50-250mg/L, if the treatment is not proper, hexavalent chromium can invade into the body through the digestive tract, the respiratory tract, the skin and the like, and mainly accumulates in liver, kidney and endocrine glands to cause chronic poisoning, so that local organs are damaged and further worsened, and serious harm is caused to the health. Among the various methods for removing Cr (vi), an adsorption method based on an activated carbon-based adsorbent has attracted attention because of its advantages such as easy operation and high removal rate. However, the conventional activated carbon adsorbent is expensive due to the problems of raw material sources, preparation processes and the like.
The traditional active carbon is mainly from non-renewable fossil fuels such as coal and the like, and the preparation process of the traditional active carbon has the problem of environmental pollution. The biomass resource is used as a renewable carbon source and has the advantages of wide source, low price, renewability, environmental friendliness and the like, so that the biomass resource is gradually concerned about the preparation of the carbon material adsorbent. For example, Shulijia et al (Shulijia, Sunpushai, Wang Tiangui, activated carbon made from peanut shell and research on removing hexavalent chromium [ J)]Chemical Engineers, 2009, (8):8-12.) used 50% H3PO4The peanut shell is impregnated in the aqueous solution according to the liquid-solid ratio of 2:1, and is pyrolyzed at the temperature of 400-600 ℃ for 2-4h to obtain the activated carbon adsorbent, and the activated carbon adsorbent is used for removing Cr (VI) in the aqueous solution. At a solution pH of 2, from H3PO4The adsorption capacity of the activated carbon to Cr (VI) can reach 125.0mg/g, but the residual concentration of Cr (VI) in the solution after adsorption is more than 300 mg/L. For another example, Li Zhuang et al (Li Zhuang, Yuaren, Yang Qian Ling, He Sanmao, Tulinchang, Li Canodo. peanut shell activated carbon has adsorption property to Cr (VI) in aqueous solution [ J]The peanut shells are cleaned by tap water, dried in an oven at 105 ℃ for 24h to constant weight, crushed by a crusher, screened by a nylon screen, and then immersed in ZnCl with the mass concentration of 25 percent according to the immersion ratio of 1:12Solutions ofSoaking for 24 hr, filtering, and oven drying. Then placing the dried peanut shells in N2Placing in a microwave oven (2.45GHz,700W) under protection for microwave activation for 15 min. And cooling, washing and drying the sample to obtain the activated carbon adsorbent. Experiments show that when the adding amount of the adsorbent is 0.2g, under the condition that the initial concentration of Cr (VI) is 20mg/L, PH value is 2.0, the removal rate of Cr (VI) by the adsorbent can be maintained to be more than 94.13 percent after the adsorption reaction is carried out for 180 min. However, the preparation methods of the carbon material adsorbent reported above all require high-temperature heat treatment of raw materials, the energy consumption for sample preparation is large, and the acid used in the preparation process causes certain pollution to the environment.
Among the various methods for preparing carbon materials, the hydrothermal method has the following advantages: (1) the equipment is simple, and the hydrothermal process is easy to control; (2) the product contains rich carboxyl, hydroxyl and other oxygen-containing groups; (3) the process factors such as hydrothermal temperature, hydrothermal time, reactant types and concentrations, pH and the like can be directionally regulated and controlled, and products with specific crystal forms, morphologies and particle sizes are prepared.
Methods for improving the adsorption capacity of heavy metal ions in water by increasing active sites on the surface of a carbon material through amino functionalization have been reported. Sharififard et al (Sharififard H, Soleimani M, Ashtiani FZ. J. evaluation of activated carbon and bio-polymer modified activated carbon for Palladium and platinum removal [ J ]. Taiwan Inst. chem. E. 2012,43(5):696.) store the activated carbon in oleic acid for 4 hours, filter, rinse, dry to form acid treated activated carbon, disperse it into oil soluble chitosan, stir it dropwise for 16 hours at about 50 ℃, add this colloidal mixture to NaOH solution to form aminated activated carbon. The activated carbon functionalized by chitosan is adopted to remove Pd (II) and Pt (II) in water, and the adsorption capacity reaches 43.5mg/g and 52.6mg/g respectively. However, the adsorption capacity of the adsorption material prepared by the method is low, the preparation and modification of the carbon material are carried out in multiple steps, the preparation procedures are more, and the periodicity is longer.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a one-step preparation method of the amino functionalized carbon material adsorbent with cheap raw materials, simple process, low energy consumption and excellent adsorption performance to Cr (VI) in water. The prepared adsorbent has the characteristics of large adsorption capacity, high adsorption rate and good cyclic adsorption performance on Cr (VI) in a water body.
The invention adopts the following technical scheme for solving the technical problems:
the invention provides a preparation method of an amino functionalized peanut shell carbon material heavy metal adsorbent, which is characterized in that a one-step hydrothermal method is adopted to prepare the adsorbent, and the method comprises the following steps:
(1) preparing peanut shell powder:
washing peanut shells with deionized water in sequence, drying the peanut shells at 80 ℃ for 12 hours, and grinding the peanut shells to obtain peanut shell powder;
(2) preparation of the suspension:
respectively weighing a certain amount of peanut shell powder and organic amine, adding the peanut shell powder and the organic amine into deionized water at room temperature, and stirring to obtain a suspension;
(3) preparation of product containing brown precipitate:
transferring the suspension into a 100ml reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction, and naturally cooling to room temperature after the reaction is finished to obtain a product containing brown precipitate;
(4) preparing an amino functionalized carbon material adsorbent:
and separating and washing the brown precipitate by using deionized water until the filtrate is clear and colorless, then washing a filter cake by using absolute ethyl alcohol for 1 time, and further drying the brown filter cake in vacuum at 60 ℃ for 12 hours to prepare the adsorbent.
In the step (1), the dried peanut shells are ground to 20-40 meshes.
In the step (2), the organic amine is one of ethylenediamine, hexamethylenediamine and N, N-dimethylformamide.
In the step (2), the mass ratio of the peanut shell powder to the organic amine to the deionized water is 1: (0.3-1.58): (6.66-8.33).
In the step (3), the hydrothermal reaction conditions are as follows: the hydrothermal temperature is 200 ℃ and 240 ℃ and the hydrothermal time is 8-12 h.
According to the method provided by the invention, the prepared amino functionalized peanut shell carbon material heavy metal adsorbent is used for adsorbing Cr (VI) solution with pH of 3 and concentration of 1-150 mg/L.
The material is used for adsorbing mixed heavy metal ion solution of Cr (VI) and 100mg/L Cd (II), Cu (II), Zn (II) and Ni (II).
After adsorbing Cr (VI), the material is desorbed by 0.01mol/L NaOH solution, and the desorbed amino functionalized peanut shell carbon material heavy metal adsorbent is recycled.
The invention is based on the following principle: the biomass can be subjected to reactions such as dehydration, decarboxylation, decarbonylation, polycondensation and the like in the hydrothermal reaction process, and an organic amine source is introduced in the process, so that on one hand, a composite solid fuel similar to lignite and peat can be formed; on the other hand, hydrothermal cross-linking reaction can occur in the hydrothermal process, so that the amino functionalized carbon material is obtained in the biomass carbonization process.
Compared with the prior art, the invention has the following main advantages:
(1) agricultural waste residue peanut shell biomass with wide sources can be used as a carbon source;
(2) the amino functionalized carbon material adsorbent can be prepared by a hydrothermal method one-step method under mild conditions, the process is simple, and the preparation efficiency is greatly improved; under certain conditions, when the peanut shell concentration is 120g/L and hexamethylenediamine is a nitrogen source, the adsorption quantity of the prepared carbon material to Cr (VI) reaches 49.34mg/g, the removal rate reaches 98.7 percent, and the removal rate can still reach more than 80.0 percent after 3 times of circulation; when the peanut shell concentration is 120g/L, DMF and is a nitrogen source, the residual concentration of Cr (VI) in the water body can be reduced to 0.39mg/L after the prepared carbon material adsorbs Cr (VI), so that the discharge standard of the Cr (VI) content in the industrial sewage specified by the state is reached;
(3) the prepared amino functional carbon material has higher removal rate to Cr (VI) in water, under a certain condition, the content of Cr (VI) after wastewater is treated by the amino functional carbon material adsorbent can reach the discharge standard of national regulated industrial wastewater, and the amino functional carbon material after adsorbing Cr (VI) can be regenerated and recycled after desorption.
Drawings
FIGS. 1-3 are graphs of adsorption kinetics for Cr (VI) for samples prepared in examples 1-3;
FIG. 4 is the removal rate of the mixed cations for the samples of example 4;
FIG. 5 is a graph showing the adsorption amounts of Cr (VI) for samples prepared in example 2 and their regeneration cycles 1, 2 and 3;
FIG. 6 is an SEM picture of a sample of PhC-HDA-2 prepared in example 2;
FIG. 7 is an SEM picture of a sample of PhC-HDA-2 prepared in example 2;
FIG. 8 is an SEM picture of a sample of PhC-2 prepared in example 2;
FIG. 9 is an SEM picture of a sample of PhC-2 prepared in example 2.
Detailed Description
The invention provides a preparation method for preparing an amino functionalized carbon material heavy metal adsorbent from peanut shells by a one-step hydrothermal method, which comprises the following steps: peanut shells are used as a carbon source, hexamethylenediamine, N-Dimethylformamide (DMF) and the like are used as nitrogen sources, and after the mixed suspension liquid is subjected to hydrothermal reaction, products are sequentially cooled, separated, washed and dried to prepare the amino functionalized carbon material adsorbent.
The present invention will be further described with reference to the following examples and accompanying drawings, which are merely illustrative of preferred embodiments of the present invention, and are not intended to limit the present invention.
Example 1
Washing peanut shells with deionized water, drying in an oven at 80 ℃ for 12h, grinding, and sieving with a 20-40-mesh sieve to obtain a biomass raw material; taking 6g of the two groups of biomass raw materials, dispersing the two groups of biomass raw materials in 45g of deionized water, adding no organic amine source in the first group, adding 1.8g of ethylenediamine in the second group, and stirring at room temperature for 20min respectively to obtain suspension, wherein the peanut shell, the organic amine and the deionized water are respectively as follows according to mass ratio: the first group is 1: 0: 7.50, the second group is 1: 0.3: 7.50.
(2) and (2) respectively transferring the two groups of suspension liquid obtained in the step (1) to a 100ml reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 200 ℃ for 8h, and naturally cooling to room temperature to obtain two groups of brown precipitate products containing carbon materials.
(3) And sequentially separating and washing the two groups of brown precipitated products with deionized water until filtrate is clear and colorless, finally washing the two groups of brown precipitated products with absolute ethyl alcohol for 1 time respectively, and then drying the two groups of brown precipitated products in a drying oven at the temperature of 60 ℃ for 12 hours in vacuum respectively to obtain two groups of adsorbent samples, wherein the samples prepared without introducing organic amine and with introducing ethylenediamine are named as PhC-1 and PhC-EDA-1 respectively.
After 50ml and 150mg/L of Cr (VI) solution is respectively adsorbed by the two groups of adsorbent samples, the pH value is adjusted to 3 by using 1mol/L hydrochloric acid solution, then 0.1g of PhC-1 and PhC-EDA-1 samples are respectively added, the parameters of a constant temperature oscillation box are set to be 25 ℃ and 180r/min, and finally, the adsorption kinetic curves of the two groups of samples to the Cr (VI) are obtained through calculation.
The adsorption kinetics curve of the sample to Cr (VI) is shown in figure 1, wherein the adsorption removal rate of the PhC-1 sample without the introduction of the ethylenediamine to the Cr (VI) at 270min is 74.3%, and the adsorption quantity is 55.7 mg/g.
The adsorption removal rate of the PhC-EDA-1 sample to Cr (VI) at 270min is 93.9%, the adsorption amount is 70.4mg/g, and the adsorption removal rate is improved by 19.6% compared with the sample without the organic amine.
Example 2
Washing peanut shells with deionized water, drying in an oven at 80 ℃ for 12h, grinding, and sieving with a 20-40-mesh sieve to obtain a biomass raw material; taking 6g of the two groups of biomass raw materials, dispersing the two groups of biomass raw materials in 50g of deionized water, adding no organic amine source in the first group, adding 2.7g of hexamethylene diamine in the second group, and stirring the mixture at room temperature for 20min to obtain suspension, wherein the peanut shell, the organic amine and the deionized water are respectively as follows according to mass ratio: the first group is 1: 0: 8.33, second set is 1: 0.45: 8.33.
(2) and (2) respectively transferring the two groups of suspension liquid obtained in the step (1) to a 100ml reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 220 ℃ for 12h, and naturally cooling to room temperature to obtain two groups of brown precipitate products containing carbon materials.
(3) And sequentially separating and washing the two groups of brown precipitate products with deionized water until filtrate is clear and colorless, finally washing the two groups of brown precipitate products with absolute ethyl alcohol for 1 time respectively, and then drying the two groups of brown precipitate products in a drying oven at the temperature of 60 ℃ for 12 hours in vacuum respectively to obtain two groups of adsorbent samples, wherein the samples prepared by introducing no organic amine and introducing hexamethylenediamine are named as PhC-2 and PhC-HDA-2 respectively.
After 50ml and 100mg/L of Cr (VI) solution is respectively adsorbed by the two groups of adsorbent samples, the pH value is adjusted to 3 by using 1mol/L hydrochloric acid solution, then 0.1g of PhC-2 and PhC-HDA-2 samples are respectively added, the parameters of a constant temperature oscillation box are set to be 25 ℃ and 180r/min, and finally, the adsorption kinetic curves of the two groups of samples to the Cr (VI) are obtained through calculation.
The adsorption kinetics curve of the sample to Cr (VI) is shown in figure 2, wherein the adsorption removal rate of the PhC-2 sample without introducing the hexamethylene diamine to the Cr (VI) at 180min is 72.0 percent, and the adsorption quantity is 36.0 mg/g.
The PhC-HDA-2 sample has the adsorption removal rate of 97.0 percent to Cr (VI) at 180min, the adsorption quantity of 48.5mg/g, and the adsorption removal rate is improved by 25.0 percent compared with the sample without introducing organic amine.
Example 3
Washing peanut shells with deionized water, drying in an oven at 80 ℃ for 12h, grinding, and sieving with a 20-40-mesh sieve to obtain a biomass raw material, wherein the name of the biomass raw material is Ph-0; taking 6g of the two groups of biomass raw materials, dispersing the two groups of biomass raw materials in 40g of deionized water, adding no organic amine source in the first group, adding 9.46g N N-dimethylformamide in the second group, and stirring the mixture at room temperature for 20min to obtain suspension, wherein the peanut shells, the organic amine and the deionized water are respectively as follows according to mass ratio: the first group is 1: 0: 6.67, second set is 1: 1.58: 6.67.
(2) and (2) respectively transferring the two groups of suspension liquid obtained in the step (1) to a 100ml reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 240 ℃ for 10h, and naturally cooling to room temperature to obtain two groups of brown precipitate products containing carbon materials.
(3) And sequentially separating and washing the two groups of brown precipitate products with deionized water until filtrate is clear and colorless, finally washing the two groups of brown precipitate products with absolute ethyl alcohol for 1 time respectively, and then drying the two groups of brown precipitate products in an oven at the temperature of 60 ℃ for 12 hours in vacuum respectively to obtain two groups of adsorbent samples, wherein the samples prepared by introducing no organic amine and introducing N, N-dimethylformamide are named as PhC-3 and PhC-DMF-3 respectively.
After 50ml and 50mg/L of Cr (VI) solution is respectively adsorbed by the two groups of adsorbent samples, the pH value is adjusted to 3 by using 1mol/L hydrochloric acid solution, then 0.1g of PhC-3 and PhC-DMF-3 samples are respectively added, the parameters of a constant temperature oscillation box are set to be 25 ℃ and 180r/min, and finally, the adsorption kinetic curves of the two groups of samples to the Cr (VI) are obtained through calculation.
The adsorption kinetics curve of the sample to Cr (VI) is shown in figure 3, wherein the PhC-3 sample without introducing N, N-dimethylformamide has 79.0% of adsorption removal rate to Cr (VI) at 180min, and the adsorption quantity is 19.7 mg/g.
The PhC-DMF-3 sample has the adsorption removal rate of 99.2 percent to Cr (VI) at 180min, the adsorption quantity is 24.8mg/g, the residual concentration of Cr (VI) in the water body is 0.39mg/L as far as possible, and the discharge standard of the Cr (VI) content in the industrial wastewater (0.5 mg/L) specified by the state is reached. Compared with the Cr (VI) adsorption amount of a sample without introducing organic amine, the adsorption amount is improved by 20.2 percent.
50ml of 50mg/L Cr (VI) solution is adsorbed, the pH is adjusted to 3 by using a hydrochloric acid solution with the concentration of 1mol/L, then 0.1g of Ph-0 sample (pure peanut shell powder which is not subjected to hydrothermal carbonization treatment) is added, and the parameters of a constant temperature shaking box are set to be 25 ℃ and 180 r/min. The adsorption removal rate of the sample to Cr (VI) at 180min is only 0.078%, and the adsorption amount is only 3.9 mg/g.
50ml of a 1mg/L Cr (VI) solution are adsorbed while the pH is adjusted to 3 with 1mol/L hydrochloric acid, and then a 0.1g sample of PhC-DMF-3 is added, the parameters of the incubator being set at 25 ℃ and 180 r/min. The adsorption removal rate of the sample on Cr (VI) at 30min is 96.3%, the residual concentration of Cr (VI) in the water body is only 0.037mg/L, the standard (<0.05mg/L) of the Cr (VI) content in national underground water quality class III indexes is reached, and the drinking water level is reached.
Example 4
Preparing a mixed heavy metal ion solution with pH of 3 and containing 100mg/L of Cr (VI), 100mg/L of LCd (II), Cu (II), Zn (II) and Ni (II). Two 50ml portions of the above solution were taken and then 0.1g of PhC-2 and 0.1g of PhC-HDA-2 samples were added, respectively, with the parameters of the incubator set at 25 ℃ and 180 r/min. And (4) determining the content of residual heavy metal ions in the solution after the adsorption is finished. (FIG. 4)
The results show that: the removal rate of Cr (VI) after 100mg/L of Cd (II), Cu (II), Zn (II) and Ni (II) are mixed by the PhC-HDA-2 sample is 99.0%, the adsorption capacity is 49.5mg/g, and the removal rate is improved by 8.3% compared with the PhC-2 sample without amino group functionalization. The sample shows good selective adsorption capacity for Cr (VI) in the presence of mixed cations, and the figure also shows that the sample shows certain adsorption capacity for other heavy metal cations, the removal rate for Cu (II) is 89.3%, the adsorption capacity is 44.65mg/g, the removal rates for Cd (II), Zn (II) and Ni (II) are relatively low, respectively 2.8%, 0.9% and 0.3%, and the adsorption capacities are respectively 1.4mg/g, 0.45mg/g and 0.15 mg/g. Therefore, the prepared PhC-HDA-2 sample also has certain potential application value in adsorbing heavy metal Cu (II) in water.
Example 5
In order to examine the cyclic regeneration adsorption performance of the one-step method for preparing the amine-functionalized carbon material, 100ml of PhC-HDA-2 sample which is prepared in example 2 and adsorbs 100mg/L of Cr (VI) solution for 14h and a PhC-2 sample which is not amine-functionalized are desorbed for 8h by using 200ml of 0.01mol/L NaOH solution, then the solution is dried and recovered, the sample which is desorbed is adsorbed again with 100ml of Cr (VI) solution which has the pH value of 3 and 100mg/L, and the parameters of a constant temperature oscillation box are set to be 25 ℃ and 180 r/min. The adsorption-desorption process was repeated 3 times to determine the amount of cr (vi) adsorbed by the original sample and each regenerated sample (fig. 5), and the amount of cr (vi) adsorbed by the original amine-based functionalized carbon material and each regenerated amine-based functionalized carbon material was determined. The result shows that the adsorption amount of the carbon material after 3 times of cycles is reduced by about 19.0 percent compared with the initial adsorption amount of the carbon material on Cr (VI), but the adsorption removal rate is still kept above 80.0 percent, and the removal rate on Cr (VI) in the water body is still higher than that of the PhC-2 sample which is not functionalized by amino groups.
The concentration of Cr (VI) in the above examples 1 to 5 was measured by a dibenzoyl dihydrazide spectrophotometry, and the UV-visible spectrophotometer used was UVmini-1240 type of Shimadzu corporation, Japan.
In the above examples 1-5, the dried peanut shells can be ground by a conventional 400Y-type electric small-sized pulverizer.
It should be emphasized that the above-described embodiments are merely examples for clearly illustrating the present invention and are not to be considered as a complete limitation of the embodiments. Other variants will be apparent to those skilled in the art on the basis of the foregoing description, and it is not necessary to exemplify all the embodiments herein, but rather obvious variations are contemplated which are within the scope of the invention.

Claims (5)

1. An application of an amino functionalized peanut shell carbon material as a heavy metal adsorbent is characterized in that the material is used for adsorbing a mixed heavy metal ion solution of Cr (VI), Cd (II), Cu (II), Zn (II) and Ni (II) with the pH value of 3;
the adsorbent is prepared by adopting a one-step hydrothermal method, and comprises the following steps:
(1) preparing peanut shell powder:
washing, drying and grinding the peanut shells in sequence to obtain peanut shell powder;
(2) preparation of the suspension:
respectively weighing a certain amount of peanut shell powder and organic amine, adding the peanut shell powder and the organic amine into deionized water at room temperature, and stirring to obtain a suspension; the mass ratio of the peanut shell powder to the organic amine to the deionized water is 1: (0.3-1.58): (6.66-8.33); the organic amine is ethylenediamine or hexamethylenediamine;
(3) preparation of product containing brown precipitate:
transferring the suspension into a 100ml reaction kettle lined with polytetrafluoroethylene for hydrothermal reaction at the hydrothermal temperature of 200 ℃ and the hydrothermal time of 8-12h, and naturally cooling to room temperature after the hydrothermal reaction is finished to obtain a product containing brown precipitate;
(4) preparing an amino functionalized carbon material adsorbent:
and separating and washing the brown precipitate by using deionized water until the filtrate is clear and colorless, then washing a filter cake by using absolute ethyl alcohol for 1 time, and further drying the brown filter cake in vacuum at 60 ℃ for 12 hours to prepare the adsorbent.
2. The use of claim 1, wherein the material is desorbed by 0.01mol/L NaOH solution after adsorbing Cr (VI), and the desorbed amino functionalized peanut shell carbon material heavy metal adsorbent is recycled.
3. Use according to claim 1, characterized in that in step (1), the peanut shells are washed with deionized water.
4. Use according to claim 1, characterized in that in step (1) the peanut shells after washing with deionized water are dried at 80 ℃ for 12 h.
5. The use according to claim 1, wherein in step (1), the peanut shells are washed with deionized water and dried, and ground to 20-40 mesh to obtain peanut shell powder.
CN201710166921.9A 2017-03-20 2017-03-20 Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent Expired - Fee Related CN106824085B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710166921.9A CN106824085B (en) 2017-03-20 2017-03-20 Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710166921.9A CN106824085B (en) 2017-03-20 2017-03-20 Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent

Publications (2)

Publication Number Publication Date
CN106824085A CN106824085A (en) 2017-06-13
CN106824085B true CN106824085B (en) 2020-04-21

Family

ID=59129927

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710166921.9A Expired - Fee Related CN106824085B (en) 2017-03-20 2017-03-20 Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent

Country Status (1)

Country Link
CN (1) CN106824085B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112295539A (en) * 2020-09-15 2021-02-02 浙江工业大学 Modified mangosteen shell activated carbon and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102974315A (en) * 2012-12-10 2013-03-20 中国矿业大学 Load type amino functional meso-porous silicon adsorbent and preparation method thereof
CN103272568A (en) * 2013-05-29 2013-09-04 浙江大学宁波理工学院 Method for preparing bifunctional modified cellulose adsorbing agent from peanut shells and application of method
CN103752279A (en) * 2013-11-27 2014-04-30 河海大学 Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof
CN104525129A (en) * 2014-12-31 2015-04-22 湖南科技大学 Preparation method of modified activated carbon used for heavy metal wastewater treatment
CN104941575A (en) * 2014-03-25 2015-09-30 南京农业大学 Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102974315A (en) * 2012-12-10 2013-03-20 中国矿业大学 Load type amino functional meso-porous silicon adsorbent and preparation method thereof
CN103272568A (en) * 2013-05-29 2013-09-04 浙江大学宁波理工学院 Method for preparing bifunctional modified cellulose adsorbing agent from peanut shells and application of method
CN103752279A (en) * 2013-11-27 2014-04-30 河海大学 Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof
CN104941575A (en) * 2014-03-25 2015-09-30 南京农业大学 Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method
CN104525129A (en) * 2014-12-31 2015-04-22 湖南科技大学 Preparation method of modified activated carbon used for heavy metal wastewater treatment

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
氨基化生物质炭吸附水中汞离子性能研究;刘明灯等;《应用化工》;20130630;第42卷(第6期);第1035-1038页 *
水热炭化废弃生物质的研究进展;吴倩芳等;《环境污染与防治》;20120731;第34卷(第7期);第70-75页 *
水热炭的制备、性质及应用;吴艳姣等;《化学进展》;20160125;第28卷(第1期);第121-130页 *
酰胺化碳微球的制备及其对铀的吸附性能影响;王晓明等;《化工新型材料》;20161031;第44卷(第10期);第130-133页 *
酰胺化碳微球的制备及其对铀的吸附性能研究;何凯丽等;《核燃料循环》;20141231;第6页 *

Also Published As

Publication number Publication date
CN106824085A (en) 2017-06-13

Similar Documents

Publication Publication Date Title
Qu et al. Multi-component adsorption of Pb (II), Cd (II) and Ni (II) onto microwave-functionalized cellulose: Kinetics, isotherms, thermodynamics, mechanisms and application for electroplating wastewater purification
Yu et al. Facile preparation of sulfonated biochar for highly efficient removal of toxic Pb (II) and Cd (II) from wastewater
Shi et al. High-efficiency removal of Cr (VI) by modified biochar derived from glue residue
Li et al. Comparison of adsorption properties for cadmium removal from aqueous solution by Enteromorpha prolifera biochar modified with different chemical reagents
Dewage et al. Lead (Pb 2+) sorptive removal using chitosan-modified biochar: batch and fixed-bed studies
Xu et al. New double network hydrogel adsorbent: Highly efficient removal of Cd (II) and Mn (II) ions in aqueous solution
Gautam et al. Biomass-derived biosorbents for metal ions sequestration: Adsorbent modification and activation methods and adsorbent regeneration
Wang et al. Adsorption of Copper (II) onto activated carbons from sewage sludge by microwave-induced phosphoric acid and zinc chloride activation
Liu et al. Adsorption of lead (Pb) from aqueous solution with Typha angustifolia biomass modified by SOCl2 activated EDTA
US9533281B2 (en) Porositization process of carbon or carbonaceous materials
CN108079949B (en) Method for removing lead in water body by using magnetic pig manure biochar
Ahmed et al. Nano-hydroxyapatite modified biochar: Insights into the dynamic adsorption and performance of lead (II) removal from aqueous solution
Hamzah et al. Characterisation and performance of thermally treated rice husk as efficient adsorbent for phosphate removal
Ma et al. Enhanced adsorption of cadmium from aqueous solution by amino modification biochar and its adsorption mechanism insight
Shaikh Adsorption of Pb (II) from wastewater by natural and synthetic adsorbents
Zhao et al. Adsorption, separation and recovery properties of blocky zeolite-biochar composites for remediation of cadmium contaminated soil
Tang et al. Efficient adsorption removal of Cd2+ from aqueous solutions by HNO3 modified bamboo-derived biochar
Hamid et al. Novel thiol-grafted composite of chitosan and rice straw biochar (TH@ CT-BC): A two-step fabrication for highly selective adsorption of cadmium from contaminated water
Liu et al. Removal of phosphorus using biochar derived from Fenton sludge: Mechanism and performance insights
CN106824085B (en) Preparation method of amino functionalized peanut shell carbon material heavy metal adsorbent
CN112108118A (en) Magnetic biomass charcoal based on Fenton sludge and cellulose and preparation method and application thereof
Karthika et al. Utilization of sago waste as an adsorbent for the removal of Pb (II) from aqueous solution: kinetic and isotherm studies
Nandiyanto et al. Removal of curcumin dyes from aqueous solutions using carbon microparticles from jackfruit seeds by batch adsorption experiment
CN113522257B (en) Preparation method and use method of high-performance Cr (VI) removing coal-based functional material
Tran et al. Facile synthesis of Fe3O4 nanoparticles loaded on activated carbon developed from Lotus seed pods for removal of Ni (II) ions

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200421

Termination date: 20210320

CF01 Termination of patent right due to non-payment of annual fee