CN118162115B - Multifunctional group modified loofah sponge heavy metal adsorbent and preparation method thereof - Google Patents

Multifunctional group modified loofah sponge heavy metal adsorbent and preparation method thereof Download PDF

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CN118162115B
CN118162115B CN202410585359.3A CN202410585359A CN118162115B CN 118162115 B CN118162115 B CN 118162115B CN 202410585359 A CN202410585359 A CN 202410585359A CN 118162115 B CN118162115 B CN 118162115B
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heavy metal
loofah
retinervus luffae
luffae fructus
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CN118162115A (en
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贾俊豪
汤皓翔
赵可翊
姚阳
朱彤
洪一鸣
杨晗
罗天羽
袁凤
秦余杨
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Changshu Institute of Technology
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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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—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
    • 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

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Abstract

The invention discloses a preparation method of a multifunctional modified loofah sponge heavy metal adsorbent, which comprises the following steps: (i) Modifying the loofah pretreated by alkali liquor by a natural multi-carboxyl compound to obtain carboxyl modified loofah, wherein the natural multi-carboxyl compound is one of malic acid, tartaric acid and citric acid; (ii) Modifying carboxyl modified loofah sponge by polyvinyl alcohol to obtain hydroxyl-rich loofah sponge; (iii) The hydroxy-rich retinervus Luffae fructus is modified by L-cysteine to obtain the multifunctional group modified retinervus Luffae fructus heavy metal adsorbent. The invention also discloses the multifunctional group modified loofah sponge heavy metal adsorbent prepared by the preparation method. The invention increases the grafting rate of the functional groups of the loofah sponge and obviously improves the adsorption quantity of the loofah sponge to various heavy metal ions.

Description

Multifunctional group modified loofah sponge heavy metal adsorbent and preparation method thereof
Technical Field
The invention relates to the technical field of solid adsorbents, in particular to a modified loofah sponge adsorbent and a preparation method thereof.
Background
The current effective methods for removing heavy metal ions in sewage mainly comprise flocculation, chemical precipitation, membrane filtration, ion exchange, adsorption and the like. The adsorption method has the advantages of simple operation, wide selection of adsorption materials, high adsorption speed and the like, and is a technical means with development prospect. The quality of the heavy metal ion removing effect of the adsorption method mainly depends on the selected adsorption material, but the conventional adsorption material is generally poor in heavy metal ion removing effect or needs a large amount of use, is difficult to recover after adsorption and sometimes causes secondary pollution, so that the selection of a proper adsorbent material is important. Most of the current researches focus on polymer synthetic porous adsorption materials, and although the materials have high performance of removing heavy metal ions, the materials have high preparation cost and are difficult to degrade naturally, so that development of low-cost, green and efficient biomass adsorption materials is urgently needed.
The loofah sponge as a fiber net biomass material which is low in cost, renewable and degradable shows great potential in the field of heavy metal removal and adsorption. But the functional groups on the surface of the loofah sponge are single in species and low in content, so that the adsorption effect on heavy metals is poor. Although the prior art has many grafting modification on the loofah to improve the adsorption performance of the loofah on heavy metal ions, the modified loofah still faces the problems of low grafting rate and single functional group types, so that the improvement of the adsorption performance of the loofah on the heavy metal ions is limited.
Disclosure of Invention
Aiming at the technical requirements, the invention provides a preparation method of a multifunctional modified loofah sponge heavy metal adsorbent, aiming at solving the problem that the loofah sponge has weaker adsorption performance on heavy metal ions.
The technical scheme of the invention is as follows: a preparation method of a multifunctional modified loofah sponge heavy metal adsorbent comprises the following steps:
(i) Adding the loofah pretreated by alkali liquor into an N, N-dimethylformamide solution dissolved with stannous chloride, and then adding a natural polycarboxylic compound to react to obtain carboxyl modified loofah, wherein the natural polycarboxylic compound is one of malic acid, tartaric acid and citric acid;
(ii) Modifying carboxyl modified loofah sponge by polyvinyl alcohol to obtain hydroxyl-rich loofah sponge;
(iii) The hydroxy-rich retinervus Luffae fructus is modified by L-cysteine to obtain the multifunctional group modified retinervus Luffae fructus heavy metal adsorbent.
Further, the dosage ratio of the luffa, the natural polycarboxylic compound, the stannous chloride and the N, N-dimethylformamide pretreated by the alkali liquor in the step (i) is 1g (0.5-1.5 g) (0.1-0.3) L.
Further, in the step (i), after the natural polycarboxylic compound is added, the reaction solution is stirred at a constant temperature of 100-120 ℃ for reaction for 3-5 hours, and after the reaction, suction filtration, washing and drying are carried out to obtain the carboxyl modified loofah sponge.
Further, in the step (ii), specifically, carboxyl modified loofah sponge is added into a dimethyl sulfoxide solution in which N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 1-hydroxybenzotriazole are dissolved, and then a dimethyl sulfoxide solution of polyvinyl alcohol is added for modification reaction, wherein the dosage ratio of the carboxyl modified loofah sponge to the N, N-dicyclohexylcarbodiimide to the 4-dimethylaminopyridine to the 1-hydroxybenzotriazole to the dimethyl sulfoxide solution of the polyvinyl alcohol is 1g: (1.5-3) g (0.2-0.6) g (0.6-0.9) g (0.1-0.3) L, and the mass ratio of the added polyvinyl alcohol to the carboxyl modified loofah is (5-15): 1.
Further, the average molecular weight of the polyvinyl alcohol in the step (ii) is 50000-100000, and the concentration of the dimethyl sulfoxide solution of the polyvinyl alcohol is 140-180 mg/ml.
Further, when the dimethyl sulfoxide solution of the polyvinyl alcohol is added in the step (ii) for modification reaction, the reaction solution is stirred at a constant temperature of 40-60 ℃ for reaction for 10-20 hours, and after the reaction, suction filtration, washing and drying are carried out to obtain the hydroxyl-rich luffa.
Further, in the step (iii), the hydroxyl-rich loofah sponge is dispersed in dimethyl sulfoxide solution, and then L-cysteine and polyphosphoric acid are sequentially added for modification reaction, wherein the dosage ratio of the hydroxyl-rich loofah sponge to the L-cysteine to the polyphosphoric acid to the dimethyl sulfoxide is 1g (1-3 g) (3-9 g) (0.05-0.2L).
Further, when L-cysteine and polyphosphoric acid are added in the step (iii) for modification reaction, the reaction solution is stirred at a constant temperature of 60-90 ℃ for reaction for 3-6 hours, and after the reaction, the multi-functional group modified loofah sponge heavy metal adsorbent is obtained through suction filtration, washing and drying.
Further, the alkali liquor pretreatment is to soak the loofah sponge into a KOH aqueous solution with the concentration of 2% -15%, stir the loofah sponge at the temperature of 60-100 ℃ for 1-5 hours, and wash the loofah sponge with deionized water to be neutral.
The other technical scheme of the invention is a multifunctional modified loofah sponge heavy metal adsorbent, which is prepared by the preparation method of the multifunctional modified loofah sponge heavy metal adsorbent, and the chemical structural formula of the multifunctional modified loofah sponge heavy metal adsorbent is as follows:
Wherein R represents retinervus Luffae fructus.
According to the invention, a natural polycarboxylic compound is used as a bridge, and the esterification reaction between carboxyl and hydroxyl is carried out, so that the bridge is linked with the luffa while being linked with the polyvinyl alcohol containing a large amount of hydroxyl; and then, taking a large amount of hydroxyl groups on polyvinyl alcohol as binding sites, and further grafting L-cysteine through esterification reaction, so that the loofah sponge adsorbing material which contains a large amount of hydroxyl groups, ester groups, mercapto groups and amino groups with strong adsorption effect on heavy metal ions and has excellent mechanical properties is obtained. Compared with the prior art, the invention has the advantages that:
(1) The natural polycarboxylic compound is used as a bridge, and the grafting rate of the polyvinyl alcohol is effectively increased by two-step grafting;
(2) The polyvinyl alcohol with rich hydroxyl groups is grafted on the surface of the loofah sponge, so that a large number of binding sites can be provided for further functionalization of the loofah sponge, and the mechanical strength and flexibility of the loofah sponge can be effectively improved;
(3) The multi-step esterification modification method greatly enriches the types of functional groups on the surface of the loofah sponge, simultaneously greatly improves the content of various functional groups, and remarkably improves the adsorption quantity of the loofah sponge on various heavy metal ions;
(4) The luffa and the corresponding modifier are both green and degradable environment-friendly materials, and have no pollution to the environment and low manufacturing cost.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
Example 1
A preparation method of a multifunctional modified loofah sponge heavy metal adsorbent comprises the following steps:
(i) Carboxyl group modification
Peeling and seeding the ripe vegetable sponge fruits, immersing in distilled water, and squeezing for several times until no impurity is removed and color is changed. Then soaking the loofah sponge in new distilled water again, changing the water every 3 hours, taking out after 12 hours, naturally airing, and cutting the loofah sponge into a sample of 0.5 cm. The sample is soaked in 10% KOH aqueous solution, stirred at 80 ℃ for 4 hours, taken out, washed to be neutral by distilled water and dried for standby.
1G of pretreated luffa is weighed and added into 150ml of N, N-dimethylformamide solution containing 1g of malic acid and 0.2 g stannous chloride, the mixture is stirred for 4 hours at a constant temperature of 100 ℃, after the reaction is finished, the solution is filtered, acetone is used for washing until filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the carboxyl modified luffa.
(Ii) Hydroxyl-rich modification
1G of carboxyl modified luffa is weighed and added into 100ml of dimethyl sulfoxide solution dissolved with 2.5g of N, N-dicyclohexylcarbodiimide, 0.4g of 4-dimethylaminopyridine and 0.8g of 1-hydroxybenzotriazole, then 70ml of polyvinyl alcohol (M n =60000) of dimethyl sulfoxide solution (160 mg/ml) is added, the mixture is stirred for 15h at a constant temperature of 50 ℃, after the reaction is finished, the mixture is filtered, acetone is washed until the filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6h to obtain the hydroxyl modified luffa.
(Iii) Multifunctional group modification
1G of hydroxyl-rich luffa is weighed and dispersed in 100ml of dimethyl sulfoxide solution, then 2g L-cysteine and 6g polyphosphoric acid are sequentially added, stirring reflux reaction is carried out for 4 hours in a water bath at 80 ℃, suction filtration is carried out, ethanol is used for washing until filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the multifunctional group modified luffa heavy metal adsorbent.
The chemical structural formula of the multifunctional group modified loofah sponge heavy metal adsorbent is as follows:
Wherein R represents retinervus Luffae fructus.
The adsorption performance experiment of the multifunctional modified retinervus luffae fructus heavy metal adsorbent of this example 1 is as follows:
100ml of aqueous solution with the concentration of lead ions (lead nitrate is a reagent) of 0.1g/l is prepared in a flask, the pH value of the solution is regulated to 7 by using 0.1 mol/l NaOH, 0.03g of the multifunctional modified retinervus luffae fructus heavy metal adsorbent is added, and then the adsorption is carried out for 3 hours in a constant temperature oscillator at 25 ℃ and a rotating speed of 200 rpm. After adsorption, the supernatant was collected, and the concentration of lead ions in the supernatant was measured by ICP-OES, and the amount of adsorption of lead ions by the adsorbent was calculated by the following formula, and the results are shown in Table 1.
Q=（C0-Ct）V/M
Q is adsorption quantity (g/g); c 0 is the initial concentration (g/l) of heavy metal ions; c t is the concentration (g/l) of heavy metal ions after adsorption; v is the volume of the solution (l); m is the mass (g) of the adsorbent.
Example 2
This embodiment differs from embodiment 1 in that: in step (i) of this example, 0.5g of tartaric acid was added. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 3
This embodiment differs from embodiment 1 in that: in step (i) of this example, 1.5g of citric acid was added. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 4
This embodiment differs from embodiment 1 in that: to step (ii) of this example, 40ml of a dimethyl sulfoxide solution (160 mg/ml) of polyvinyl alcohol (M n =60000) was added. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 5
This embodiment differs from embodiment 1 in that: to step (ii) of this example, 90ml of a solution of polyvinyl alcohol (M n =60000) in dimethyl sulfoxide (160 mg/ml) was added. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 6
This embodiment differs from embodiment 1 in that: 1g L-cysteine was added to step (iii) of this example. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 7
This embodiment differs from embodiment 1 in that: in step (iii) of this example, 3g L-cysteine was added. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 8
A preparation method of a multifunctional modified loofah sponge heavy metal adsorbent comprises the following steps:
(i) Carboxyl group modification
Peeling and seeding the ripe vegetable sponge fruits, immersing in distilled water, and squeezing for several times until no impurity is removed and color is changed. Then soaking the loofah sponge in new distilled water again, changing the water every 2 hours, taking out after 10 hours, naturally airing, and cutting the loofah sponge into a sample of 0.5 cm. The sample is soaked in a 2% KOH aqueous solution, stirred at 100 ℃ for 1h, taken out, washed to be neutral by distilled water and dried for standby.
1G of pretreated luffa is weighed and added into 100ml of N, N-dimethylformamide solution containing 1g of malic acid and 0.1 g stannous chloride, the mixture is stirred for 5 hours at a constant temperature of 110 ℃, after the reaction is finished, the solution is filtered, acetone is used for washing until filtrate is neutral, and the product is dried in vacuum for 6 hours at 60 ℃ to obtain the carboxyl modified luffa.
(Ii) Hydroxyl-rich modification
1G of carboxyl modified luffa is weighed and added into 200ml of dimethyl sulfoxide solution dissolved with 1.5g of N, N-dicyclohexylcarbodiimide, 0.2g of 4-dimethylaminopyridine and 0.6g of 1-hydroxybenzotriazole, then 50ml of polyvinyl alcohol (M n =50000) of dimethyl sulfoxide solution (140 mg/ml) is added, the mixture is stirred for 20h at a constant temperature of 40 ℃, after the reaction is finished, the mixture is filtered, acetone is washed until the filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6h to obtain the hydroxyl modified luffa.
(Iii) Multifunctional group modification
1G of hydroxyl-rich luffa is weighed and dispersed in 50ml of dimethyl sulfoxide solution, then 1g L-cysteine and 3g of polyphosphoric acid are sequentially added, stirring reflux reaction is carried out for 3 hours in a water bath at 60 ℃, suction filtration is carried out, ethanol is used for washing until filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the multifunctional group modified luffa heavy metal adsorbent. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Example 9
A preparation method of a multifunctional modified loofah sponge heavy metal adsorbent comprises the following steps:
(i) Carboxyl group modification
Peeling and seeding the ripe vegetable sponge fruits, immersing in distilled water, and squeezing for several times until no impurity is removed and color is changed. Then soaking the loofah sponge in new distilled water again, changing the water every 5 hours, taking out after 15 hours, naturally airing, and cutting the loofah sponge into a sample of 0.5 cm. The sample is soaked in 15% KOH aqueous solution, stirred at 60 ℃ for 5 hours, taken out, washed to be neutral by distilled water and dried for standby.
1G of pretreated luffa is weighed and added into 300ml of N, N-dimethylformamide solution containing 1.5g of malic acid and 0.3g of stannous chloride, the mixture is stirred for 3 hours at the constant temperature of 120 ℃, after the reaction is finished, the solution is filtered, acetone is used for washing until filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the carboxyl modified luffa.
(Ii) Hydroxyl-rich modification
1G of carboxyl modified luffa is weighed and added into 300ml of dimethyl sulfoxide solution dissolved with 3.0g of N, N-dicyclohexylcarbodiimide, 0.6g of 4-dimethylaminopyridine and 0.9g of 1-hydroxybenzotriazole, then 80ml of polyvinyl alcohol (M n = 100000) of dimethyl sulfoxide solution (180 mg/ml) is added, the mixture is stirred for 10 hours at a constant temperature of 60 ℃, after the reaction is finished, the mixture is filtered, acetone is washed until the filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the hydroxyl modified luffa.
(Iii) Multifunctional group modification
1G of hydroxyl-rich luffa is weighed and dispersed in 200ml of dimethyl sulfoxide solution, then 3g L-cysteine and 9g of polyphosphoric acid are sequentially added, stirring reflux reaction is carried out for 3 hours in a water bath at 90 ℃, suction filtration is carried out, ethanol is used for washing until filtrate is neutral, and the product is dried in vacuum at 60 ℃ for 6 hours to obtain the multifunctional group modified luffa heavy metal adsorbent. The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Comparative example 1
A preparation method of carboxyl modified retinervus Luffae fructus comprises the same steps as those in (i) in example 1, but without (ii) and (iii). The adsorption properties of the products were determined by the adsorption property test of the product of example 1, and the results are shown in Table 1.
Comparative example 2
A preparation method of a polyvinyl alcohol direct modified loofah sponge mainly grafts the polyvinyl alcohol on the surface of the loofah sponge by a one-step esterification method, and comprises the following specific steps:
1g of pretreated retinervus Luffae fructus (pretreated by the same method as in example 1) was weighed, immersed in 15% 50ml of H 2O2 solution, stirred at 50 o C for 3 hours, and washed with deionized water to neutrality. The sample was dried in a vacuum oven at 60℃for 6 hours, then added to a solution of 2.5g of N, N' -dicyclohexylcarbodiimide, 0.4g of 4-dimethylaminopyridine and 0.8g of 1-hydroxybenzotriazole in 100ml of dimethyl sulfoxide, followed by 70ml of a solution of polyvinyl alcohol in dimethyl sulfoxide (160 mg/ml), stirred at a constant temperature of 50℃for 15 hours, after the completion of the reaction, suction-filtered, acetone-washed until the filtrate became neutral, and the product was vacuum-dried at 60℃for 6 hours to obtain a polyvinyl alcohol-directly modified retinervus luffae fructus, the adsorption properties of which were measured according to the adsorption property test of the product of example 1, the results of which are shown in Table 1.
Comparative example 3
A preparation method of hydroxyl-enriched modified retinervus Luffae fructus comprises the same steps as those in (i) and (ii) in example 1, but without step (iii). The product's performance was measured by the adsorption performance test of the product of example 1, and the results are shown in Table 1.
Comparative example 4
A preparation method of L-cysteine modified retinervus Luffae fructus comprises the following steps:
1g of pretreated retinervus Luffae fructus (pretreatment method is the same as in example 1) was weighed and dispersed in 100ml of dimethyl sulfoxide solution, then 2g L-cysteine and 6g polyphosphoric acid were sequentially added, the mixture was stirred and refluxed in a water bath at 80 ℃ for 4 hours, suction filtration was performed, ethanol was washed until the filtrate was neutral, and the product was dried in vacuo at 60 ℃ for 6 hours to obtain L-cysteine modified retinervus luffae fructus, the adsorption performance of which was determined according to the adsorption performance test of the product of example 1, and the results are shown in Table 1.
TABLE 1 adsorption amount of lead ions by modified retinervus Luffae fructus prepared in examples 1-9 and comparative examples 1-4
The above results show that the more the functional groups on the surface of the loofah sponge are, the stronger the adsorption capacity of heavy metals is. In comparative example 1, only the retinervus Luffae fructus was modified with carboxyl groups, and the surface active sites (-OH) of retinervus Luffae fructus were limited, so that the amount of carboxyl groups introduced was limited, and the adsorption amount of lead ions was limited. In comparative example 2, polyvinyl alcohol with rich hydroxyl groups was directly grafted on the surface of retinervus Luffae fructus by a one-step esterification method. Because polyvinyl alcohol molecules are larger, a small number of binding sites are difficult to fix on the surface of the loofah in a large number and stably, and the adsorption quantity of lead ions of the modified loofah is not obviously improved. In comparative example 3, a polycarboxylic compound was used as a "bridge", and polyvinyl alcohol was grafted onto the surface of retinervus Luffae fructus by two-step esterification. As can be seen from comparison of comparative examples 2 and 3, the multi-step grafting method effectively increases the grafting rate of polyvinyl alcohol, so that a large number of hydroxyl groups are introduced into the surface of the loofah sponge, and the adsorption capacity of the loofah sponge on lead ions is remarkably improved. In comparative example 4, the hydroxyl groups on the surface of the pretreated retinervus luffae fructus are directly used as anchor points, and L-cysteine is directly grafted on the surface of the retinervus luffae fructus, compared with the example (a large number of hydroxyl groups on polyvinyl alcohol grafted on the surface of the retinervus luffae fructus are used as anchor points), the grafting rate of the L-cysteine is affected due to the small number of anchor points in comparative example 4, so that the adsorption performance of the material is affected.

Claims (7)

1. The preparation method of the multifunctional modified loofah sponge heavy metal adsorbent is characterized by comprising the following steps of:
(i) Adding the loofah pretreated by alkali liquor into an N, N-dimethylformamide solution dissolved with stannous chloride, and then adding a natural polycarboxy compound to react to obtain carboxyl modified loofah, wherein the natural polycarboxy compound is one of malic acid, tartaric acid and citric acid, and the dosage ratio of the loofah pretreated by alkali liquor, the natural polycarboxy compound, the stannous chloride and the N, N-dimethylformamide is 1g (0.5-1.5) g (0.1-0.3) L;
(ii) The carboxyl modified loofah is modified by polyvinyl alcohol to obtain hydroxyl-rich loofah, specifically, the carboxyl modified loofah is added into a dimethyl sulfoxide solution in which N, N-dicyclohexylcarbodiimide, 4-dimethylaminopyridine and 1-hydroxybenzotriazole are dissolved, and then the dimethyl sulfoxide solution of the polyvinyl alcohol is added for modification reaction, wherein the dosage ratio of the carboxyl modified loofah to the N, N-dicyclohexylcarbodiimide to the 4-dimethylaminopyridine to the 1-hydroxybenzotriazole to the dimethyl sulfoxide before the dimethyl sulfoxide solution of the polyvinyl alcohol is added is 1mg: (1.5-3) g (0.2-0.6) g (0.6-0.9) g (0.1-0.3) L, and the mass ratio of the added polyvinyl alcohol to the carboxyl modified loofah is (5-15) 1;
(iii) The hydroxy-rich loofah sponge is modified by L-cysteine to obtain a multifunctional group modified loofah sponge heavy metal adsorbent, specifically, the hydroxy-rich loofah sponge is dispersed in dimethyl sulfoxide solution, then L-cysteine and polyphosphoric acid are sequentially added to carry out modification reaction, wherein the dosage ratio of the hydroxy-rich loofah sponge to the L-cysteine to the polyphosphoric acid to the dimethyl sulfoxide is 1g (1-3 g) (3-9 g) (0.05-0.2) L.
2. The method for preparing the multifunctional modified retinervus luffae fructus heavy metal adsorbent according to claim 1, wherein the reaction solution obtained after adding the natural polycarboxy compound in the step (i) is stirred at a constant temperature of 100-120 ℃ for reaction for 3-5 hours, and the carboxyl modified retinervus luffae fructus is obtained after the reaction, suction filtration, washing and drying.
3. The method for preparing the multifunctional modified retinervus luffae fructus heavy metal adsorbent according to claim 1, wherein the average molecular weight of the polyvinyl alcohol in the step (ii) is 50000-100000, and the concentration of the dimethyl sulfoxide solution of the polyvinyl alcohol is 140-180 mg/ml.
4. The method for preparing the multifunctional modified retinervus luffae fructus heavy metal adsorbent according to claim 1, wherein in the step (ii), when the dimethyl sulfoxide solution of polyvinyl alcohol is added for modification reaction, the reaction solution is stirred at a constant temperature of 40-60 ℃ for reaction for 10-20 hours, and after the reaction, the hydroxyl-rich retinervus luffae fructus is obtained by suction filtration, washing and drying.
5. The method for preparing the multifunctional modified retinervus luffae fructus heavy metal adsorbent according to claim 1, wherein in the step (iii), when L-cysteine and polyphosphoric acid are added for modification reaction, the reaction solution is stirred at a constant temperature of 60-90 ℃ for reaction for 3-6 hours, and after the reaction, suction filtration, washing and drying are performed to obtain the multifunctional modified retinervus luffae fructus heavy metal adsorbent.
6. The preparation method of the multifunctional modified retinervus Luffae fructus heavy metal adsorbent according to claim 1, wherein the alkali liquor pretreatment is to soak retinervus Luffae fructus in 2% -15% KOH aqueous solution, stir at 60-100deg.C for 1-5 h, and wash with deionized water to neutrality.
7. A multifunctional modified retinervus luffae fructus heavy metal adsorbent, which is characterized by being prepared by the preparation method of the multifunctional modified retinervus luffae fructus heavy metal adsorbent according to any one of claims 1 to 6, wherein the chemical structural formula of the multifunctional modified retinervus luffae fructus heavy metal adsorbent is as follows:
Wherein R represents retinervus Luffae fructus.
CN202410585359.3A 2024-05-13 2024-05-13 Multifunctional group modified loofah sponge heavy metal adsorbent and preparation method thereof Active CN118162115B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101670273A (en) * 2009-09-28 2010-03-17 济南大学 Preparation method and application of hydrosulphonyl functionalized loofah
CN103447009A (en) * 2013-09-26 2013-12-18 济南大学 Preparation and application of cysteine modified loofah adsorbent

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CN103566907B (en) * 2013-11-13 2015-07-08 济南大学 Preparation method and application of pyromellitic dianhydride modified loofah sponge adsorbent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101670273A (en) * 2009-09-28 2010-03-17 济南大学 Preparation method and application of hydrosulphonyl functionalized loofah
CN103447009A (en) * 2013-09-26 2013-12-18 济南大学 Preparation and application of cysteine modified loofah adsorbent

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