CN115055170A - Wood-based modified nano-cellulose water purification material with high adsorption performance and preparation method and application thereof - Google Patents
Wood-based modified nano-cellulose water purification material with high adsorption performance and preparation method and application thereof Download PDFInfo
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—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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- 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
- C02F2101/203—Iron or iron compound
-
- 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
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- Chemical & Material Sciences (AREA)
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- 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 invention belongs to the technical field of natural polymer modified materials, and particularly relates to a wood-based modified nano-cellulose water purification material with high adsorption performance, and a preparation method and application thereof. According to the invention, basha is used as a raw material, a porous wood with good elasticity is obtained through delignification treatment, and then a silica coupling agent and functional polymer polyethyleneimine are used for carrying out functional modification on the porous wood, so that the amino-rich composite material is prepared. The water purification material realizes the capability of adsorbing metal ions by utilizing the coordination effect of the amino and the metal ions. The cellulose-based water purification material is prepared by a one-pot method, has mild reaction conditions and extremely short time consumption, has ultrahigh adsorption performance, can quickly and efficiently adsorb metal ions from a water body, and is a water purification material with great potential for adsorbing heavy metal ions in wastewater.
Description
Technical Field
The invention belongs to the technical field of natural polymer modified materials, and particularly relates to a wood-based modified nano-cellulose water purification material with high adsorption performance, and a preparation method and application thereof.
Background
Heavy metals are one of the major pollutants in industrial wastewater. Industrial processes such as mechanical manufacturing, mineral smelting, electroplating, electronic manufacturing, oil refining and chemical processing are main sources of heavy metals, and enter a water environment through sewage discharge, atmospheric sedimentation, rainwater erosion and the like. Heavy metals have the characteristics of high toxicity, difficult degradation, easy biological accumulation and the like, and can generate toxic action on aquatic organisms even at low concentration. Therefore, how to efficiently remove common heavy metal ions from industrial wastewater is one of the major challenges facing researchers.
At present, technologies such as adsorbents, electrospun nanofiber membranes (ENFMs), Porous Organic Polymers (POPs), sulfate-based advanced oxidation processes, carbon-polymer nanocomposite membranes and the like developed from agricultural wastes show huge capacity and potential in the aspect of removing heavy metal pollutants, however, most of researches on the technologies are still in the laboratory exploration stage, and practical application in heavy metal wastewater treatment has many challenges.
Common methods for removing heavy metal ions include membrane separation, extraction, ion exchange, chemical precipitation, and adsorption. The adsorption method is considered as a main method for wastewater treatment because of its advantages such as high efficiency and simple process. Adsorption is a surface phenomenon based on a phase transfer process, in which a substance is transferred from a liquid or gaseous state to a solid surface using an adsorbent as a medium. Generally, the adsorbent is placed in a solution containing the adsorbate and shaken up, and the contaminants are adsorbed on the surface of the adsorbent by chemical or physicochemical action under specific conditions until the adsorption reaches equilibrium. The traditional adsorbent (activated carbon and the like) is limited in practical application due to high cost, poor adsorption capacity and weak cyclic adsorption capacity.
Cellulose is the most abundant natural organic matter in the world, and hemp, wheat straw, rice straw, bagasse, wood and the like are abundant sources of cellulose, and are characterized by being renewable, low in pollution and wide in distribution. The wood as a carbon neutral biomass resource with extremely large application has the advantages of wide source, environmental friendliness, green processing, low price, degradability and the like. The unique multi-stage porous and multi-channel structure of the wood provides a new opportunity for wastewater treatment. The wood-based cellulose material is subjected to oxidation bleaching treatment to remove lignin, so that the fibers are more hydrophilic and porous, and hemicellulose is removed through strong acid hydrolysis, thereby obtaining the fibers with higher aromaticity and lower polarity. Wood-based cellulosic materials tend to consist of interconnected pore systems, providing a relatively high surface area per unit mass. However, untreated cellulose has almost no adsorption capacity, and thus it is necessary to modify hydroxyl groups abundant in cellulose by chemical modification such as oxidation, polymer adsorption, and formation of chemical derivatives or graft polymers on the surface of cellulose material, thereby imparting some groups (amine groups, carboxyl groups, phosphate groups, etc.) chelating heavy metal ions to cellulose, and making it a water purification material having excellent adsorption performance.
The preparation method and application of the modified cellulose-based adsorbent are reported in patent documents. The Chinese patent with the application number of CN201810045195.X discloses a preparation method of modified cellulose aerogel for adsorbing heavy metals, which utilizes corn straws to obtain a cellulose aerogel adsorbent by means of extraction of straw stalk cellulose, preparation of the cellulose aerogel, graft copolymerization of cellulose and the like, but in the preparation process of the adsorbent, a metal solution is required to be heated and dissolved, the conditions are harsh, the energy consumption is high, the obtained modified cellulose adsorbent can be stirred in a heavy metal ion solution for 3 days to achieve adsorption balance, and the efficiency of adsorbing copper ions is low (57 mg/g). The Chinese patent with the application number of CN202010049053.8 discloses an amphiphilic cellulose-based adsorbing material which is prepared by using cellulose as a raw material, firstly performing water-bath ultrasonic-assisted alkalization treatment on the cellulose to prepare regenerated cellulose, then performing free radical polymerization on the regenerated cellulose and styrene to obtain hydrophobic cellulose, and finally introducing carboxyl into the hydrophobic cellulose and anhydride through a Friedel-crafts acylation reaction. However, the pretreatment cost of the technology is high, the operation is complex, the reaction conditions are harsh, and hydrophilic groups are introduced firstly, and then hydrophobic ends are introduced, which often causes the obtained product to have strong hydrophobicity, insufficient dispersibility in water, difficult contact with pollutants, and low copper absorption efficiency (120 mg/g).
Therefore, it is necessary to research a cellulose-based water purification material which is prepared by using biomass resources as raw materials, has a simple preparation process, high heavy metal ion adsorption efficiency and good cyclic regeneration adsorption capacity.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a wood-based modified nano-cellulose water purification material with high adsorption performance, the second purpose of the invention is to provide the wood-based modified nano-cellulose water purification material prepared by the preparation method, and the third purpose of the invention is to provide the application of the wood-based modified nano-cellulose water purification material.
According to a first aspect of the present invention, there is provided a method for preparing a wood-based modified nanocellulose water purification material, comprising the steps of:
mixing delignified porous wood with a silica coupling agent aqueous solution, reacting for 1-2h, then adding Polyethyleneimine (PEI) into a reaction system to obtain a mixed solution, continuing to react for 15-30min, and freeze-drying after the reaction is finished to obtain the wood-plastic composite material.
In an aqueous solution system, polyethyleneimine does not react with cellulose and can not be attached to the surface of the cellulose with strong binding force; in the presence of water, the silica coupling agent is hydrolyzed to generate silicon hydroxyl, and when the polyethyleneimine and the silica coupling agent aqueous solution are simultaneously added into the delignified porous wood, the silicon hydroxyl preferentially reacts with the polyethyleneimine, so that the polyethyleneimine cannot be crosslinked on the cellulose. Therefore, in the process of preparing the wood-based modified nano-cellulose water purification material, delignified porous wood is firstly mixed with a silica coupling agent aqueous solution, the silica coupling agent is hydrolyzed to generate silicon hydroxyl, the silicon hydroxyl and hydroxyl on cellulose are subjected to condensation reaction, then polyethyleneimine is added, and at the moment, an epoxy group at the other end of the silica coupling agent is subjected to ring-opening reaction with an amino group on the polyethyleneimine, so that a polymer network rich in the amino group is formed. Thus, the chelating action of the amine group of polyethyleneimine on metal ions can be utilized to adsorb and treat heavy metal ions in wastewater.
In some embodiments, the method of making delignified porous wood comprises the steps of:
cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, soaking 6-9 blocks in 400-500 mL of boiling deionized water containing 5-10 g of sodium hydroxide and 10-20 g of sodium sulfite, reacting for 4-10 h, taking out after the reaction is finished, then soaking in 50-100mL of sodium chlorite solution with the mass fraction of 0.5-1% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and freeze-drying to obtain the balsa wood.
In some embodiments, the mass-to-volume ratio of delignified porous wood to aqueous silica coupling agent solution is (0.1 to 0.5) g: (50-100) mL.
In some embodiments, the silicone coupling agent is any one of 3-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.
In some embodiments, the silicon-oxygen coupling agent is 3-glycidyloxypropyltrimethoxysilane (KH-560), and the mass fraction of the 3-glycidyloxypropyltrimethoxysilane in the aqueous silicon-oxygen coupling agent solution is 1 to 3%.
In some embodiments, the mass fraction of polyethyleneimine in the mixed solution is 1% to 9%.
In some embodiments, the mass fraction of 3-glycidyloxypropyltrimethoxysilane in the aqueous solution of the silicone coupling agent is 1% and the mass fraction of polyethyleneimine in the mixed solution is 5%.
According to a second aspect of the present invention, there is provided the wood-based modified nanocellulose water purification material prepared by the above-mentioned preparation method.
According to a third aspect of the invention, the application of the wood-based modified nano-cellulose water purification material in the preparation of the heavy metal ion wastewater adsorbent is provided.
In some embodiments, the heavy metal ions are any one or more of Cu, Fe, Cr, Co, Ni, Pb, and Cd ions.
The beneficial effects of the invention include:
(1) according to the invention, basha is used as a raw material, a porous wood with good elasticity is obtained through delignification treatment, and then a silica coupling agent and functional polymer polyethyleneimine are used for carrying out functional modification on the porous wood, so that the amino-rich composite material is prepared. The composite material prepared by the invention realizes the capability of adsorbing metal ions by utilizing the coordination effect of the amino and the metal ions. According to the invention, the copper ions are used as an adsorption model to research the adsorption performance of the prepared composite material, and the composite material has ultrahigh adsorption performance under proper conditions.
(2) The method applies the wood to preparing the adsorption material, and has positive reference value for widening the application range of biomass resource wood and improving the added value of the biomass resource wood. The wood contains a large amount of cellulose, and the cellulose contains abundant primary and secondary hydroxyl groups, and the groups are beneficial to the chemical modification of the wood cellulose. In addition, the nano wood has a better porous structure and excellent compressibility, which provides convenient conditions for the application of the nano wood in subsequent modification and heavy metal ion adsorption.
(3) Nowadays, activated carbon is a common adsorbing material on the market, but the preparation process has harsh conditions, consumes too long time, has poor adsorption capacity, has low recycling rate and is expensive. The wood-based water purification material prepared by the method is prepared by a one-pot method, and grafting modification can be completed within about two and a half hours. The invention uses biomass carbon neutral resource wood in the field of sewage treatment and adsorption, and has positive promotion effect on expanding the types of adsorption materials, replacing commercial adsorbents and the like.
Drawings
FIG. 1 shows the cross-linking ratio of KH-560 to PEI in the adsorption experiment of the invention to Cu of wood-based modified nano-cellulose water purification material 2+ Influence of adsorption capacity results are shown.
FIG. 2 shows Cu of wood-based modified nano-cellulose water purification material by sample mass in adsorption experiment of the invention 2+ Influence of adsorption capacity results are shown.
FIG. 3 shows Cu in the adsorption experiment of the present invention 2+ Cu of wood-based modified nano-cellulose water purification material with initial concentration of solution 2+ Influence of adsorption capacity results are shown.
FIG. 4 shows the adsorption time versus Cu of wood-based modified nano-cellulose water purification material in the adsorption experiment of the present invention 2+ Influence of adsorption capacity results are shown.
FIG. 5 shows Cu in the adsorption experiment of the present invention 2+ Cu of wood-based modified nano-cellulose water purification material by pH of solution 2 + Influence of adsorption capacity results are shown.
FIG. 6 shows the adsorption temperature versus Cu of wood-based modified nano-cellulose water purification material in the adsorption experiment of the present invention 2+ Influence of adsorption capacity results are shown.
FIG. 7 shows the infrared characterization results of the products prepared in example 3 of the present invention and comparative examples 1-2.
Fig. 8 is a scanning electron microscope characterization result of samples prepared in example 3 and comparative example 1 of the present invention.
FIG. 9 shows the EDS characterization results of the sample prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. It should be noted that the term "normal temperature" in the present invention means 15 to 30 ℃; unless otherwise specified, the reagents used in the present invention are commercially available.
Example 1
The preparation method of the wood-based modified nano-cellulose water purification material comprises the following steps:
(1) cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, taking 20g (about 10 blocks) to soak in about 500mL of boiling deionized water containing about 6g of sodium hydroxide and about 18g of sodium sulfite to react for about 5h, taking out after the reaction is finished, then soaking in about 80mL of sodium chlorite solution with the mass fraction of about 1% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and freezing and drying to obtain the delignified porous wood.
(2) Weighing about 0.1g of delignified porous wood, adding about 50mL of 3-glycidyloxypropyltrimethoxysilane (KH-560) aqueous solution with the mass fraction of about 1%, reacting for about 2h, then adding about 1g of Polyethyleneimine (PEI) into the reaction system to obtain a mixed solution with the mass fraction of polyethyleneimine of about 1%, continuing to react for about 30min, and freeze-drying after the reaction is finished to obtain the wood-based modified nano-cellulose water purification material.
Example 2
This example is different from example 1 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 3%.
Example 3
This example is different from example 1 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 5%.
Example 4
This example is different from example 1 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 7%.
Example 5
The preparation method of the wood-based modified nano-cellulose water purification material comprises the following steps:
(1) cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, taking 10g (about 5 blocks) to soak in about 300mL of boiling deionized water containing about 10g of sodium hydroxide and about 15g of sodium sulfite, reacting for about 8h, taking out after the reaction is finished, then soaking in about 50mL of sodium chlorite solution with the mass fraction of about 0.5% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and freeze-drying to obtain the delignified porous wood.
(2) Weighing about 0.1g of delignified porous wood, adding about 50mL of 3-glycidyloxypropyltrimethoxysilane (KH-560) aqueous solution with the mass fraction of about 2%, reacting for about 2 hours, then adding about 1g of Polyethyleneimine (PEI) into the reaction system to obtain a mixed solution with the mass fraction of polyethyleneimine of about 1%, continuing to react for about 30 minutes, and freeze-drying after the reaction is finished to obtain the wood-based modified nano-cellulose water purification material.
Example 6
This example is different from example 5 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution is about 3%.
Example 7
This example is different from example 5 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 5%.
Example 8
This example is different from example 5 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 7%.
Example 9
The preparation method of the wood-based modified nano-cellulose water purification material comprises the following steps:
(1) cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, taking 10g (about 5 blocks) to soak in about 300mL of boiling deionized water containing about 9g of sodium hydroxide and about 20g of sodium sulfite to react for about 8h, taking out after the reaction is finished, then soaking in about 60mL of sodium chlorite solution with the mass fraction of about 0.5% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and obtaining the delignified porous wood after freeze drying.
(2) Weighing about 0.1g of delignified porous wood, adding about 50mL of 3-glycidyloxypropyltrimethoxysilane (KH-560) aqueous solution with the mass fraction of about 3%, reacting for about 2h, then adding about 1g of Polyethyleneimine (PEI) into the reaction system to obtain a mixed solution with the mass fraction of polyethyleneimine of about 1%, continuing to react for about 30min, and freeze-drying after the reaction is finished to obtain the wood-based modified nano-cellulose water purification material.
Example 10
This example is different from example 9 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 3%.
Example 11
This example is different from example 9 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution is about 5%.
Example 12
This example is different from example 9 in that the mass fraction of Polyethyleneimine (PEI) in the mixed solution was about 7%.
Comparative example 1
The preparation method of the unmodified wood-based water purification material of the comparative example comprises the following steps:
(1) cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, taking 10g (about 5 blocks) to soak in about 500mL of boiling deionized water containing about 7g of sodium hydroxide and about 20g of sodium sulfite to react for about 10h, taking out after the reaction is finished, then soaking in about 70mL of sodium chlorite solution with the mass fraction of about 1% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and freeze-drying to obtain the balsa wood.
Cu with a concentration of about 1mg/mL is formulated 2+ About 50mL of the aqueous solution, about 50mg of the porous wood prepared above was sampled, and about 10mL of Cu was charged 2+ Adsorption studies were performed in solution. Sampling and determining Cu after adsorbing for about 10h at normal temperature 2+ The concentration and the result show that the concentration of the copper ions is not basically changed, indicating that the concentration is not changedThe porous wood has no adsorption capacity at all.
Comparative example 2
The preparation method of the KH-560 modified wood-based water purification material of the comparative example comprises the following steps:
(1) cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, taking 20g (about 10 blocks) to soak in about 400mL of boiling deionized water containing about 8g of sodium hydroxide and about 15g of sodium sulfite to react for about 6h, taking out after the reaction is finished, then soaking in about 100mL of sodium chlorite solution with the mass fraction of about 0.5% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and obtaining the delignified porous wood after freeze drying.
(2) Weighing about 0.2g delignified porous wood, adding about 50mL of 3-glycidyloxypropyltrimethoxysilane (KH-560) aqueous solution with the mass fraction of about 1%, reacting for about 2h, and freeze-drying after the reaction is finished to obtain the KH-560 modified wood-based water purification material.
Cu with a concentration of about 1mg/mL is formulated 2+ About 50mL of the aqueous solution, about 50mg of the wood-based water purification material prepared above was charged with about 10mL of Cu 2+ Adsorption studies were performed in solution. Sampling and determining Cu after adsorbing for about 10h at normal temperature 2+ The results show that there was essentially no change in the copper ion concentration, indicating that the modified sample without grafted PEI had no adsorption capacity at all.
Next, in order to verify the adsorption effect of the wood-based modified nano-cellulose water purification material on heavy metal ions, the adsorption performance of the prepared composite material is studied by using copper ions as an adsorption model.
1. Cu of wood-based modified nano-cellulose water purification material based on cross-linking ratio of KH-560 to PEI 2+ Influence of adsorption Capacity
In examples 1-12, the cross-linking ratio of KH-560 to PEI was 1:1, 1:3, 1:5, 1:7, 2:1, 2:3, 2:5, 2:7, 3:1, 3:3, 3:5, 3:7, respectively. To explore the cross-linking ratio of KH-560 to PEI to Cu 2+ Influence of adsorption Capacity, Cu was formulated at a concentration of about 1mg/mL 2+ About 200mL of the aqueous solution was obtained by taking 12 different crosslinking ratios prepared in examples 1 to 12 aboveThe wood-based modified nano-cellulose water-purifying material of example was about 50mg, and about 10mL of Cu was added to each of the materials 2+ Adsorption study is carried out in the solution, and samples are taken for measuring Cu after about 10 hours of normal temperature adsorption 2+ The concentration, specific adsorption results are shown in fig. 1.
As can be seen from FIG. 1, the adsorption amount gradually decreased as the concentration of KH-560 increased, and the adsorption amount gradually increased as the concentration of PEI increased, but when the concentration was too high, the adsorption amount decreased. This is because a gel reaction occurs at a high concentration of the crosslinking ratio. When the crosslinking ratio of KH-560 to PEI is 1:5 th, namely the wood-based modified nano-cellulose water purification material prepared in example 3 to Cu 2+ The adsorption amount of (2) is the highest. Therefore, experimental studies were carried out later using the wood-based modified nanocellulose water purification material prepared in example 3.
2. Cu of sample mass on wood-based modified nano-cellulose water purification material 2+ Influence of adsorption Capacity
Cu with a concentration of about 1mg/mL is formulated 2+ About 300mL of aqueous solution was added to about 10mL of each of 2.5, 5, 7.5, 10, 20, 30, 40, and 50mg of the wood-based modified nanocellulose water-purifying material prepared in example 3 2+ Adsorption studies were performed in solution. Simultaneously, 3 parallel experiments are carried out, and samples are taken to determine Cu after the samples are adsorbed for about 10 hours at normal temperature 2+ The concentration, specific adsorption results are shown in fig. 2.
As can be seen from fig. 2, the amount of adsorption increases with the mass of the sample, because more copper ions can be chelated as the mass of the sample increases. When the mass of the sample exceeds 0.5g/L, the amount of adsorption is gradually decreased because the metal chelate sites of the sample are limited and the adsorption is saturated. When the sample mass is 0.5g/L, the adsorption amount is 158.39mg/g, so that the following experimental study is carried out by adopting 0.5g/L adsorbent.
3、Cu 2+ Cu of wood-based modified nano-cellulose water purification material with initial concentration of solution 2+ Influence of adsorption Capacity
Cu concentrations of about 0.05, 0.1, 0.2, 0.4, 0.6, 0.8 and 1mg/mL were prepared separately 2+ About 50mL of the aqueous solution was taken for each of the different concentrations of copper ionsAbout 10mL of the solution was added, and about 5mg of the wood-based modified nanocellulose water-purifying material prepared in example 3 was added. Simultaneously, 3 parallel experiments are carried out, and samples are taken to determine Cu after the samples are adsorbed for about 10 hours at normal temperature 2+ The concentration, specific adsorption results are shown in fig. 3.
As can be seen from FIG. 3, when Cu 2+ When the initial concentration of the solution is lower, the adsorption capacity of the sample is remarkably increased along with the increase of the concentration, and when the concentration is increased to 0.6mg/mL or higher, the reaction sites of the sample are gradually saturated, and the adsorption capacity gradually approaches to the equilibrium. The overall adsorption curve is a typical L-shaped isotherm indicating residual Cu in the solution 2+ Capacity and sample adsorbed Cu 2+ Capacity ratio with Cu 2+ The initial concentration increases and decreases. Cu 2+ When the initial concentration of the solution is 0.6mg/mL, the adsorption amount is 160.28mg/g, so that 0.6mg/mL Cu is adopted in the following steps 2+ The initial concentration of the solution was investigated experimentally.
4. Cu of wood-based modified nano-cellulose water purification material with adsorption time 2+ Influence of adsorption Capacity
Cu with a concentration of about 0.6mg/mL was formulated 2+ 300mL of aqueous solution, about 50mg of the wood-based modified nanocellulose water-purifying material prepared in example 3 was charged with about 100mL of Cu 2+ In the solution, adsorption studies were performed at 25 ℃. Sampling at adsorption time of about 5, 10, 15, 20, 25, 30, 40, 50, 60, 80, 100, 150, 200, 250, 300, 400, 500, 600min for Cu determination 2+ The concentration, specific adsorption results are shown in fig. 4.
As can be seen from FIG. 4, the adsorption amount increases with time at the first 300min of adsorption, and gradually reaches equilibrium after 300min, and the adsorption amount reaches 156.5 mg/g. Compared with other adsorbents, the wood-based modified nano-cellulose water purification material prepared by the method has high adsorption efficiency because a large amount of amino groups are exposed on the surface of the adsorbent, so that adsorbed cations can easily reach chelating sites; in addition, the adsorbent has porosity and compressibility, which are beneficial to the rapid chelation of heavy metal ions.
5、Cu 2+ pH of solution to wood-based modified nanocelluloseCu of water purifying material 2+ Influence of adsorption Capacity
The pH of the metal ion solution is an important factor affecting the adsorption process. In earlier studies, it was found that, at a pH of 5.5 or more, Cu (OH) visible to the naked eye appears in a copper ion solution 2 Precipitation, therefore solutions with pH below 5.5 were selected for adsorption studies.
Cu concentrations of about 0.6mg/mL at pH of about 2, 2.5, 3, 3.5, 4, 4.5 and 5, respectively 2+ About 50mL of the aqueous solution, and about 10mL of each copper ion solution having different pH was added to about 5mg of the wood-based modified nanocellulose water-purifying material prepared in example 3. Simultaneously, 3 parallel experiments are carried out, and samples are taken to determine Cu after the samples are adsorbed for about 10 hours at normal temperature 2+ The concentration, specific adsorption results are shown in fig. 5.
As can be seen from FIG. 5, the adsorption capacity gradually increased with the increase of pH, and the maximum adsorption amount of 161.79mg/g was reached at pH 4.5. When the pH is low, a high concentration of protons competes with metal ions for adsorption sites of the adsorbent, and therefore, the surface of the sample is positively charged due to electrostatic repulsion, and metal ions of the same charge are difficult to approach active sites of the sample. When the pH was increased to 4.5, the proton concentration in the solution decreased and there were enough amine groups in the sample to chelate Cu 2+ The adsorption capacity increases.
6. Cu of wood-based modified nano-cellulose water purification material by reaction temperature 2+ Influence of adsorption Capacity
Cu with a concentration of about 0.6mg/mL was formulated 2+ About 250mL of aqueous solution, about 5mg of the wood-based modified nano-cellulose water-purifying material prepared in example 3 was added to about 10mL of Cu 2+ In the solution, the adsorption studies were performed in water baths at 4, 15, 25, 35, 45 and 55 ℃ respectively. 3 parallel experiments are carried out simultaneously, samples are taken after the adsorption for about 10 hours to determine Cu 2+ The concentration, specific adsorption results are shown in fig. 6.
As can be derived from FIG. 6, Cu 2+ The adsorption amount of (a) decreases with increasing temperature, indicating that the adsorption process is exothermic. Furthermore, the adsorption enthalpy Δ H<0, the adsorption of the wood-based modified nano-cellulose water purifying material on Cu (II) is also proved to be a releaseAnd (4) carrying out a thermal process. The negative entropy of adsorption Δ S explains the decrease in randomness of the solid-liquid interface during its adsorption process, which is attributed to the substitution of metal ions for hydrated molecules by chelation. The adsorption free energy deltaG is negative, which indicates that the adsorbent sample is opposite to Cu 2+ The adsorption of (b) is spontaneous. So the adsorption efficiency is higher at normal temperature.
In conclusion, the wood-based modified nano-cellulose water purification material prepared by the invention is used for treating Cu 2+ Has higher adsorption capacity, particularly when the cross-linking ratio of KH-560 to PEI is 1:5, the obtained wood-based modified nano-cellulose water purifying material is used for treating Cu 2+ The adsorption amount of (2) is the highest. When the wood-based modified nano-cellulose water purifying material prepared by the invention is used for adsorbing copper ions, the mass of a sample is 0.5g/L, Cu 2+ The initial concentration of the solution is 0.6mg/mL, the adsorption time is 300min, the pH value of the solution is 4.5, and the adsorption temperature has higher adsorption performance at normal temperature.
In addition, the invention also characterizes the products prepared in example 3 and comparative examples 1-2.
The sample prepared in example 3 (PEI-PW for short), the sample prepared in comparative example 1 (PW for short), the sample prepared in comparative example 2 (KH 560-PW for short), and the sample after the copper ions are Adsorbed in example 3 (Adsorbed PEI-PW for short) were subjected to infrared characterization, and the results are shown in FIG. 7. As can be seen from FIG. 7, the KH-560 modified samples prepared in comparative example 2 were 1200 and 900cm, compared to the unmodified samples prepared in comparative example 1 -1 Two peaks appear, which are assigned to the characteristic peaks of the epoxy groups on KH-560. After further modification with PEI, 851cm was obtained due to the ring opening reaction -1 The peak disappears, while some typical peaks belonging to PEI are evident, e.g. 3280cm -1 The new peak is caused by the N-H stretching vibration of the secondary amine; 1570cm -1 And 1475cm -1 The new peak at (A) is caused by N-H bending vibration, 820cm -1 The new peak at (a) is caused by the N-H oscillatory vibration; 2935cm -1 And 2867cm -1 The C-H stretching vibration peak intensity is caused by aliphatic CH 2 -CH 2 The increase of spacers; 1316cm -1 The new peak belongs to C-N elongationAnd (5) contracting and vibrating. The success of the crosslinking reaction is confirmed by the appearance of new peaks and the disappearance of epoxy groups.
Scanning electron microscope characterization is performed on the samples prepared in example 3 and comparative example 1, and the result is shown in fig. 8. From fig. 8(a), we observed that the unmodified sample prepared by comparative example 1 is composed of fibrous and sheet-like structures in a network structure, in which the fibrous structure is dominant. The fiber bundles are loosely interconnected to form a porous network. In contrast, the modified sample prepared in example 3 in fig. 8(b) had a denser structure and more fibrous sheets. This is related to the cross-linking effect of KH-560, which makes the fibers more nearly sheet-like during freezing, and more pronounced after PEI modification, its sheets are tightly connected into a dense network with significantly fewer fiber bundles. It can be seen that, although the samples prepared in example 3 and comparative example 1 have three-dimensional porous structures, the morphologies of the samples are very different.
The sample prepared in example 3 was characterized by EDS, and the results are shown in fig. 9, and it can be seen from fig. 9 that the modified wood contains not only C and O elements belonging to cellulose but also Si and N elements. Wherein Si is the element in the coupling agent KH-560 and N is the elemental composition in the grafted PEI. These results all confirm the success of the crosslinking reaction.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a wood-based modified nano-cellulose water purification material with high adsorption performance is characterized by comprising the following steps:
mixing delignified porous wood with a silica coupling agent aqueous solution, reacting for 1-2h, then adding polyethyleneimine into a reaction system to obtain a mixed solution, continuing to react for 15-30min, and performing freeze drying after the reaction is finished to obtain the lignin-free porous wood.
2. The method for preparing the wood-based modified nano-cellulose water purification material according to claim 1, wherein the method for preparing the delignified porous wood comprises the following steps:
cutting the balsa into blocks with the size of 2.5 multiplied by 1cm, soaking 6-9 blocks in 400-500 mL of boiling deionized water containing 5-10 g of sodium hydroxide and 10-20 g of sodium sulfite, reacting for 4-10 h, taking out after the reaction is finished, then soaking in 50-100mL of sodium chlorite solution with the mass fraction of 0.5-1% until the wood is whitened, fully rinsing with deionized water after the reaction is finished, and freeze-drying to obtain the balsa wood.
3. The method for preparing the wood-based modified nano-cellulose water purification material according to claim 1 or 2, wherein the mass-to-volume ratio of the delignified porous wood to the silica coupling agent aqueous solution is (0.1-0.5) g: (50-100) mL.
4. The method for preparing a wood-based modified nanocellulose water purification material according to claim 1 or 2, wherein said silica coupling agent is any one of 3-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, or 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane.
5. The method for preparing the wood-based modified nano-cellulose water purification material as claimed in claim 4, wherein the silica coupling agent is 3-glycidyloxypropyltrimethoxysilane, and the mass fraction of the 3-glycidyloxypropyltrimethoxysilane in the silica coupling agent aqueous solution is 1-3%.
6. The method for preparing the wood-based modified nano-cellulose water purification material as claimed in claim 5, wherein the mass fraction of polyethyleneimine in the mixed solution is 1% -9%.
7. The method for preparing the wood-based modified nano-cellulose water purification material according to claim 6, wherein the mass fraction of 3-glycidyloxypropyltrimethoxysilane in the silica coupling agent aqueous solution is 1%, and the mass fraction of polyethyleneimine in the mixed solution is 5%.
8. The wood-based modified nanocellulose water purification material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the wood-based modified nanocellulose water purification material of claim 8 in the preparation of heavy metal ion wastewater adsorbents.
10. The use according to claim 9, wherein the heavy metal ions are any one or more of Cu, Fe, Cr, Co, Ni, Pb and Cd ions.
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| CN115401757A (en) * | 2022-09-30 | 2022-11-29 | 荆州文物保护中心 | Dehydration and shaping method of water-saturated wooden cultural relics |
| CN115608331A (en) * | 2022-11-01 | 2023-01-17 | 吉林大学 | Preparation method of hemp material for circularly adsorbing heavy metals |
| CN115709055A (en) * | 2022-11-28 | 2023-02-24 | 东北林业大学 | Wood cellulose-based carbon dioxide adsorption and desorption foam and preparation method thereof |
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| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
| CN111495334A (en) * | 2020-04-22 | 2020-08-07 | 华南农业大学 | Cellulose adsorbent, preparation method and application thereof |
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| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
| CN111495334A (en) * | 2020-04-22 | 2020-08-07 | 华南农业大学 | Cellulose adsorbent, preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115401757A (en) * | 2022-09-30 | 2022-11-29 | 荆州文物保护中心 | Dehydration and shaping method of water-saturated wooden cultural relics |
| CN115401757B (en) * | 2022-09-30 | 2023-08-25 | 荆州文物保护中心 | Dehydration shaping method for saturated wooden cultural relics |
| CN115608331A (en) * | 2022-11-01 | 2023-01-17 | 吉林大学 | Preparation method of hemp material for circularly adsorbing heavy metals |
| CN115608331B (en) * | 2022-11-01 | 2024-01-26 | 吉林大学 | Preparation method of China hemp material for circularly adsorbing heavy metals |
| CN115709055A (en) * | 2022-11-28 | 2023-02-24 | 东北林业大学 | Wood cellulose-based carbon dioxide adsorption and desorption foam and preparation method thereof |
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