CN112973807B - Preparation method of spherical bagasse lignocellulose-based anion exchanger - Google Patents
Preparation method of spherical bagasse lignocellulose-based anion exchanger Download PDFInfo
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- CN112973807B CN112973807B CN202110165927.0A CN202110165927A CN112973807B CN 112973807 B CN112973807 B CN 112973807B CN 202110165927 A CN202110165927 A CN 202110165927A CN 112973807 B CN112973807 B CN 112973807B
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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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/16—Cellulose or wood; 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a preparation method of a spherical bagasse lignocellulose-based anion exchanger, which comprises the following steps: (1) pretreatment; (2) dissolution and regeneration forming; (3) quaternization modification; (4) washing and transformation. According to the invention, the lignocellulose pellets with uniform size and consistent appearance are prepared by directly dissolving bagasse with ionic liquid and then regenerating and forming, and the spherical bagasse lignocellulose-based anion exchanger with low cost is obtained by quaternization modification.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a preparation method of a spherical bagasse lignocellulose-based anion exchanger.
Background
Common anionic contaminants in water are chromic acid radicals (CrO 4 2- ) Sulfate radical (SO) 4 2- ) Nitrate radical (NO) 3 - ) Phosphate radical (PO) 4 3- ) Arsenate (AsO) 4 3- ) Cyanate radical (CN-), etc. The anionic pollutants are of a plurality of types and have different biotoxicity and environmental hazard, and the anionic pollutants are characterized by electronegativity in aqueous solution, strong mobility and difficult removal and separation. Ion exchange adsorption is generally considered to be the most direct and efficient method of separating and removing low concentration ionic contaminants from a body of water. The anionic pollutants are not easy to be captured by common water treatment adsorbents such as activated carbon, zeolite and the likeThe anion adsorption materials used and studied at present mainly comprise anion exchange resins (such as domestic D201 and the like), clay mineral materials (such as bentonite and the like), metal oxides, loading materials (such as ZrOOH, feOOH, LDHs and the like) and the like. Among these materials, anion resins have the advantages of high exchange adsorption capacity, stable mechanical and chemical properties, convenient regeneration and recovery of valuable ions, and the like, and are widely used in practical water treatment engineering. However, the ionic resins are expensive and unfavorable for mass application, and the raw materials of the popular styrene and acrylic resins are petrochemical products, so researchers in various countries in the world are always searching and developing alternative functional materials along with the gradual exhaustion of petrochemical resources.
Cellulose is one of the most abundant natural polymers on earth as an important alternative to petrochemicals. Ion exchange adsorption materials based on cellulose have been successfully developed, and it is studied that cellulose-based ion exchangers are superior in protein separation, chromatographic applications and the like, but have defects in water treatment and are not used much. The main reasons are that the steps for extracting and purifying cellulose from natural biomass materials such as straw, wood and the like are complex, the cost is high, and the exchange adsorption capacity of the cellulose-based ion exchanger is generally lower than that of similar commercial anion resins. The natural biomass powder rich in lignocellulose and modified materials thereof are directly applied to remove pollutants in water. However, although the powder type biological adsorbent has better adsorption performance in experimental study, the powder type biological adsorbent is difficult to separate and regenerate, has weaker chemical stability and mechanical property, is not suitable for bed (column) filtration operation, and is difficult to popularize and apply in practice.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a spherical bagasse lignocellulose-based anion exchanger.
The technical scheme of the invention is as follows:
a method for preparing a spherical bagasse lignocellulose-based anion exchanger, comprising the following steps:
(1) Washing bagasse with tap water, drying, and crushing and screening to obtain bagasse powder of 70-90 meshes;
(2) Slowly adding bagasse powder prepared in the step (1) and NaHCO into ionic liquid 1-allyl-3-methylimidazole chloride salt 3 Continuously stirring at 105-115 ℃ for reaction for 0.8-1.2h, extracting the reaction solution by using a syringe, extruding and dripping into 0.1M HCl aqueous solution drop by drop to separate out solidified pellets, standing, washing with deionized water, and drying to obtain lignocellulose pellets;
(3) Mixing the lignocellulose pellets prepared in the step (2), epichlorohydrin and dimethylformamide, stirring and reacting for 1.5-2.5 hours at 95-105 ℃, slowly dripping pyridine, stirring and reacting for 0.5-1.5 hours at 95-105 ℃, slowly adding trimethylamine solution with the concentration of 28-32%, and continuously stirring and reacting for 0.4-0.6 hour at 95-105 ℃;
(4) Washing the material obtained in the step (3) by 45-55% ethanol water solution, 0.08-0.12M NaOH water solution and deionized water in sequence, then soaking in 0.08-0.12M HCl water solution for transformation to Cl - And (3) carrying out loading, then washing with deionized water to be neutral, and drying to obtain the spherical bagasse lignocellulose-based anion exchanger.
In a preferred embodiment of the present invention, the drying in step (1) is carried out at a temperature of 55-65℃for a period of 20-25 hours.
In a preferred embodiment of the present invention, in said step (2), the ionic liquid 1-allyl-3-methylimidazole chloride salt, bagasse powder, naHCO 3 The mass ratio of (2) is 9-11:0.2-0.4:0.02-0.04.
Further preferably, in the step (2), the ionic liquid is 1-allyl-3-methylimidazole chloride, bagasse powder, naHCO 3 The mass ratio of (2) is 10:0.3:0.03.
In a preferred embodiment of the present invention, the temperature of the stirring reaction in step (2) is 110 ℃.
In a preferred embodiment of the present invention, the temperature of the drying in said step (2) is 55-65 ℃ for 10-13 hours.
In a preferred embodiment of the present invention, in the step (3), the ratio of the lignocellulosic pellets, epichlorohydrin, dimethylformamide, pyridine, trimethylamine solution is 0.1-0.3 g:2.5-3.5 mL:3.5-3.7 mL:0.1-0.3 mL:4-6 mL.
Further preferably, in the step (3), the ratio of the lignocellulose pellets, epichlorohydrin, dimethylformamide, pyridine and trimethylamine solution is 0.2 g/3 mL/3.6 mL/0.2 mL/5 mL.
In a preferred embodiment of the present invention, the temperature of the stirring reaction in step (3) is 100 ℃.
In a preferred embodiment of the present invention, the temperature of the drying in step (4) is 55-65 ℃ for 10-13 hours.
The beneficial effects of the invention are as follows: according to the invention, the lignocellulose pellets (LCB) with uniform size and consistent appearance are prepared by directly dissolving the lignocellulose pellets in ionic liquid and then regenerating and forming the lignocellulose pellets, and the spherical bagasse lignocellulose-based anion exchanger (LCB-AE) with low cost is obtained by quaternization modification.
Drawings
Fig. 1 is a process flow diagram of example 1 of the present invention.
FIG. 2 is a photograph showing the appearance of a spherical bagasse lignocellulose-based anion exchanger prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a spherical bagasse lignocellulose-based anion exchanger prepared in example 1 of the present invention.
FIG. 4 is a graph showing the adsorption isotherms of several anions in aqueous solutions of the spherical bagasse lignocellulose-based anion exchanger prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further illustrated and described below by the specific embodiments in combination with the accompanying drawings.
Example 1
As shown in fig. 1, a preparation method of the spherical bagasse lignocellulose-based anion exchanger comprises the following steps:
(1) Pretreatment: washing bagasse with tap water for several times, drying in an air drying oven at 60deg.C for 24 hr, pulverizing and sieving with a plant pulverizer to obtain bagasse powder with particle size of 80 mesh, and storing in a glass dryer.
(2) Dissolving and regenerating and forming: 10g of ionic liquid 1-allyl-3-methylimidazole chloride (AMIMCl) is taken in a three-neck flask, and 0.3g of bagasse powder prepared in the step (1) and 0.03g of NaHCO are weighed 3 Slowly adding, continuously stirring at 110 ℃ for reaction for 1h, extracting the reaction solution by using a syringe, extruding and dropwise adding into 0.1M HCl aqueous solution to separate out solidified pellets, standing for several hours, washing with deionized water for 2-3 times, and drying in a 60 ℃ oven for 12h to obtain the lignocellulose pellets LCB.
(3) Quaternization modification: weighing 0.2g of LCB material in a three-neck flask, respectively weighing 3mL of Epichlorohydrin (ECH) and 3.6mL of Dimethylformamide (DMF), adding, and stirring at 100 ℃ for reaction for 2h; then slowly dropwise adding 0.2mL of pyridine, and stirring for reaction for 1h; next, 5mL of trimethylamine solution (30% strength) was slowly added to the flask, and the reaction was continued with stirring at 100℃for 5 hours.
(4) Cleaning and transformation: washing the material obtained in the step (4) with 50% ethanol water solution and 0.1M NaOH water solution respectively, washing with deionized water for several times, soaking and washing in 0.1M HCl water solution to convert the product into Cl - Washing the loaded type with deionized water to neutrality; finally, placing the mixture into a vacuum drying oven for drying at 60 ℃ for 12 hours to obtain the spherical bagasse lignocellulose-based anion exchanger LCB-AE.
As shown in FIG. 1, the LCB-AE is light brown, spherical, complete in shape and uniform in diameter, has an average particle diameter of 2.2+/-0.2 mm, is hard to touch and has certain mechanical strength. As shown in FIG. 2, the above LCB-AE pellets were observed under a scanning electron microscope at low magnification and high magnificationLoose surface and porous inside, which belongs to the material with developed pore structure. The chemical element composition of the LCB-AE is found to contain 45.05 percent of C, 6.630 percent of O and 2.28 percent of N through element analysis, and the theoretical maximum anion exchange capacity (namely quaternary ammonium group content) of the LCB-AE is calculated to be 1.63mEq/g from the N content. As shown in FIG. 3, the LCB-AE was tested for CrO in aqueous solution under adsorption conditions of an adsorbent amount of 1g/L, a reaction time of 24h, a temperature of 298.15K and a solution pH of 6.8 4 2- 、NO 3 - 、PO 4 3- 、SO 4 2- Adsorption capacity of plasma, measured adsorption isotherms show that the LCB-AE is specific for CrO at neutral pH 4 2- 、NO 3 - 、PO 4 3- 、SO 4 2- The ion exchange adsorption capacity of the plasma can reach 48.89, 41.35, 31.5 and 39.42mg/g respectively. Experiments also find that the exchange adsorption of the LCB-AE on anions can obtain better adsorption effect under acidic conditions. In conclusion, the LCB-AE material of the invention has stable spherical morphology, uniform particle size and no pollution to CrO in water 4 2- 、NO 3 - 、PO 4 3- 、SO 4 2- The plasma anions have good adsorption effect, are convenient for bed layer filtering operation, and have higher applicability and popularization in the relevant water treatment field.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (3)
1. A preparation method of a spherical bagasse lignocellulose-based anion exchanger is characterized in that: the method comprises the following steps:
(1) Washing bagasse with tap water, drying, and crushing and screening to obtain bagasse powder of 70-90 meshes; drying at 55-65deg.C for 20-25 hr;
(2) Slowly adding the bagasse powder prepared in the step (1) into ionic liquid 1-allyl-3-methylimidazole chloride saltAnd NaHCO 3 Continuously stirring at 110 ℃ for reaction for 0.8-1.2h, extracting the reaction solution by using a syringe, extruding and dripping into 0.1M HCl aqueous solution drop by drop to separate out solidified pellets, standing, washing by using deionized water, and drying at 55-65 ℃ for 10-13h to obtain lignocellulose pellets; ionic liquid 1-allyl-3-methylimidazole chloride salt, bagasse powder and NaHCO 3 The mass ratio of (2) is 9-11, 0.2-0.4, and 0.02-0.04;
(3) Mixing the lignocellulose pellets prepared in the step (2), epichlorohydrin and dimethylformamide, stirring at 95-105 ℃ for reaction of 1.5-2.5-h, slowly dripping pyridine, stirring at 100 ℃ for reaction of 0.5-1.5-h, slowly adding trimethylamine solution with concentration of 28-32%, and continuously stirring at 100 ℃ for reaction for 0.4-0.6h; the ratio of the lignocellulose pellets, the epichlorohydrin, the dimethylformamide, the pyridine and the trimethylamine solution is 0.1-0.3g, 2.5-3.5mL, 3.5-3.7 and mL, 0.1-0.3 and mL, 4-6mL;
(4) Washing the material obtained in the step (3) by 45-55% ethanol water solution, 0.08-0.12M NaOH water solution and deionized water in sequence, then soaking in 0.08-0.12M HCl water solution for transformation to Cl - And (3) carrying out loading, then washing with deionized water to be neutral, and drying at 55-65 ℃ for 10-13 hours to obtain the spherical bagasse lignocellulose-based anion exchanger.
2. The method of manufacturing according to claim 1, wherein: in the step (2), ionic liquid 1-allyl-3-methylimidazole chloride salt, bagasse powder and NaHCO 3 The mass ratio of (2) is 10:0.3:0.03.
3. The method of manufacturing according to claim 1, wherein: in the step (3), the ratio of the lignocellulose pellets, the epichlorohydrin, the dimethylformamide, the pyridine and the trimethylamine solution is 0.2 g/3 mL/3.6 mL/0.2 mL/5 mL.
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Citations (5)
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| CN102423694A (en) * | 2011-08-31 | 2012-04-25 | 广西师范大学 | Preparation method and application of cassava stalk-based anion adsorbent |
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| CN106040177A (en) * | 2016-07-20 | 2016-10-26 | 华侨大学 | Modified activated carbon for removing sulfate radicals in water and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423694A (en) * | 2011-08-31 | 2012-04-25 | 广西师范大学 | Preparation method and application of cassava stalk-based anion adsorbent |
| CN102641728A (en) * | 2012-04-25 | 2012-08-22 | 大连中汇达科学仪器有限公司 | Cellulose/collagen biological adsorbent prepared based on ionic liquid serving as solvent |
| CN102797187A (en) * | 2012-09-07 | 2012-11-28 | 南开大学 | Method for extracting cellulose in biomass raw material by utilizing ionic liquid |
| CN104403110A (en) * | 2014-10-17 | 2015-03-11 | 南开大学 | Method for extracting lignin in biomass material by using ion liquid |
| CN106040177A (en) * | 2016-07-20 | 2016-10-26 | 华侨大学 | Modified activated carbon for removing sulfate radicals in water and preparation method thereof |
Non-Patent Citations (1)
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| Removal of sulphate from aqueous solution using modified rice straw: Preparation, characterization and adsorption performance;Wei Cao et al.;《Carbohydrate Polymers》;20110316;第85卷;摘要，第572页第2.1-2.2节 * |
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