CN113214513B - Porous regenerated cellulose derivative and preparation method and application thereof - Google Patents
Porous regenerated cellulose derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a porous regenerated cellulose derivative and a preparation method and application thereof, comprising the following steps: step 1, adding a raw material into a mixed solution of an ionic liquid and a solvent, and stirring until the raw material is completely dissolved to obtain a raw material solution; the raw material is one of microcrystalline cellulose, absorbent cotton, softwood pulp or hardwood pulp; step 2, adding an epoxy component and an initiator into the raw material liquid, adding amino acid after reaction, and continuing the reaction to obtain a reaction liquid; and 3, pouring the reaction liquid into a mould or casting and paving a film on a support material, then placing the film in a gel bath, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous regenerated cellulose derivative. The regenerated cellulose derivative has obviously different morphological structures and crystal structures, which is also beneficial to improving the adsorption performance of the regenerated cellulose derivative.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a porous regenerated cellulose derivative, and a preparation method and application thereof.
Background
The synthetic dye has the advantages of low cost, bright color, washing resistance and the like, and is widely applied to the industries of textile, pulping, papermaking, leather, food, printing, plastics and the like. However, 10-15% of the dye is discharged into the wastewater after the production process because it is not utilized, thereby generating a large amount of colored wastewater. At present, the colored wastewater is treated by a combined method of flocculation sedimentation/activated sludge biodegradation and the like. However, the chroma of the wastewater treated by the method is still high, the discharge requirement cannot be met, and further deep decolorization treatment is required.
Adsorption is the most widely used dye removal method at present, and has the obvious advantages that: the process flow and the operation are simple, the investment cost is low, the treatment capacity is large, the decolorization rate is high, no chemical is added, the energy consumption is low, the secondary pollution is less, and the adsorbent is expected to be regenerated and reused; the method is particularly suitable for removing the non-biodegradable dye with low content and good water solubility in the wastewater. In recent years, researches on an adsorption decolorization method mainly focus on developing a novel efficient environment-friendly adsorbent which is wide in dye application range and can be repeatedly used, so that the accumulation of dye in the environment is reduced or eliminated, the colored wastewater is safer and more economical to treat, and increasingly strict environment-friendly requirements are met.
Cellulose is the most abundant renewable polymer in nature. Cellulose molecules contain a plurality of reactive hydroxyl groups, and a novel cellulose derivative adsorbent is expected to be obtained through functional modification. Cellulose is insoluble in general organic solvents and water. Heterogeneous functionalization modification of cellulose in an aqueous phase has low efficiency and poor effect, and a satisfactory cellulose derivative is difficult to obtain.
The adsorption performance of cellulose derivatives is influenced by factors such as chemical composition, aggregation structure and specific surface area. At present, cellulose derivatives are mainly prepared by two modification methods, namely heterogeneous modification and homogeneous modification. The cellulose derivative prepared by the heterogeneous modification method of cellulose has an aggregation structure (including crystallinity and crystal form) similar to that of a cellulose raw material, and the change degree is small; and the form is basically not different from the cellulose raw material, which is not beneficial to the improvement of the adsorption performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a porous regenerated cellulose derivative, a preparation method and application thereof, and the porous regenerated cellulose derivative has better adsorption performance.
The invention is realized by the following technical scheme:
a method for preparing a porous regenerated cellulose derivative, comprising the steps of:
step 1, adding a raw material into a mixed solution of an ionic liquid and a solvent, and stirring until the raw material is completely dissolved to obtain a raw material solution; the raw material is one of microcrystalline cellulose, absorbent cotton, softwood pulp or hardwood pulp;
step 2, adding an epoxy component and an initiator into the raw material liquid, adding amino acid after reaction, and continuing the reaction to obtain a reaction liquid;
and 3, pouring the reaction liquid into a mould or casting and spreading a film on a support material, then placing the mould into a gel bath, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous regenerated cellulose derivative.
Preferably, in step 3, the gel bath is one or more of water, formic acid and ethyl acetate.
Preferably, in step 2, after the reaction, the amino acid and the amino silicone oil are added for continuous reaction to obtain a reaction solution.
Further, the dosage of each component is as follows according to the mass portion: 40-100 parts of raw materials; 400-1000 parts of ionic liquid; 80-150 parts of a solvent; 30-70 parts of an epoxy component; 0.5-2.0 parts of an initiator; 20-50 parts of amino acid and 1.0-5.0 parts of amino silicone oil.
Preferably, in step 1, the ionic liquid is one of 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole trifluoromethanesulfonate and 1-allyl-3-methylimidazole chloride salt.
Preferably, in step 1, the solvent is one or more of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in the step 2, the initiator is one of potassium persulfate and ammonium persulfate; the amino acid is one of lysine, glutamine, asparagine, arginine, histidine and tryptophan.
Preferably, in step 2, the epoxy component is one of glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
The porous regenerated cellulose derivative obtained by the preparation method is adopted.
The porous regenerated cellulose derivative is used as an adsorbent in the decolorization of industrial wastewater.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a cellulose homogeneous phase modification method, takes ionic liquid/solvent as a reaction medium, and cellulose derivatives obtained by modification in the ionic liquid/solvent medium are in a dissolved state; meanwhile, the modification degree is higher, and the regeneration process of the cellulose derivative also changes the aggregation state structure (the crystallization index is reduced, and the crystallization crystal form is changed from the original cellulose I form to the cellulose II form). Therefore, compared with the cellulose raw material, the regenerated cellulose derivative has obviously different morphological structure and crystal structure, which is also beneficial to improving the adsorption performance.
Furthermore, when the cellulose is subjected to functional modification, a small amount of amino silicone oil is added, so that the toughness of the regenerated cellulose derivative adsorbent can be improved.
Further, at present, there are very few cellulose derivative adsorbents that can simultaneously process anionic dyes and cationic dyes and are renewable. According to the invention, a polymerizable epoxy component is firstly adopted to carry out graft polymerization modification on cellulose, and then amino acid (lysine, glutamine, asparagine, arginine, histidine and tryptophan) is adopted to further functionalize a reaction product, so that the obtained cellulose derivative contains an amino acid structure, and the pH-responsive adsorption/desorption effect is endowed with, namely, the anionic dye can be adsorbed under an acidic condition, and the anionic dye can be desorbed under an alkaline condition; and can adsorb the cationic dye under the alkaline condition and desorb the cationic dye under the acidic condition.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of (a) microcrystalline cellulose and (b) a porous regenerated cellulose derivative.
FIG. 2 is an X-ray diffraction curve of microcrystalline cellulose and porous regenerated cellulose derivatives.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the porous regenerated cellulose derivative comprises the following steps in parts by weight:
dissolving 40-100 parts of raw materials in 400-1000 parts of ionic liquid and 80-150 parts of solvent, and stirring at 25-100 ℃ until the raw materials are dissolved. Then adding 30-70 parts of epoxy component and 0.5-2.0 parts of initiator, reacting for 0.5-2 hours, adding 20-50 parts of amino acid and 1.0-5.0 parts of amino silicone oil, and continuing to react for 0.5-3 hours. Pouring the reactant into a mould or casting and spreading a film on a supporting material, finally placing the reactant into a gel bath, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
In the preparation method of the porous regenerated cellulose derivative, the raw material is one of microcrystalline cellulose, absorbent cotton, softwood or hardwood pulp; the ionic liquid is one of 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole trifluoromethylsulfonate and 1-allyl-3-methylimidazole chloride salt; the initiator is one of potassium persulfate and ammonium persulfate; the solvent is one or a mixture of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the epoxy component is one of glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate; the amino acid is one of lysine, glutamine, asparagine, arginine, histidine and tryptophan; the molecular weight of the amino silicone oil is 900-4600, and the amino equivalent is 450-2300; the gel bath is one or more of water, formic acid and ethyl acetate.
The invention also provides application of the porous regenerated cellulose derivative in the aspect of industrial wastewater decolorization, which comprises the following steps:
(1) preparing simulated wastewater.
(2) Adding a certain amount of porous regenerated cellulose derivative, and stirring at room temperature.
(3) And (4) measuring the decolorization rate of the wastewater.
In the decolorization application of the above materials, the simulated wastewater contains commercial dyes, anhydrous sodium sulfate, acids (hydrochloric acid, formic acid, acetic acid, sulfuric acid, and the like) and bases (sodium bicarbonate, sodium carbonate, sodium hydroxide, sodium phosphate, and the like); the dye can be a single commercial dye or a plurality of commercial dyes; the dye concentration is 10-1000 mg/L; the concentration of the anhydrous sodium sulfate is 0-80 g/L; the dosage of the porous regenerated cellulose derivative is 10-1000 mg/L.
The properties of the porous regenerated cellulose derivative can be detected by adopting the following indexes:
(1) the appearance is as follows: the adsorbent is brittle-broken by liquid nitrogen, and the appearance of the adsorbent is observed under 5kV high pressure by using an SU-1510 type scanning electron microscope of Hitachi, Japan after the section is sprayed with gold.
(2) The crystal structure is as follows: the test was carried out using an X-ray diffractometer. And (3) testing conditions are as follows: the copper target Cu K α (λ ═ 0.1541nm), power 1600W (40kV × 40mA), 2 θ angle scan range 5 to 40 °, scan speed 2 °/min. The crystallinity of the sample is expressed as a crystallinity index, which is calculated by the formula:
crystallization index ═ I (I)cr-Iam)/Icr×100％
In the formula: i iscrIs the intensity of the diffraction peak of the crystal face, IamAmorphous region diffraction peak intensity. The diffraction angles of the 002 crystal face and the amorphous region corresponding to the cellulose I type are 22.6 degrees and 18.3 degrees respectively; the diffraction angles of the 020 crystal plane and the amorphous region of the cellulose II are respectively 21.5 degrees and 16.0 degrees.
(3) Tensile property: placing the porous regenerated cellulose derivative adsorbent in a constant temperature and humidity chamber (temperature is 25 deg.C, relative humidity is 65%) for balancing for 48 hr, and cutting into strips with width of 1 cm; the thickness was measured with a film thickness gauge, and the tensile breaking strength and elongation were measured with a microcomputer controlled universal material testing machine (WDW-20 Shanghai Hualong testing Instrument Co., Ltd.), with a test nip of 5cm and a tensile speed of 50 mm/min.
(4) Decolorization rate (D,%): and (3) measuring the absorbance of the dye solution by adopting an ultraviolet-infrared visible spectrophotometer.
The calculation method comprises the following steps:
wherein, C0C is the concentration (mg/L) before and after the wastewater is decolorized respectively; v0And V is the volume (mL) of the wastewater before and after decolorization.
Example 1
(1) 40 parts of microcrystalline cellulose, 800 parts of 1-butyl-3-methylimidazolium chloride ionic liquid and 80 parts of dimethyl sulfoxide are added into a three-neck flask which is provided with mechanical stirring, nitrogen introduction and condensation reflux, and the mixture is heated and mechanically stirred until the microcrystalline cellulose is completely dissolved. After the system was cooled to room temperature, 1.0 part of potassium persulfate was transferred to the three-necked flask, and after 105 parts of glycidyl methacrylate was added, the reaction was carried out at room temperature for 0.5 hour. After that, the nitrogen introduction was stopped, and 108 parts of L-lysine were added to continue the reaction for 3 hours. Pouring the reactant into a mould, placing the mould into gel bath water, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
(2) Preparing 100mL of reactive brilliant red X-3B dye simulation wastewater (pH is 2 and salt is not added) of 150mg/L at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation; preparing 100mL of 150mg/L methylene blue dye simulated wastewater (pH is 12, salt is not added) at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation.
The chemical structural formula of the porous regenerated cellulose derivative prepared in this example is as follows:
the sectional electron scanning electron microscope images of the microcrystalline cellulose and the porous regenerated cellulose derivative are shown in figure 1, and it can be seen that the microcrystalline cellulose and the porous regenerated cellulose derivative are porous structures and are obviously different from the original microcrystalline cellulose. The X-ray diffraction patterns of the microcrystalline cellulose and the porous regenerated cellulose derivative are shown in figure 2, and it can be seen that the diffraction angles corresponding to the diffraction peaks of the microcrystalline cellulose and the porous regenerated cellulose derivative are obviously different, the crystalline form of the microcrystalline cellulose is cellulose I, and the crystalline form of the porous regenerated cellulose derivative is cellulose II.
Example 2
(1) 40 parts of microcrystalline cellulose, 800 parts of 1-butyl-3-methylimidazolium chloride ionic liquid and 80 parts of dimethyl sulfoxide are added into a three-neck flask which is provided with mechanical stirring, nitrogen introduction and condensation reflux, and the mixture is heated and mechanically stirred until the microcrystalline cellulose is completely dissolved. After the system was cooled to room temperature, 1.0 part of potassium persulfate was transferred to the three-necked flask, and after 105 parts of glycidyl methacrylate was added, the reaction was carried out at room temperature for 0.5 hour. After that, the nitrogen introduction was stopped, and 108 parts of L-lysine and 1.0 part of aminosilicone oil were added to continue the reaction for 3 hours. Pouring the reactant into a mould, placing the mould into gel bath water, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
(2) Preparing 100mL of reactive brilliant red X-3B dye simulation wastewater (the pH is 3 and salt is not added) of 150mg/L at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation; preparing 100mL of 150mg/L methylene blue dye simulated wastewater (pH is 11, salt is not added) at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation.
Example 3
(1) 40 parts of microcrystalline cellulose, 800 parts of 1-butyl-3-methylimidazolium chloride ionic liquid and 80 parts of dimethyl sulfoxide are added into a three-neck flask which is provided with mechanical stirring, nitrogen introduction and condensation reflux, and the mixture is heated and mechanically stirred until the microcrystalline cellulose is completely dissolved. After the system was cooled to room temperature, 1.0 part of potassium persulfate was transferred to the three-necked flask, and after 105 parts of glycidyl methacrylate was added, the reaction was carried out at room temperature for 0.5 hour. After that, the nitrogen introduction was stopped, and 108 parts of L-lysine and 1.5 parts of aminosilicone oil were added to continue the reaction for 3 hours. Pouring the reactant into a mould, placing the mould into gel bath water, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
(2) Preparing 100mL of reactive brilliant red X-3B dye simulation wastewater (pH is 4 and salt is not added) of 150mg/L at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation; preparing 100mL of 150mg/L methylene blue dye simulated wastewater (pH is 10, salt is not added) at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation.
Example 4
(1) 40 parts of microcrystalline cellulose, 800 parts of 1-butyl-3-methylimidazolium chloride ionic liquid and 80 parts of dimethyl sulfoxide are added into a three-neck flask which is provided with mechanical stirring, is filled with nitrogen and is subjected to condensation reflux, and the mixture is heated and mechanically stirred until the microcrystalline cellulose is completely dissolved. The system was cooled to room temperature, 1.0 part of potassium persulfate was transferred to the three-necked flask, and 105 parts of glycidyl methacrylate was added thereto to react at room temperature for 0.5 hour. After that, the nitrogen introduction was stopped, and 108 parts of L-lysine and 2.0 parts of aminosilicone oil were added to continue the reaction for 3 hours. Pouring the reactant into a mould, placing the mould into gel bath water, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
(2) Preparing 100mL of reactive brilliant red X-3B dye simulation wastewater (pH is 5 and salt is not added) of 150mg/L at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation; preparing 100mL of 150mg/L methylene blue dye simulated wastewater (pH is 9, salt is not added) at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation.
Example 5
(1) 40 parts of microcrystalline cellulose, 800 parts of 1-butyl-3-methylimidazolium chloride ionic liquid and 80 parts of dimethyl sulfoxide are added into a three-neck flask which is provided with mechanical stirring, nitrogen introduction and condensation reflux, and the mixture is heated and mechanically stirred until the microcrystalline cellulose is completely dissolved. After the system was cooled to room temperature, 1.0 part of potassium persulfate was transferred to the three-necked flask, and after 105 parts of glycidyl methacrylate was added, the reaction was carried out at room temperature for 0.5 hour. After that, the nitrogen introduction was stopped, and 108 parts of L-lysine and 2.5 parts of aminosilicone oil were added to continue the reaction for 3 hours. Pouring the reactant into a mould, placing the mould into gel bath water, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous adsorbent.
(2) Preparing 100mL of reactive brilliant red X-3B dye simulation wastewater (the pH is 6 and salt is not added) of 150mg/L at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation; preparing 100mL of 150mg/L methylene blue dye simulated wastewater (pH is 8, salt is not added) at room temperature, adding 20mg of adsorbent, mechanically stirring at 200rpm/min for 24 hours, and measuring the decolorization rate after centrifugal separation.
The crystalline index, tensile strength, elongation at break and decolorization rate of the porous regenerated cellulose derivative prepared by the invention are shown in table 1:
TABLE 1 crystallinity index, tensile strength, elongation at break and decolorization ratio of porous regenerated cellulose derivatives
The above data show that: the porous regenerated cellulose derivative adsorbent prepared by the invention has a obviously reduced crystallization index (the crystallization index of microcrystalline cellulose is 79.9%) and pH response adsorptivity. In addition, the introduction of a small amount of amino silicone oil can surely improve the tensile properties (toughness) of the adsorbent.
The invention respectively adopts materials containing cellulose (such as absorbent cotton, wood pulp, microcrystalline cellulose and the like) as raw materials and ionic liquid/solvent such as 1-butyl-3-methylimidazolium chloride as a reaction medium, firstly adds epoxy components and an initiator to react for a period of time, then adds amino acid and amino silicone oil to react for a period of time, then introduces the solution into a mould or spreads a film on a support material by casting, and finally places the solution in a gel bath to obtain the porous regenerated cellulose derivative. The organic silicon-based organic silicon composite adsorbent is used as an adsorbent to be applied to deep decolorization treatment of industrial colored wastewater, so that the decolorization efficiency is high, and the application range of a decolorizing application dye is wide; the separation and regeneration of the adsorbent after decolorization are very easy.
The ionic liquid/solvent is used as a reaction medium to perform homogeneous functionalization on the cellulose, the modification efficiency is high, the modified cellulose derivative has obviously reduced crystallinity, and the crystallinity of the cellulose derivative can be adjusted by changing the reaction molar ratio of the cellulose to the functional modifier; in addition, the invention adopts an immersion gel phase conversion method to regenerate the cellulose derivative dissolved in the ionic liquid/solvent in the forms of porous foam, porous membrane and the like, and the process has strong variability, namely the pore structure of the regenerated cellulose derivative is adjustable.
Claims (10)
1. A method for preparing a porous regenerated cellulose derivative, comprising the steps of:
step 1, adding a raw material into a mixed solution of an ionic liquid and a solvent, and stirring until the raw material is completely dissolved to obtain a raw material solution; the raw material is one of microcrystalline cellulose, absorbent cotton, softwood pulp or hardwood pulp;
step 2, adding an epoxy component and an initiator into the raw material solution, adding amino acid after reaction, and continuing to react to obtain a reaction solution;
and 3, pouring the reaction liquid into a mould or casting and paving a film on a support material, then placing the film in a gel bath, slowly precipitating and regenerating the cellulose derivative, and freeze-drying to obtain the porous regenerated cellulose derivative.
2. The method for preparing a porous regenerated cellulose derivative according to claim 1, characterized in that in step 3, the gel bath is one or more of water, formic acid and ethyl acetate.
3. The method for preparing a porous regenerated cellulose derivative according to claim 1, characterized in that, in step 2, amino acid and amino silicone oil are added after the reaction to continue the reaction to obtain a reaction solution.
4. The method for preparing a porous regenerated cellulose derivative according to claim 3, characterized in that the amounts of the components are, in parts by mass: 40-100 parts of raw materials; 400-1000 parts of ionic liquid; 80-150 parts of a solvent; 30-70 parts of an epoxy component; 0.5-2.0 parts of an initiator; 20-50 parts of amino acid and 1.0-5.0 parts of amino silicone oil.
5. The method for preparing a porous regenerated cellulose derivative according to claim 1, wherein in step 1, the ionic liquid is one of 1-butyl-3-methylimidazole chloride salt, 1-butyl-3-methylimidazole trifluoromethanesulfonate, and 1-allyl-3-methylimidazole chloride salt.
6. The method for preparing a porous regenerated cellulose derivative according to claim 1, characterized in that in step 1, the solvent is one or more of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
7. The method for producing a porous regenerated cellulose derivative according to claim 1, characterized in that in step 2, the initiator is one of potassium persulfate and ammonium persulfate; the amino acid is one of lysine, glutamine, asparagine, arginine, histidine and tryptophan.
8. The method for preparing a porous regenerated cellulose derivative according to claim 1, wherein in step 2, the epoxy component is one of glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate.
9. A porous regenerated cellulose derivative obtained by the production method according to any one of claims 1 to 8.
10. Use of the porous regenerated cellulose derivative according to claim 9 as an adsorbent for the decolorization of industrial waste water.
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