CN109012638B - Preparation method of carboxylated hierarchical porous cellulose adsorption balls - Google Patents
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Abstract
The invention relates to a preparation method of cellulose spheres, in particular to a preparation method of carboxylated hierarchical porous cellulose adsorption spheres, and belongs to the technical field of functional materials. The invention dissolves cellulose base raw material in the mixed solution of urea and sodium hydroxide to prepare cellulose solution, and the cellulose solution is dropped into H2SO4/Na2SO4In the coagulation bath, cellulose spheres are prepared. Then adding the cellulose spheres into a mixed solution of citric acid/trisodium citrate, and heating for reaction to prepare different cellulose porous microspheres. The cellulose adsorption balls prepared by the method have good adsorption effect on cationic pollutants, and realize purification treatment on dye wastewater and heavy metal ions.
Description
Technical Field
The invention relates to a preparation method of cellulose spheres, in particular to a preparation method of carboxylated hierarchical porous cellulose adsorption spheres, and belongs to the technical field of functional materials.
Background
With the rapid development of social economy and the continuous acceleration of the modernization process, the water environment pollution becomes a significant problem restricting the green sustainable development of the economic society in China. Therefore, the control and treatment of water pollution become a very urgent task in the current environmental protection work of China. The national science and technology special project of the national science and technology innovation plan also clearly indicates that a batch of core key technologies need to be researched and developed in the aspects of water pollution control and treatment, a batch of integrally-assembled complete technologies and equipment are integrated, three technical systems of watershed water pollution treatment, water environment management and drinking water safety guarantee are formed, and a water environment monitoring and monitoring big data platform is constructed. Therefore, the national importance of water pollution control and treatment can be seen, and the future national investment of energy in the aspect can be expected to continuously rise, which also accords with the trend that the global large pattern continuously attaches importance to the water environment problem. Especially in the population countries, the water resources are scarce, and the treatment problem of the water environment problem is self-evident.
Cellulose is a natural renewable resource with the largest reserve in nature, has the unique advantages of biodegradability, good mechanical properties, easy chemical modification and the like, and is widely concerned in various fields of chemical industry, materials, biology, medicine and the like. In recent years, with the continuous attention of all countries around the world to energy and environmental issues, cellulose and its derivatives have been widely studied in the field of water pollution control.
At present, the treatment methods of industrial wastewater mainly comprise flocculation, extraction, adsorption, membrane separation and other methods. Among them, the adsorption method is considered to be the most potential sewage purification measure and has a good application prospect due to the advantages of simple operation, wide application range, good treatment effect, no secondary pollution, recyclable useful substances, renewable and reusable adsorbents, and the like.
Disclosure of Invention
The invention provides a preparation method of a carboxylated multi-stage pore cellulose adsorption ball, and the cellulose adsorption ball prepared by the method has good adsorption effect on cationic pollutants, and realizes purification treatment on dye wastewater and heavy metal ions.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a carboxylated multi-stage pore cellulose adsorption ball comprises the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/LNa2SO4Dripping the 4% cellulose solution prepared in the step (1) into a coagulating bath by a peristaltic pump with a needle head to obtain uniform cellulose balls with good mechanical properties;
(3) 10g of wet cellulose balls are placed in a treatment fluid for 30min-60min by ultrasonic treatment, the treatment fluid is an aqueous solution containing 2-8% of citric acid and 0.5-2% of trisodium citrate, the aqueous solution is dried and then heated to 100 ℃ and 130 ℃ for reaction for 2-8 hours, and the carboxylated hierarchical porous cellulose adsorption balls are obtained.
The invention dissolves cellulose base raw material in the mixed solution of urea and sodium hydroxide to prepare cellulose solution, and the cellulose solution is dropped into H2SO4/Na2SO4In the coagulation bath, cellulose spheres are prepared. Then adding the cellulose spheres into a mixed solution of citric acid/trisodium citrate, and heating for reaction to prepare different cellulose porous microspheres.
The specific surface area of the multi-stage pore cellulose adsorption ball is 156.86m2And the catalyst has good adsorption effect on cationic pollutants, and realizes purification treatment on dye wastewater and heavy metal ions. The method has the advantages of simple preparation process, wide raw material source, low price, little pollution, cyclic utilization and environmental protection. The porous cellulose microsphere prepared by the method is more regular, the maximum adsorption capacity reaches 461.621mg/g, and the porous cellulose microsphere has quick response.
Preferably, the waste cellulose-based material is selected from one or more of waste cotton fiber, waste hemp fiber, waste viscose fiber, rice straw, sugarcane, chaff and corncob.
Preferably, the surface of the carboxylated hierarchical porous cellulose adsorption ball is provided with macro pores of 30-50 μm and macro pores of 1-2 μm, the interior of the adsorption ball is of a mutually communicated rich pore structure, the surface functional group content is high, and the carboxyl content is 1.6-3.8 mol/g.
Preferably, the drying time of the step (3) is 4-8 h. The invention puts the wet cellulose porous microsphere into the mixed solution of citric acid and trisodium citrate, carries out ultrasonic treatment for 0.5h, dries at 65 ℃ for 6h, and continuously increases the acidity in water along with the continuous increase of aqueous solution in the drying process to generate a certain degree of acidolysis on the amorphous area of the cellulose sphere, and because the acidity of the citric acid is not strong and the acidolysis on the cellulose sphere is very slow, the drying time is controlled to be 4-8h, the surface of the modified cellulose porous sphere has 30-50 mu m macropores and 1-2 mu m macropores, and the quick response of the modified cellulose porous sphere is improved.
Compared with the prior art, the invention has the following and positive effects:
(1) the surface of the carboxylated multi-stage porous cellulose adsorption ball is provided with giant pores of 30-50 mu m and macropores of 1-2 mu m, the interior of the adsorption ball is of a mutually communicated rich pore structure, and the content of carboxyl is 1.6-3.8 mol/g.
(2) The porous cellulose microspheres are prepared by adopting the waste cellulose base as a raw material, so that the manufacturing cost is reduced, and the porous cellulose microspheres are environment-friendly and pollution-free.
(3) The citric acid has wide source, low cost and little pollution.
(4) The prepared cellulose porous microspheres have high regularity, the maximum adsorption capacity of 461.621mg/g, quick response, high adsorption efficiency and strong recycling capacity, and the adsorption capacity of 10 th time of cyclic adsorption is still 87.99 +/-2.26% of the first adsorption capacity (288.81 mg/g).
Drawings
FIG. 1 is an electron micrograph of a cellulose protosphere and a carboxyl-modified cellulose porous sphere of examples 1 to 3 of the present invention;
FIG. 2 is an infrared image of cellulose raw spheres and carboxyl-modified cellulose porous spheres of examples 1 to 3 of the present invention;
FIG. 3 adsorption performance of cellulose raw spheres and carboxyl-modified cellulose porous spheres of examples 1 to 3 of the present invention on methylene blue at different initial concentrations.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of a carboxylated multi-stage pore cellulose adsorption ball comprises the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/L Na2SO4Dripping the 4% cellulose solution prepared in the step (1) into the coagulating bath by a peristaltic pump with a needle head, and cleaning the balls until the pH value of washing water is neutral to obtain uniform cellulose balls with good mechanical properties;
(3) weighing 10g of the wet cellulose porous microspheres obtained in the step (2), soaking the wet cellulose porous microspheres in a mixed solution of 4g of citric acid and 1g of trisodium citrate, carrying out ultrasonic treatment for 0.5h, drying the microspheres at 65 ℃ for 6h, heating the dried microspheres to 120 ℃ for reaction for 6h, and finally washing and soaking the obtained carboxylated cellulose porous microspheres in clean water until the pH value of the washing water is neutral.
(4) And (3) testing the adsorption performance: weighing 0.1g (dry weight) of the carboxylated porous cellulose microspheres obtained in the step (3), adding 100mL of methylene blue solution with the concentration of 100-600mg/L, oscillating at the temperature of 30 ℃ for 4h at the speed of 120 r/min, and calculating the adsorption amount of the carboxylated porous cellulose microspheres to the dye through the concentration change before and after the methylene blue dye is adsorbed, wherein the concentration change can be measured by an ultraviolet spectrophotometer, the characteristic absorption peak of the methylene blue is 664nm, and the concentration before and after the adsorption is measured by an ultraviolet spectrometer to calculate the adsorption amount, and the result is shown in figure 3.
Example 2
A preparation method of a carboxylated multi-stage pore cellulose adsorption ball comprises the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/LNa2SO4Dripping the 4% cellulose solution prepared in the step (1) into the coagulating bath by a peristaltic pump with a needle head, and cleaning the balls until the pH value of washing water is neutral to obtain uniform cellulose balls with good mechanical properties;
(3) weighing 10g of the wet cellulose porous microspheres obtained in the step (2), soaking the wet cellulose porous microspheres in a mixed solution of 4g of citric acid and 1g of trisodium citrate, carrying out ultrasonic treatment for 0.5h, drying the microspheres at 65 ℃ for 6h, heating the dried microspheres to 110 ℃ for reaction for 6h, and finally washing and soaking the obtained carboxylated cellulose porous microspheres in clean water until the pH value of the washing water is neutral.
(4) And (3) testing the adsorption performance: weighing 0.1g (dry weight) of the carboxylated porous cellulose microspheres obtained in the step (3), adding 100mL of methylene blue solution with the concentration of 100-600mg/L, oscillating at the temperature of 30 ℃ for 4h at the speed of 120 r/min, and calculating the adsorption amount of the carboxylated porous cellulose microspheres to the dye through the concentration change before and after the methylene blue dye is adsorbed, wherein the concentration change can be measured by an ultraviolet spectrophotometer, the characteristic absorption peak of the methylene blue is 664nm, and the concentration before and after the adsorption is measured by an ultraviolet spectrometer to calculate the adsorption amount, and the result is shown in figure 3.
Example 3
A preparation method of a carboxylated multi-stage pore cellulose adsorption ball comprises the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/L Na2SO4Dripping the 4% cellulose solution prepared in the step (1) into the coagulating bath by a peristaltic pump with a needle head, and cleaning the balls until the pH value of washing water is neutral to obtain uniform cellulose balls with good mechanical properties;
(3) weighing 10g of the wet cellulose porous microspheres obtained in the step (2), soaking the wet cellulose porous microspheres in a mixed solution of 4g of citric acid and 1g of trisodium citrate, carrying out ultrasonic treatment for 0.5h, drying the microspheres at 65 ℃ for 6h, heating the dried microspheres to 110 ℃ for reaction for 2h, and finally washing and soaking the obtained carboxylated cellulose porous microspheres in clean water until the pH value of the washing water is neutral.
(4) And (3) testing the adsorption performance: weighing 0.1g (dry weight) of the carboxylated porous cellulose microspheres obtained in the step (3), adding 100mL of methylene blue solution with the concentration of 100-600mg/L, oscillating at the temperature of 30 ℃ for 4h at the speed of 120 r/min, and calculating the adsorption amount of the carboxylated porous cellulose microspheres to the dye through the concentration change before and after the methylene blue dye is adsorbed, wherein the concentration change can be measured by an ultraviolet spectrophotometer, the characteristic absorption peak of the methylene blue is 664nm, and the concentration before and after the adsorption is measured by an ultraviolet spectrometer to calculate the adsorption amount, and the result is shown in figure 3.
Example 4
A preparation method of a carboxylated multi-stage pore cellulose adsorption ball comprises the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/L Na2SO4Dripping the 4% cellulose solution prepared in the step (1) into the coagulating bath by a peristaltic pump with a needle head, and cleaning the balls until the pH value of washing water is neutral to obtain uniform cellulose balls with good mechanical properties;
(3) weighing 10g of the wet cellulose porous microspheres obtained in the step (2), soaking the wet cellulose porous microspheres in a mixed solution of 6g of citric acid and 1.5g of trisodium citrate, carrying out ultrasonic treatment for 0.5h, drying the microspheres at 65 ℃ for 6h, heating the dried microspheres to 110 ℃ for reaction for 6h, and finally washing and soaking the obtained carboxylated cellulose porous microspheres in clear water until the pH value of the washing water is neutral.
(4) And (3) testing the adsorption performance: weighing 0.1g (dry weight) of the carboxylated porous cellulose microspheres obtained in the step (3), adding 100mL of methylene blue solution with the concentration of 100-600mg/L, oscillating at the temperature of 30 ℃ for 4h at the speed of 120 r/min, and calculating the adsorption amount of the carboxylated porous cellulose microspheres to the dye through the concentration change before and after the methylene blue dye is adsorbed, wherein the concentration change can be measured by an ultraviolet spectrophotometer, and the characteristic absorption peak of the methylene blue is 664nm, and the concentration before and after the adsorption is measured by an ultraviolet spectrometer to calculate the adsorption amount.
The reaction conditions, carboxyl group contents, and specific surface areas measured after freeze-drying of the carboxyl groups of examples 1 to 3 of the present invention are shown in Table 1.
TABLE 1
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (3)
1. A preparation method of a carboxylated multi-stage pore cellulose adsorption ball is characterized by comprising the following steps:
(1) preparation of cellulose solution: putting the waste cellulose-based material into a dissolving solution containing 7% of sodium hydroxide and 12% of urea, freezing the mixture at-12 ℃ for 2 hours, and performing centrifugal deaeration and impurity removal to obtain a 4% cellulose solution;
(2) preparation of cellulose spheres: at 1M/L H2SO4、80g/LNa2SO4Dripping the 4% cellulose solution prepared in the step (1) into a coagulating bath by a peristaltic pump with a needle head to obtain uniform cellulose balls with good mechanical properties;
(3) 10g of wet cellulose balls are placed in a treatment solution for 30min-60min by ultrasonic treatment, the treatment solution is an aqueous solution containing 2-8% of citric acid and 0.5-2% of trisodium citrate by mass percent, the drying is carried out at the temperature of 65 ℃ for 4-8h, and the drying is carried out at the temperature of 100 ℃ and 130 ℃ for reaction for 2-8 h, so as to obtain the carboxylated hierarchical porous cellulose adsorption balls.
2. The method for preparing carboxylated multi-stage porous cellulose adsorption balls according to claim 1, wherein the method comprises the following steps: the waste cellulose-based material is selected from one or more of waste cotton fiber, waste hemp fiber, waste viscose fiber, rice straw, sugarcane, rice husk and corn cob.
3. The method for preparing carboxylated multi-stage porous cellulose adsorption balls according to claim 1, wherein the method comprises the following steps: the surface of the carboxylated multi-stage pore cellulose adsorption ball is provided with macro pores of 30-50 mu m and macro pores of 1-2 mu m, the interior of the adsorption ball is of a mutually communicated rich pore structure, the surface functional group content is high, and the carboxyl content is 1.6-3.8 mol/g.
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| CN110523389A (en) * | 2019-07-12 | 2019-12-03 | 华南理工大学 | A kind of carboxylated banian aerial root fiber adsorbing substance and the preparation method and application thereof |
| CN110681361A (en) * | 2019-09-21 | 2020-01-14 | 天津大学 | Preparation method and application of magnetic cellulose microspheres with core-shell structure |
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| CN112774639A (en) * | 2020-12-07 | 2021-05-11 | 中国林业科学研究院林产化学工业研究所 | Cellulose magnetic microsphere prepared by improving eucalyptus fiber reactivity and preparation method and application thereof |
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