CN109265611B - Functionalized cellulose-based porous material and preparation method and application thereof - Google Patents

Functionalized cellulose-based porous material and preparation method and application thereof Download PDF

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CN109265611B
CN109265611B CN201811052316.XA CN201811052316A CN109265611B CN 109265611 B CN109265611 B CN 109265611B CN 201811052316 A CN201811052316 A CN 201811052316A CN 109265611 B CN109265611 B CN 109265611B
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CN109265611A (en
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李澧
陈泰文
杨亚莉
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Jiangsu Academy of Agricultural Sciences
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Abstract

The invention discloses a functionalized cellulose-based porous material, which is prepared by the following method: dispersing cellulose main material and functional polymer in mixed aqueous solution of sodium hydroxide and urea or thiourea, freezing at-30-0 ℃, stirring at normal temperature to obtain cellulose-based sol, gelatinizing at normal temperature to obtain porous cellulose gel containing acylamino, and washing with water to neutrality to obtain the cellulose-based functionalized porous material. The invention also discloses application of the functionalized cellulose-based porous material in preventing and treating chroma sewage. The invention can realize the copolymerization of N, N' -methylene bisacrylamide and cellulose molecules without an initiator under the conditions of normal temperature and alkaline environment, and introduces amido bonds on the cellulose molecules in one step, the preparation method is safe, the prepared amidated cellulose-based porous adsorption material contains a large amount of amide groups on the surface and has a porous structure, and the BET specific surface area is not less than 350m2(ii) in terms of/g. Can realize the purification of industrial and food high-chroma waste water.

Description

Functionalized cellulose-based porous material and preparation method and application thereof
Technical Field
The invention belongs to the field of sewage treatment, and relates to a functionalized cellulose-based porous material, a preparation method thereof, and application of the functionalized cellulose-based porous material in treatment of dye sewage, food sewage and colored heavy metal ion sewage.
Background
The chroma sewage has the characteristics of complex components, deep chroma, high salinity, strong acidity and alkalinity and the like. 1) The chroma is deep. Organic matters in the chromaticity sewage mostly take aromatic groups such as benzene, naphthalene, anthracene, quinone and the like as parent bodies, the chromaticity is deep, light cannot enter rivers, algae and other plants cannot perform photosynthesis, and the ecological environment discharged into a water area is seriously influenced. 2) The composition is complex. The chroma sewage not only contains organic matters, but also some colored heavy metal ions and chelates of iron, copper, manganese and the like, and has strong carcinogenic and mutagenic effects on fishes and human beings. 3) The salinity is high. The chroma sewage contains inorganic salts such as chloride, sulfide and the like, and has high concentration and high toxicity. 4) High Chemical Oxygen Demand (COD) and poor biodegradability. The Biochemical Oxygen Demand (BOD)/COD value of organic matters such as benzene series, naphthalene series, anthraquinone series, aniline series, nitro series, phenols and the like is low, and the microbial degradation capability is poor.
At present, the main decolorizing methods of chroma sewage comprise: flocculation, oxidation, biochemical and adsorption. The flocculation method realizes the decolorization of the high-chroma sewage through the mechanisms of the compression of a double electric layer by a flocculating agent, electric neutralization, a bridge action, net-catching sedimentation and the like. The flocculation method has mature process and stable decolorization effect; however, the sludge generated after flocculation and sedimentation can not be recovered, which causes secondary pollution to the environment. The oxidation method is to destroy chromophoric groups of organic matters by using an oxidant to realize the decoloration of high-chroma sewage. The Fenton method has strong oxidation capacity, mild reaction conditions and wide application range, but a large amount of sludge needing incineration treatment is generated in the treatment process, so that secondary pollution to the environment is caused; the photocatalytic oxidation method has the advantages of high energy efficiency, high decolorization efficiency, thorough sludge degradation and the like, but the separation and recovery of the catalyst are difficult, so that potential safety hazards are increased, and the application of the photocatalytic oxidation technology is limited; the electrochemical oxidation method does not need chemical reagents, does not produce sludge, has no toxicity in degradation industry, and can directly discharge the treated sewage. Therefore, the method improves the catalytic performance and the decoloring stability of the electrode material, reduces energy consumption, and is a key research direction of an electrochemical oxidation method. The biochemical method is to degrade colored substances by using microorganisms to realize the decolorization of the high-chroma sewage, and the microorganisms have selectivity on the decomposition of the colored substances, so that the total decolorization effect of a single group of microorganisms on the chroma sewage is poor. The adsorption method is used for removing high-chroma substances in the chroma sewage by means of physical adsorption, chemical adsorption, exchange adsorption and the like, and has the advantages of simple adsorption method, stable decoloring effect and the like. The porous activated carbon is the most commonly used chroma adsorbent, but the activated carbon needs to be regenerated by hot steam after adsorption saturation, so the steps are complicated and the cost is high. Therefore, the development of a novel polymer adsorbent which has high-abundance active groups, low price, safety, no toxicity and no secondary pollution has scientific value and market value.
Cellulose is a long-chain molecule composed of glucopyranose monomers, and the surface of the cellulose contains a large number of hydroxyl groups. The cellulose-based functional materials reported in the literature at present fully utilize active hydroxyl in cellulose monomers, and carry out multi-step modification on the cellulose-based functional materials, so that the aim of functionalizing the cellulose-based materials is finally fulfilled. Such as quaternary amine chain introduced on the surface of cellulose molecule to realize the capability of adsorbing anionic dye[1](ii) a By graft copolymerizing acrylic acid, acrylamide and N, N-methylene-bis (acrylamide), the cellulose adsorbent with surface amide is synthesized to realize the purpose of removing the anionic dye acid blue 93(AB93) and the cationic dye Methylene Blue (MB)[2]. However, no matter the method adopts the method of firstly modifying cellulose to prepare a cellulose-based derivative product and then preparing a functional porous material; and the method for preparing the functional porous material by firstly preparing the cellulose gel and then modifying the gel has the problems of low modification efficiency, complex process, long time consumption and the like.
The most commonly used cellulose solvents today are ionic solvents and sodium hydroxide/urea (thiourea) solutions. The ionic solvent is a strong polar solvent, is difficult to dissolve various organic functional molecules and initiators, is high in price and is not beneficial to industrialization; the sodium hydroxide/urea (thiourea) solution is a strongly alkaline aqueous solution and is difficult to dissolve various organic functional monomers and initiators. Therefore, at present, no method for preparing the porous adsorption material by adopting a cross-linking copolymerization method while preparing the cellulose sol exists.
Reference documents:
[1]Liqiang Jin,Qiucun Sun,Qinghua Xu,Yongjian Xu.Adsorptive removal of anionic dyes from aqueous solutions using microgel based on nanocellulose and polyvinylamine[J].Bioresource Technology,2015,197:348-355
[2]Liu L,Gao Z Y,Su X P,et al.Adsorption Removal of Dyes from Single and Binary Solutions Using a Cellulose-based Bioadsorbent[J].Acs Sustainable Chemistry,2015,3(3):150205104824003.
disclosure of Invention
The invention aims to overcome the defects of complex and tedious process, long consumed time, low modification efficiency and the like of the existing cellulose modification process, and provides a method for preparing a functional cellulose-based porous adsorption material in one step by using cellulose as a main material and crosslinking and copolymerizing functional polymers while the cellulose forms sol, wherein the adsorption material is an amidated cellulose-based adsorption material, can adsorb colored heavy metal ions, anionic dyes and pigments, and can realize purification of industrial high-chroma wastewater.
The purpose of the invention is realized by the following technical scheme:
a functionalized cellulose-based porous material is prepared by the following method: dispersing cellulose main material and functional polymer in mixed aqueous solution of sodium hydroxide and urea or thiourea, freezing at-30-0 ℃, stirring at normal temperature to obtain cellulose-based sol, gelatinizing at normal temperature to obtain porous cellulose gel containing acylamino, and finally washing with water to neutrality to obtain the cellulose-based functionalized porous material.
Another object of the present invention is to provide a method for preparing the functionalized cellulose-based porous material, comprising: dispersing cellulose main materials and functional polymers in a mixed aqueous solution of sodium hydroxide and urea or thiourea, freezing for 30 minutes to 10 hours at the temperature of minus 30 ℃ to 0 ℃, and stirring for 5 minutes to 30 minutes at normal temperature after freezing to obtain cellulose-based sol; standing for 2-36 hours at normal temperature to obtain the porous cellulose gel containing the amide group; and (4) washing with water to be neutral to obtain the amidated porous cellulose adsorbing material.
The cellulose main body material is purified cellulose, paper pulp, alpha-cellulose and the like. The purified cellulose is high-purity fiber extracted from plants, and the cellulose content is 85-95%; the paper pulp is straw pulp, needle leaf pulp and the like, and the water content in the paper pulp is not more than 20%.
The functional polymer is N, N' -methylene bisacrylamide (CAS number: 110-26-9).
The mass ratio of the cellulose main body material to the functional polymer is 1: 0.2-1.5, preferably 1: 0.2-1, more preferably 1: 0.5-1, and most preferably 1: 0.5-0.6.
The mass ratio of the cellulose main body material to the mixed aqueous solution of sodium hydroxide and urea or thiourea is 1: 14-50, and preferably 1: 19-49.
The mass ratio of the sodium hydroxide to the urea or the thiourea to the water is 2-10: 3-15: 75-95, and preferably 3-8: 10-15: 77-87.
The normal temperature is 15-35 ℃.
The invention also aims to provide application of the functionalized cellulose-based porous material in controlling color sewage.
The color sewage contains at least one of copper ions, iron ions, cobalt ions, manganese ions, methyl orange, acid black, acid red, acid blue, methylene blue, methyl green, caramel pigment, carmine, lemon yellow, sunset yellow and brilliant blue.
Preferably, the chroma sewage is colored heavy metal sewage, dye wastewater or pigment wastewater.
Compared with the prior art, the invention has the beneficial effects that:
the invention can realize the copolymerization of N, N' -methylene bisacrylamide and cellulose molecules without an initiator under the conditions of normal temperature and alkaline environment, and introduces amido bonds on the cellulose molecules in one step, the preparation method is safe, the prepared amidated cellulose-based porous adsorption material contains a large amount of amide groups on the surface and has a porous structure, and the BET specific surface area is not less than 350m2(iv)/g, with no N, N' -methylene-bis-propeneCompared with the amide modified cellulose-based porous adsorption material, the BET specific surface area is improved by at least 16 percent and can reach about 65 percent at most.
The amidated cellulose-based porous adsorption material can realize the purification of industrial and food high-chroma wastewater. The concrete expression is as follows:
(1) within 2 hours, the removal amount of copper ions by the amidated cellulose-based porous adsorption material is more than 200 mg/g;
(2) within 2 hours, the removal rate of the amidated cellulose-based porous adsorption material to iron ions can reach 250 mg/g;
(3) within 2 hours, the removal rate of the amidated cellulose-based porous adsorption material to cobalt ions can reach 130 mg/g;
(4) within 2 hours, the removal rate of the amidated cellulose-based porous adsorption material to manganese ions can reach 150 mg/g;
(5) within 2 hours, the removal rate of the amidated cellulose-based porous adsorption material to methyl orange can reach 450 mg/g;
(6) within 2 hours, the removal rate of the amidated cellulose base porous adsorption material to the acid black 1 can reach 450 mg/g;
(7) within 2 hours, the removal rate of acid fuchsin by the amidated cellulose-based porous adsorption material can reach 200 mg/g;
(8) and within 2 hours, the removal rate of the amidated cellulose-based porous adsorption material to the acid blue can reach 200 mg/g.
Drawings
FIG. 1 is a Fourier infrared spectrum of a porous adsorption material prepared by using alpha-cellulose as a main material; a is the Fourier infrared spectrum of the alpha-cellulose-based porous adsorption material prepared in comparative example 1, and B is the Fourier infrared spectrum of the 0.6Bis alpha-cellulose-based porous adsorption material prepared in example 2; the 0.6Bis alpha-cellulose-based porous adsorption material is in the range of 1590-1650cm-11 new strong absorption peak appears in the wave band, which is corresponding to the expansion vibration peak of amido N-H, and the Fourier infrared spectrum of the Bis alpha-cellulose base porous adsorption material prepared in the examples 1 and 3 is also 1590-1650cm-11 new strong absorption peak appears in the wave band, wherein, 0.6Bis alpha-cellulose base porous adsorption materialThe material is 1590-1650cm-1The absorption peak of the wave band is strongest; the copolymerization of N, N' -methylene bisacrylamide and alpha-cellulose molecules at normal temperature and in an alkaline environment without an initiator is shown.
Fig. 2 is a graph showing the effect of a porous adsorbent material prepared using α -cellulose as a main material on removal of copper ions.
Fig. 3 is a graph showing the effect of a porous adsorbent material prepared using α -cellulose as a main material on removal of iron ions.
Fig. 4 is a graph showing the effect of removing cobalt ions by a porous adsorbent material prepared using α -cellulose as a host material.
Fig. 5 is a graph showing the effect of a porous adsorbent material prepared using α -cellulose as a main material on removal of manganese ions.
Fig. 6 is a graph showing the effect of a porous adsorbent prepared using α -cellulose as a main material on removing methyl orange.
Fig. 7 is a graph showing the effect of removing acid black 1 by a porous adsorbent prepared using α -cellulose as a host material.
Fig. 8 is a graph showing the effect of a porous adsorbent prepared using α -cellulose as a host material on the removal of acid fuchsin.
Fig. 9 is a graph showing the effect of removing acid blue by a porous adsorbent prepared using α -cellulose as a host material.
FIG. 10 is a Fourier transform infrared spectrum of a porous adsorbent material prepared with straw pulp as a main material; a is a Fourier infrared spectrum of the straw pulp porous adsorbing material prepared in comparative example 2, and B is a Fourier infrared spectrum of the 0.5Bis straw pulp porous adsorbing material prepared in example 5; the 0.5Bis straw pulp porous adsorption material is in 1590--1The wave band shows 1 new absorption peak corresponding to the expansion vibration peak (within the dotted circle) of the amido N-H, and the Fourier infrared spectrum of the Bis straw pulp porous adsorbing materials prepared in the examples 4 and 6 is also 1590--11 new strong absorption peak appears in the wave band, which indicates that N, N' -methylene bisacrylamide is copolymerized with cellulose molecules in straw pulp at normal temperature and in an alkaline environment without an initiator.
Fig. 11 is a graph showing the effect of removing copper ions by a porous adsorbent material prepared using straw pulp as a main material.
Fig. 12 is a graph showing the effect of removing iron ions by a porous adsorbent material prepared using rice straw pulp as a main material.
Fig. 13 is a graph showing the effect of removing cobalt ions by a porous adsorbent material prepared using straw pulp as a main material.
Fig. 14 is a graph showing the effect of removing manganese ions by a porous adsorbent material prepared using rice straw pulp as a main material.
Fig. 15 is a graph showing the effect of a porous adsorbent prepared from straw pulp as a main material on removing methyl orange.
Fig. 16 is a graph showing the effect of removing acid black 1 by a porous adsorbent prepared using straw pulp as a main material.
Fig. 17 is a graph showing the effect of removing acid fuchsin by a porous adsorbent material prepared using rice straw pulp as a main material.
Fig. 18 is a graph showing the effect of removing acid blue from a porous adsorbent material prepared using straw pulp as a main material.
FIG. 19 is a Fourier transform infrared spectrum of a porous adsorbent material prepared with needle pulp as the host material; a is the Fourier infrared spectrum of the needle pulp porous adsorption material prepared in comparative example 3, and B is the 0.5 amidated needle pulp porous adsorption material. The 0.5 amidation needle pulp porous adsorption material is 1590-1650cm-1In the wave band, 1 new absorption peak appears, which is correspondingly an expansion vibration peak (in a dotted circle) of an amide N-H, and shows that N, N' -methylene bisacrylamide and cellulose molecules in needle pulp are copolymerized under normal temperature and alkaline environment without initiating materials.
Fig. 20 is a graph showing the effect of removing copper ions by a porous adsorbent material prepared using needle pulp as a main material.
Fig. 21 is a graph showing the effect of removing iron ions by a porous adsorbent prepared using needle pulp as a main material.
Fig. 22 is a graph showing the effect of removing cobalt ions by a porous adsorbent prepared using a needle blade slurry as a main material.
Fig. 23 is a graph showing the effect of removing manganese ions by a porous adsorbent material prepared using needle blade pulp as a main material.
Fig. 24 is a graph showing the effect of a porous adsorbent prepared using needle blade pulp as a main material on the removal of methyl orange.
Fig. 25 is a graph showing the effect of removing acid black 1 by a porous adsorbent prepared using needle pulp as a main material.
Fig. 26 is a graph showing the effect of removing acid fuchsin by a porous adsorbent prepared using needle pulp as a main material.
Fig. 27 is a graph showing the effect of removing acid blue from a porous adsorbent prepared using needle pulp as a main material.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode.
Example 1
Weighing 5g of alpha-cellulose and 1g N, N '-methylene bisacrylamide, dispersing the alpha-cellulose and the 1g N, N' -methylene bisacrylamide in 245g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 3:12:85), freezing the mixture at the temperature of-12 ℃ for 30 minutes, stirring the frozen mixture at the normal temperature for 5 minutes, standing the frozen mixture at the normal temperature for 2 hours, and soaking the frozen mixture in pure water to be neutral to obtain a 0.2Bis alpha-cellulose-based porous adsorption material, wherein the BET specific surface area of the Bis alpha-cellulose-based porous adsorption material reaches 472m2/g。
Example 2
Weighing 5g of alpha-cellulose and 3g N, N' -methylene bisacrylamide, dispersing in 245g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 3:12:85), freezing at-12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 2 hours at normal temperature, soaking in pure water to be neutral to obtain 0.6Bis alpha-cellulose porous adsorption material, wherein the BET specific surface area of the alpha-cellulose porous adsorption material can reach 456m2/g。
Example 3
Weighing 5g of alpha-cellulose and 5g N, N' -methylene bisacrylamide in parts by mass, dispersing in 245g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 3:12:85), freezing at 12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 2 hours at normal temperature, soaking in pure water to neutrality to obtain 1.0Bis alpha-cellulose porousThe BET specific surface area of the Bis alpha-cellulose porous adsorbing material can reach 437m2/g。
Comparative example 1
Weighing 5g of alpha-cellulose, dispersing the alpha-cellulose in 245g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 3:12:85), freezing the alpha-cellulose at 12 ℃ for 30 minutes, stirring the alpha-cellulose and the urea at normal temperature after freezing the alpha-cellulose for 5 minutes, standing the alpha-cellulose for 2 hours at normal temperature, soaking the alpha-cellulose in pure water to be neutral to obtain the porous adsorption material of the Bis alpha-cellulose, wherein the BET specific surface area of the porous adsorption material of the Bis alpha-cellulose reaches 376m2/g。
Application example 1
Preparing a copper sulfate solution with the concentration of 500 mg/L. 0.05g of each of the α -cellulose porous adsorbing materials prepared in examples 1, 2 and 3 and comparative example 1 was weighed, 50mL of 500mg/L copper sulfate solution was added, and shaking was performed horizontally for 2 hours (200 rpm). As shown in FIG. 2, the atomic absorption spectrum of the supernatant showed that the removal amount of copper sulfate by the Bis α -cellulose porous adsorption material was as low as 301.8mg/g, which is much higher than that of 47.3mg/g by the α -cellulose porous adsorption material prepared in comparative example 1.
Preparing ferric chloride solution with the concentration of 500 mg/L. 0.05g of each of the α -cellulose porous adsorbing materials prepared in examples 1, 2 and 3 and comparative example 1 was weighed, and 50mL of 500mg/L ferric chloride solution was added thereto, followed by horizontal shaking for 2 hours (200 rpm). As shown in FIG. 3, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of ferric chloride by the Bis alpha-cellulose porous adsorbing material can reach 426.7mg/g at least, which is much higher than the removal amount of ferric chloride by the alpha-cellulose porous adsorbing material of 61.2 mg/g.
Preparing a cobalt chloride solution with the concentration of 500 mg/L. 0.1g of each of the α -cellulose porous adsorbing materials prepared in examples 1, 2 and 3 and comparative example 1 was weighed, and 50mL of 500mg/L cobalt chloride solution was added and shaken horizontally for 2 hours (200 rpm). As shown in FIG. 4, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of cobalt chloride by the Bis alpha-cellulose porous adsorption material can reach 196.5mg/g at least, which is much higher than 39.9 mg/g.
Preparing a manganese chloride solution with the concentration of 500 mg/L. 0.1g of each of the α -cellulose porous adsorbing materials prepared in examples 1, 2 and 3 and comparative example 1 was weighed, and 50mL of 500mg/L manganese chloride solution was added and shaken horizontally for 2 hours (200 rpm). As shown in FIG. 5, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of manganese chloride by the Bis alpha-cellulose porous adsorption material can reach 182.9mg/g at least, which is much higher than the removal amount of manganese chloride by the alpha-cellulose porous adsorption material of 37.1 mg/g.
Preparing a methyl orange solution with the concentration of 1000 mg/L. 0.05g of the α -cellulose porous adsorbent obtained in examples 1, 2 and 3 and comparative example 1 was weighed, and 50mL of 1000mg/L methyl orange solution was added and shaken horizontally for 2 hours (200 rpm). As shown in FIG. 6, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of methyl orange by the Bis alpha-cellulose porous adsorbing material can reach 671.2mg/g at least, which is far higher than the removal amount of methyl orange by the alpha-cellulose porous adsorbing material of 103.8 mg/g.
Preparing an acid black 1 solution with the concentration of 1000 mg/L. 0.05g of the α -cellulose porous adsorbent materials prepared in examples 1, 2 and 3 and comparative example 1 were weighed, respectively, and 50mL of 1000mg/L acid black 1 solution was added and shaken horizontally for 2 hours (200 rpm). As shown in FIG. 7, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of the Bis alpha-cellulose porous adsorption material to the acid black 1 can reach as low as 852.8mg/g, which is far higher than the removal amount of the alpha-cellulose porous adsorption material to the acid black 1 of 199.4 mg/g.
An acid fuchsin solution with the concentration of 1000mg/L is prepared. 0.1g of each of the α -cellulose porous adsorbents obtained in examples 1, 2, and 3 and comparative example 1 was weighed, 50mL of 1000mg/L acid fuchsin solution was added, and the mixture was horizontally shaken for 2 hours (200 rpm). As shown in FIG. 8, the atomic absorption spectrum of the supernatant showed that the removal amount of acid fuchsin by Bis alpha-cellulose porous adsorbent was at least 310.1mg/g, which is much higher than the removal amount of acid fuchsin by alpha-cellulose porous adsorbent of 76.3 mg/g.
Preparing an acid blue solution with the concentration of 1000 mg/L. 0.1g of the porous adsorbents for alpha-cellulose prepared in examples 1, 2 and 3 and comparative example 1 were weighed, respectively, and 50mL of 1000mg/L acid blue solution was added and shaken horizontally for 2 hours (200 rpm). As shown in FIG. 9, the atomic absorption spectrum of the supernatant showed that the removal amount of acid blue by Bis α -cellulose porous adsorbent was at least 347.3mg/g, which is much higher than the removal amount of acid blue by α -cellulose porous adsorbent of 95.5 mg/g.
Example 4
Weighing 5g of rice straw pulp (Yingjietong biotechnology, Inc.) and 1.5g N, N' -methylene bisacrylamide, dispersing in 95g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 5:10:85), freezing at-12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 8 hours at normal temperature, soaking in pure water to be neutral to obtain 0.3Bis rice straw pulp porous adsorption material, wherein the BET specific surface area of the rice straw pulp porous adsorption material reaches 395m2/g。
Example 5
Weighing 5g of rice straw pulp and 2.5g N, N' -methylene bisacrylamide, dispersing in 95g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 5:10:85), freezing at-12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 8 hours at normal temperature, soaking in pure water to be neutral to obtain 0.5Bis rice straw pulp porous adsorption material, wherein the BET specific surface area of the rice straw pulp porous adsorption material reaches 421m2/g。
Example 6
Weighing 5g of rice straw pulp and 4.5g N, N' -methylene bisacrylamide, dispersing in 95g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 5:10:85), freezing at-12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 8 hours at normal temperature, and soaking in pure water to be neutral to obtain the 0.9Bis rice straw pulp porous adsorption material. The BET specific surface area of the rice straw pulp porous adsorbing material of the embodiment reaches 417m2/g。
Comparative example 2
Weighing 5g of rice straw pulp, dispersing the rice straw pulp in 95g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 5:10:85), freezing the rice straw pulp at-12 ℃ for 30 minutes, stirring the rice straw pulp at normal temperature for 5 minutes after freezing, standing the rice straw pulp at normal temperature for 8 hours, soaking the rice straw pulp in pure water to be neutral to obtain the rice straw pulp porous adsorption material, wherein the BET specific surface area of the rice straw pulp porous adsorption material reaches 311m2/g。
Application example 2
Preparing a copper sulfate solution with the concentration of 500 mg/L. 0.05g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, and 50mL of 500mg/L copper sulfate solution was added thereto, followed by shaking horizontally for 2 hours (200 rpm). As shown in FIG. 11, the atomic absorption spectrum of the supernatant showed that the removal amount of copper sulfate by the Bis rice straw pulp porous adsorption material was 213.7mg/g at least, which is much higher than 40.4mg/g of copper sulfate by the rice straw pulp porous adsorption material prepared in comparative example 2.
Preparing ferric chloride solution with the concentration of 500 mg/L. 0.05g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, and 50mL of 500mg/L ferric chloride solution was added thereto, followed by shaking horizontally for 2 hours (200 rpm). As shown in FIG. 12, the atomic absorption spectrum of the supernatant showed that the removal amount of ferric chloride by the Bis rice straw pulp porous adsorption material was 281.2mg/g at least, which is much higher than the removal amount of ferric chloride 52.9mg/g by the rice straw pulp porous adsorption material.
Preparing a cobalt chloride solution with the concentration of 500 mg/L. 0.05g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, and 50mL of 500mg/L cobalt chloride solution was added thereto, followed by shaking horizontally for 2 hours (200 rpm). As shown in FIG. 13, the atomic absorption spectrum of the supernatant showed that the removal amount of cobalt chloride by the Bis rice straw pulp porous adsorption material was as low as 232.7mg/g, which is much higher than 49.5 mg/g.
Preparing a manganese chloride solution with the concentration of 500 mg/L. 0.05g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, and 50mL of 500mg/L manganese chloride solution was added thereto, followed by shaking horizontally for 2 hours (200 rpm). As shown in FIG. 14, the atomic absorption spectrum of the supernatant showed that the removal amount of manganese chloride by the Bis rice straw pulp porous adsorption material was as low as 214.6mg/g, which is much higher than 50.3 mg/g.
Preparing a methyl orange solution with the concentration of 1000 mg/L. 0.05g of each of the porous adsorbing materials of straw pulp obtained in examples 4, 5 and 6 and comparative example 2 was weighed, 50mL of 1000mg/L methyl orange solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 15, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of methyl orange per gram of Bis rice straw pulp porous adsorbing material can reach 473.9mg/g at least, which is far higher than the removal amount of methyl orange of 85.1 mg/g.
Preparing an acid black 1 solution with the concentration of 1000 mg/L. 0.05g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, 50mL of 1000mg/L acid black 1 solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 16, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of the acid black 1 per gram of Bis rice straw pulp porous adsorbing material can reach 641.7mg/g at least, which is much higher than 126.8mg/g of the acid black 1 per gram of rice straw pulp porous adsorbing material.
An acid fuchsin solution with the concentration of 1000mg/L is prepared. 0.1g of each of the porous adsorbent materials of rice straw pulp obtained in examples 4, 5 and 6 and comparative example 2 was weighed, 50mL of 1000mg/L acid fuchsin solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in fig. 17, the atomic absorption spectrum of the supernatant showed that the amount of acid fuchsin removed by the Bis rice straw pulp porous adsorbing material was as low as 246.2mg/g, which is much higher than 54.7 mg/g.
Preparing an acid blue solution with the concentration of 1000 mg/L. 0.1g of each of the rice straw pulp porous adsorbing materials obtained in examples 4, 5 and 6 and comparative example 2 was weighed, 50mL of 1000mg/L acid blue solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 18, the atomic absorption spectrum of the supernatant showed that the removal amount of acid blue by Bis straw pulp porous adsorbing material was 298.5mg/g at least, which is much higher than 61.9 mg/g.
Example 7
Weighing 5g of needle leaf pulp (Yinianjiao International trade Co., Ltd.) and 1g N, N' -methylene bisacrylamide, dispersing in 120g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 7:14:79), freezing at 12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing at normal temperature for 36 hours, soaking in pure water to neutrality to obtain 0.2Bis (BET) porous adsorption materialThe specific surface area reaches 619m2/g。
Example 8
Weighing 5g of needle leaf pulp and 2.5g N, N' -methylene bisacrylamide, dispersing in 120g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 7:14:79), freezing at-12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 36 hours at normal temperature, soaking in pure water to neutrality to obtain 0.5Bis (Becton Dickinson) needle pulp fiber porous adsorption material, wherein the BET specific surface area of the needle pulp porous adsorption material can reach 733m2/g。
Example 9
Weighing 5g of needle leaf pulp and 5g N, N' -methylene bisacrylamide, dispersing in 120g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 7:14:79), freezing at 12 ℃ for 30 minutes, and stirring at normal temperature for 5 minutes after freezing to obtain cellulose-based sol; standing for 36 hours at normal temperature, soaking in pure water to neutrality to obtain 1.0Bis (BET) porous adsorption material with BET specific surface area up to 805m2/g。
Comparative example 3
Weighing 5g of needle pulp, dispersing the needle pulp in 120g of mixed aqueous solution of sodium hydroxide and urea (the mass ratio of the sodium hydroxide to the urea to the water is 7:14:79), freezing the mixture at the temperature of-12 ℃ for 30 minutes, stirring the mixture at normal temperature for 5 minutes after freezing, standing the mixture at normal temperature for 36 hours, soaking the mixture in pure water to be neutral to obtain a needle pulp cellulose-based porous adsorption material, wherein the BET specific surface area of the needle pulp porous adsorption material reaches 490m2/g。
Application example 3
Preparing a copper sulfate solution with the concentration of 500 mg/L. 0.05g of each of the needle-pulp porous adsorbing materials obtained in examples 7, 8 and 9 and comparative example 3 was weighed, and 50mL of 500mg/L copper sulfate solution was added thereto, followed by horizontal shaking for 2 hours (200 rpm). As shown in FIG. 20, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of copper sulfate by the Bis needle pulp porous adsorption material can reach 393.2mg/g at least, which is much higher than 58.8mg/g of copper sulfate by the needle pulp fiber porous adsorption material.
Preparing ferric chloride solution with the concentration of 1000 mg/L. 0.05g of each of the needle-pulp porous adsorbing materials prepared in examples 7, 8 and 9 and comparative example 3 was weighed, 50mL of 1000mg/L ferric chloride solution was added, and the mixture was horizontally shaken for 2 hours (200 rpm). As shown in FIG. 21, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of ferric chloride by the Bis needle pulp porous adsorption material can reach 729.8mg/g at least, which is much higher than 158.2 mg/g.
Preparing a cobalt chloride solution with the concentration of 500 mg/L. 0.1g of each of the needle-pulp porous adsorbing materials obtained in examples 7, 8 and 9 and comparative example 3 was weighed, and 50mL of 500mg/L cobalt chloride solution was added thereto, followed by horizontal shaking for 2 hours (200 rpm). As shown in FIG. 22, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of cobalt chloride per gram of Bis (softwood pulp) porous adsorbing material can reach 155.7mg/g at least, and is much higher than the removal amount of cobalt chloride per gram of softwood pulp porous adsorbing material of 42.1 mg/g.
Preparing a manganese chloride solution with the concentration of 500 mg/L. 0.1g of each of the needle-pulp porous adsorbing materials obtained in examples 7, 8 and 9 and comparative example 3 was weighed, and 50mL of 500mg/L manganese chloride solution was added thereto, followed by horizontal shaking for 2 hours (200 rpm). As shown in FIG. 23, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of manganese chloride by the Bis needle-pulp porous adsorption material can reach 172.8m/g g at least, which is much higher than the removal amount of manganese chloride by the needle-pulp porous adsorption material of 38.5 mg/g.
Preparing a methyl orange solution with the concentration of 1000 mg/L. 0.05g of each of the needle-pulp porous adsorbing materials prepared in examples 7, 8 and 9 and comparative example 3 was weighed, 50mL of 1000mg/L methyl orange solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 24, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of methyl orange by the Bis needle-pulp porous adsorbing material can reach 462.1mg/g at least, which is much higher than the removal amount of methyl orange by the needle-pulp porous adsorbing material 79.1 mg/g.
Preparing an acid black 1 solution with the concentration of 1000 mg/L. 0.05g of each of the needle-pulp porous adsorbing materials prepared in examples 7, 8 and 9 and comparative example 3 was weighed, 50mL of 1000mg/L acid black 1 solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 25, the atomic absorption spectrum of the supernatant showed that the removal amount of acid black 1 by the Bis needle pulp porous adsorbent was at least 505.2mg/g, which is much higher than the removal amount of acid black 1 by the needle pulp porous adsorbent, 134.9 mg/g.
An acid fuchsin solution with the concentration of 1000mg/L is prepared. 0.1g of each of the needle-pulp porous adsorbing materials prepared in examples 7, 8 and 9 and comparative example 3 was weighed, 50mL of 1000mg/L acid fuchsin solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 26, the atomic absorption spectrum of the supernatant showed that the amount of acid fuchsin removed by the Bis needle pulp porous adsorbent was as low as 216.2mg/g, which is much higher than the amount of acid fuchsin removed by the needle pulp porous adsorbent, 47.2 mg/g.
Preparing an acid blue solution with the concentration of 1000 mg/L. 0.1g of each of the needle-pulp porous adsorbing materials prepared in examples 7, 8 and 9 and comparative example 3 was weighed, 50mL of 1000mg/L acid blue solution was added, and the mixture was shaken horizontally for 2 hours (200 rpm). As shown in FIG. 27, the atomic absorption spectrum of the supernatant liquid shows that the removal amount of acid blue by the Bis needle pulp porous adsorption material can reach 259.1mg/g at least, which is much higher than the removal amount of acid blue by the straw fiber porous adsorption material 42.8 mg/g.

Claims (10)

1. A functionalized cellulose-based porous material is characterized by being prepared by the following method: dispersing a cellulose main body material and a functional polymer cross-linking agent into a mixed aqueous solution of sodium hydroxide and urea or thiourea, freezing at-30-0 ℃, stirring at normal temperature to obtain cellulose-based sol, gelatinizing at normal temperature to obtain porous cellulose gel containing acylamino, and finally washing with water to be neutral to obtain the cellulose-based functionalized porous material; wherein the functional polymer cross-linking agent is N, N' -methylene bisacrylamide.
2. The functionalized cellulose-based porous material according to claim 1, characterized in that the cellulose-based host material is purified cellulose, pulp, alpha-cellulose.
3. The functionalized cellulose-based porous material according to claim 1, wherein the mass ratio of the cellulose main body material to the functional polymer cross-linking agent is 1: 0.2-1.5; the mass ratio of the cellulose main body material to the mixed aqueous solution of sodium hydroxide and urea or thiourea is 1: 14-50; the mass ratio of the sodium hydroxide to the urea or the thiourea to the water is 2-10: 3-15: 75-95.
4. The functionalized cellulose-based porous material according to claim 3, wherein the mass ratio of the cellulose main body material to the functional polymer cross-linking agent is 1: 0.2-1; the mass ratio of the cellulose main body material to the mixed aqueous solution of sodium hydroxide and urea or thiourea is 1: 19-49; the mass ratio of the sodium hydroxide to the urea or the thiourea to the water is 3-8: 10-15: 77-87.
5. The method for preparing a functionalized cellulose-based porous material according to claim 1, characterized in that it comprises: dispersing a cellulose main body material and a functional polymer cross-linking agent in a mixed aqueous solution of sodium hydroxide and urea or thiourea, freezing for 30 minutes to 10 hours at the temperature of-30 ℃ to 0 ℃, and stirring for 5 minutes to 30 minutes at normal temperature after freezing to obtain cellulose-based sol; standing for 2-36 hours at normal temperature to obtain the porous cellulose gel containing the amide group; washing with water to neutrality to obtain amidated porous cellulose adsorbing material; wherein the functional polymer cross-linking agent is N, N' -methylene bisacrylamide.
6. The method for preparing a functionalized cellulose-based porous material according to claim 5, wherein the cellulose-based host material is purified cellulose, pulp, alpha-cellulose.
7. The preparation method of the functionalized cellulose-based porous material according to claim 5, wherein the mass ratio of the cellulose main body material to the functional polymer cross-linking agent is 1: 0.2-1.5; the mass ratio of the cellulose main body material to the mixed aqueous solution of sodium hydroxide and urea or thiourea is 1: 14-50; the mass ratio of the sodium hydroxide to the urea or the thiourea to the water is 2-10: 3-15: 75-95.
8. The preparation method of the functionalized cellulose-based porous material according to claim 7, wherein the mass ratio of the cellulose main body material to the functional polymer cross-linking agent is 1: 0.2-1; the mass ratio of the cellulose main body material to the mixed aqueous solution of sodium hydroxide and urea or thiourea is 1: 19-49; the mass ratio of the sodium hydroxide to the urea or the thiourea to the water is 3-8: 10-15: 77-87.
9. Use of the functionalized cellulose-based porous material according to claim 1 for controlling chromatic sewage.
10. The use of claim 9, wherein the colored effluent comprises at least one of copper ions, iron ions, cobalt ions, manganese ions, methyl orange, acid black, acid red, acid blue, methylene blue, methyl green, caramel color, carmine, lemon yellow, sunset yellow, and brilliant blue.
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