CN104226268A - Modified cellulose/graphene oxide composite microsphere and preparation method thereof - Google Patents
Modified cellulose/graphene oxide composite microsphere and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 69
- 239000001913 cellulose Substances 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000004005 microsphere Substances 0.000 title claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 229920002310 Welan gum Polymers 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a modified cellulose/graphene oxide composite microsphere and a preparation method thereof. The composite microspheres are compounded by cellulose and graphene oxide materials and are further modified by welan gum. The cellulose is compounded with the graphene oxide, so that the mechanical strength of the composite adsorbing material is enhanced, the adsorption capacity of the adsorbent is further improved, and the performance of the adsorbent is well improved. The cellulose/graphene oxide composite microsphere is modified on the surface by using welan gum, and a branched chain structure and a functional group are introduced, so that the multilayer adsorption can be carried out, and the adsorption performance of the adsorbent is further enhanced. The modified cellulose/graphene oxide composite microspheres have the characteristics of no toxicity, no pollution, good biocompatibility and the like, and can be applied to the fields of sewage treatment, environmental management and the like.
Description
Technical field:
The present invention relates to a kind of composite being applied in the field such as sewage disposal and environmental improvement, particularly relate to a kind of modified cellulose/graphene oxide complex microsphere and preparation method thereof.
Background technology:
Cellulose base composite take cellulose as matrix, adds other functional component wherein, improve the material of its performance.Utilize harmful substance in cellulose composite material Adsorption water body to start to cause the concern of researchers in recent years, the people such as Luo by blended method by cellulose, γ-Fe
2o
3the spherical sorbing material of magnetic cellulose [Luo X is made with active carbon, Zhang L.High effective adsorption of organic dyes on magnetic cellulose beads entrapping activated carbon.Journal of Hazardous Materials, 2009,171 (1): 340-347].The people such as Zhu by ferroferric oxide magnetic nano-particles and active carbon because cellulose, prepare cellulose composite material [Zhu H Y, Fu Y Q, Jiang R, et al.Adsorption removal of congo red onto magnetic cellulose/Fe
3o
4/ activated carbon composite:Equilibrium, kinetic and thermodynamic studies.Chemical Engineering Journal, 2011,173 (2): 494-502].The people such as Deng have prepared cellulose, CNT complex spherical sorbing material [Deng C by emulsion liquid membrane, Liu J, Zhou W, et al.Fabrication of spherical cellulose/carbon tubes hybrid adsorbent anchored with welan gum polysaccharide and its potential in adsorbing methylene blue.Chemical Engineering Journal, 2012,200:452-458].
It is large that ball shaped cellulose has specific area, fluid force such as to learn well at the advantage, therefore than general fibre shape or powdery cellulose adsorbent better effects if, but the absorption property of pure cellulose microballoon itself and bad mechanical strength, in order to improve its mechanical strength and absorption property, support and part are two key factors.Introduce nano material, its structure can be improved, improve mechanical strength.But most nano-filled thing, due to itself poor absorption property, can reduce the active sites of adsorbent itself, have impact on the adsorption capacity of adsorbent on the contrary.The introducing of part can carry out modification to adsorbent, improves the adsorption capacity of adsorbent.Grafting whisker type part more and more receives the concern of people to supporter skeleton, because it can form multilayer absorption to dye molecule, thus improve the adsorption capacity of adsorbent.
Weilan gum (Welan gum) is a kind of extracellular polysaccharides, is secreted by Bacillus alcaligenes.Its main chain has many branched structures, and shape, as tentacle, contains a large amount of carboxyls and oh group, and these groups can by the dyestuff in ion exchange or chelation adsorbed water or heavy metal ion.In addition, the existence of these branched structures and functional group, makes it to carry out multilayer absorption, is also easy to carry out chemical graft to cellulose surface.And because Weilan gum is the natural materials that fermentable produces, there is the features such as nontoxic, pollution-free, bio-compatibility is good.
Summary of the invention:
The object of the present invention is to provide and a kind ofly to dyes, there is excellent absorption property, can at the modified cellulose/graphene oxide complex microsphere of the field such as sewage disposal and environmental improvement application; The present invention also aims to the preparation method that a kind of modified cellulose/graphene oxide complex microsphere is provided.
Modified cellulose of the present invention/graphene oxide complex microsphere forms a step of going forward side by side by Weilan gum modification by cellulose and graphene oxide composite material compound, and the particle diameter of described modified cellulose/graphene oxide complex microsphere is 500-5000nm.
Cellulose/concrete preparation process of graphene oxide complex microsphere is as follows: NaOH/thiocarbamide/urea liquid high-speed stirred dissolving cellulos at low temperatures, obtains transparent cellulose solution.Subsequently product is removed insoluble matter and bubble by high speed centrifugation.By graphene oxide ultrasonic disperse 1h, mix for subsequent use with cellulose solution.
Atoleine and Span80 is added in there-necked flask, at ambient temperature, at the uniform velocity stirring and emulsifying.Next step, slowly add above-mentioned cellulose mixed solution at same temperature and mixing speed.Continue to stir 1-4h under identical condition.Then while stirring, slowly drip watery hydrochloric acid adjust ph to neutral, then stop stirring and leaving standstill, after waiting for reaction system layering, remove the liquid paraffin layer on upper strata, and with deionized water and absolute ethanol washing, to remove residual atoleine and Span80.Finally, by the freeze drying of complex microsphere product (or being kept in 20% ethanolic solution under 0-5 DEG C of condition).
Carry out epoxidation modification to complex microsphere, the solution of configuration containing epoxychloropropane, NaOH and dimethyl sulfoxide (DMSO), pour in there-necked flask, extracting cellulose/graphene oxide complex microsphere is poured in above-mentioned solution.Thermostat water bath is used to stir 3h in a heated condition.After completion of the reaction, stop heating and stir, and repeatedly washing by deionized water, removing unreacted solvent and reactant.
Secondly, take Weilan gum to join sodium hydroxide solution and mix.Use high pure nitrogen to pass in above-mentioned Weilan gum solution, remove the oxygen in solution.Then epoxidation complex microsphere is joined in Weilan gum solution, mix, at the uniform velocity stir 24h in a heated condition.Products therefrom uses bag filter to carry out dialysis 24h, removes the Weilan gum of non-grafting.Finally, the freeze drying of complex microsphere product is preserved.
In described cellulose/graphene oxide complex microsphere, the content of graphene oxide is 0.5wt%-5.0wt%.
In described modified cellulose/graphene oxide complex microsphere, the content of Weilan gum is 1.0wt%-10.0wt%.
Described cellulose origin is in cotton, straw, fiber crops, straw, bagasse or paper.
Compared with prior art, tool of the present invention has the following advantages:
Cellulose and graphene oxide compound, not only increase the mechanical strength of composite adsorbing material, also further increases the adsorption capacity of adsorbent, well improves the performance of adsorbent.Utilize Weilan gum to cellulose/graphene oxide complex microsphere modifying surface, introduce branched structure and functional group, make it to carry out multilayer absorption, further enhancing the absorption property of adsorbent.Modified cellulose/graphene oxide complex microsphere has the features such as nontoxic, pollution-free, bio-compatibility is good, can be applicable to the field such as sewage disposal and environmental improvement.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope (SEM) photograph of modified cellulose/graphene oxide complex microsphere
Fig. 2 is single modified cellulose/graphene oxide complex microsphere scanning electron microscope (SEM) photograph
Detailed description of the invention:
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1:
The aqueous solution 200mL of 8.0wt% NaOH/8.0wt% thiocarbamide/6.5wt% urea is bathed by cryosel and is chilled to-10 DEG C in advance.Add 10g cellulose immediately in solution, and under 16,000rpm/min rotating speed, stir 5min simultaneously, namely obtain transparent cellulose solution.Subsequently product is passed through 8,000rpm centrifugation 10min, removing insoluble matter and bubble.By 0.05g graphene oxide ultrasonic disperse 1h, mix for subsequent use with cellulose solution.
The atoleine of 300mL and the Span80 of 10g is added, at ambient temperature, with l, 000rpm rotating speed stirring and emulsifying 40min in the there-necked flask of 500mL.Next step, slowly add the above-mentioned cellulose mixed solution of 50mL at same temperature and mixing speed.Continue to stir 4h under identical condition.Then while stirring, slowly drip watery hydrochloric acid adjust ph to neutral, then stop stirring and leaving standstill, after waiting for reaction system layering, remove the liquid paraffin layer on upper strata, and with deionized water and absolute ethanol washing, to remove residual atoleine and Span80.Finally, by the freeze drying of complex microsphere product (or being kept in 20% ethanolic solution under 0-5 DEG C of condition).
Carry out epoxidation modification to complex microsphere, configuration is containing 2.5mL epoxychloropropane, 10mL NaOH (1mol L
-1) and the solution of 10mL dimethyl sulfoxide (DMSO), pour in there-necked flask, the cellulose/graphene oxide complex microsphere getting 5g drying is poured in above-mentioned solution.Use thermostat water bath to be heated to 40 DEG C, under 150 rpm rotating speeds, stir 3h.After completion of the reaction, stop heating and stir, and repeatedly washing by deionized water, removing unreacted solvent and reactant.
Secondly, NaOH (the 0.1mol L that 0.1g Weilan gum joins 150mL is taken
-1) mix.Use high pure nitrogen to pass in above-mentioned Weilan gum solution, remove the oxygen in solution.Then epoxidation complex microsphere is joined in Weilan gum solution, mix.Under 40 DEG C of conditions, stir 24h with 150rpm rotating speed.Products therefrom uses bag filter to carry out dialysis 24h, removes the Weilan gum of non-grafting.Finally, the freeze drying of complex microsphere product is preserved.The transmission electron microscope results of modified cellulose/graphene oxide complex microsphere as depicted in figs. 1 and 2.
Embodiment 2:
The aqueous solution 200mL of 8.0wt% NaOH/8.0wt% thiocarbamide/6.5wt% urea is bathed by cryosel and is chilled to-10 DEG C in advance.Add 10g cellulose immediately in solution, and under 16,000rpm/min rotating speed, stir 5min simultaneously, namely obtain transparent cellulose solution.Subsequently product is passed through 8,000rpm centrifugation 10min, removing insoluble matter and bubble.By 0.5g graphene oxide ultrasonic disperse 1h, mix for subsequent use with cellulose solution.
The atoleine of 300mL and the Span80 of 10g is added, at ambient temperature, with l, 000rpm rotating speed stirring and emulsifying 40min in the there-necked flask of 500mL.Next step, slowly add the above-mentioned cellulose mixed solution of 50mL at same temperature and mixing speed.Continue to stir 4h under identical condition.Then while stirring, slowly drip watery hydrochloric acid adjust ph to neutral, then stop stirring and leaving standstill, after waiting for reaction system layering, remove the liquid paraffin layer on upper strata, and with deionized water and absolute ethanol washing, to remove residual atoleine and Span80.Finally, by the freeze drying of complex microsphere product (or being kept in 20% ethanolic solution under 0-5 DEG C of condition).
Carry out epoxidation modification to complex microsphere, configuration is containing 2.5mL epoxychloropropane, 10mL NaOH (1mol L
-1) and the solution of 10mL dimethyl sulfoxide (DMSO), pour in there-necked flask, the cellulose/graphene oxide complex microsphere getting 5g drying is poured in above-mentioned solution.Use thermostat water bath to be heated to 40 DEG C, under 150rpm rotating speed, stir 3h.After completion of the reaction, stop heating and stir, and repeatedly washing by deionized water, removing unreacted solvent and reactant.
Secondly, NaOH (the 0.1mol L that 0.5g Weilan gum joins 150mL is taken
-1) mix.Use high pure nitrogen to pass in above-mentioned Weilan gum solution, remove the oxygen in solution.Then epoxidation complex microsphere is joined in Weilan gum solution, mix.Under 40 DEG C of conditions, stir 24h with 150rpm rotating speed.Products therefrom uses bag filter to carry out dialysis 24h, removes the Weilan gum of non-grafting.Finally, the freeze drying of complex microsphere product is preserved.The transmission electron microscope results of modified cellulose/graphene oxide complex microsphere as depicted in figs. 1 and 2.
Be only in sum the preferred embodiment of invention and oneself, be not used for limiting practical range of the present invention.Namely all equivalences done according to the content of the present patent application the scope of the claims change and modify, and all should be technology category of the present invention.
Claims (5)
1. modified cellulose/graphene oxide complex microsphere, is characterized in that: form a step of going forward side by side by Weilan gum modification by cellulose and graphene oxide composite material compound, and the particle diameter of described modified cellulose/graphene oxide complex microsphere is 500-5000nm.
2. the preparation method of modified cellulose/graphene oxide complex microsphere, it is characterized in that: concrete preparation process is as follows: NaOH/thiocarbamide/urea liquid high-speed stirred dissolving cellulos at low temperatures, obtain transparent cellulose solution, subsequently product is removed insoluble matter and bubble by high speed centrifugation, by graphene oxide ultrasonic disperse 1h, mix for subsequent use with cellulose solution;
Atoleine and Span80 is added in there-necked flask, at ambient temperature, at the uniform velocity stirring and emulsifying, next step, above-mentioned cellulose mixed solution is slowly added at same temperature and mixing speed, continue to stir 1-4h under identical condition, then while stirring, slow dropping watery hydrochloric acid adjust ph is to neutral, then stop stirring and leaving standstill, after waiting for reaction system layering, remove the liquid paraffin layer on upper strata, and with deionized water and absolute ethanol washing, to remove residual atoleine and Span80, finally, by the freeze drying of complex microsphere product (or being kept in 20% ethanolic solution under 0-5 DEG C of condition),
Epoxidation modification is carried out to complex microsphere, the solution of configuration containing epoxychloropropane, NaOH and dimethyl sulfoxide (DMSO), pour in there-necked flask, extracting cellulose/graphene oxide complex microsphere is poured in above-mentioned solution, use thermostat water bath to stir 3h in a heated condition, after completion of the reaction, stop heating and stir, and repeatedly wash by deionized water, remove unreacted solvent and reactant;
Secondly, take Weilan gum to join sodium hydroxide solution and mix, use high pure nitrogen to pass in above-mentioned Weilan gum solution, remove the oxygen in solution, then epoxidation complex microsphere is joined in Weilan gum solution, mix, at the uniform velocity stir 24h in a heated condition, products therefrom uses bag filter to carry out dialysis 24h, removes the Weilan gum of non-grafting, finally, the freeze drying of complex microsphere product is preserved.
3. according to the preparation method of the modified cellulose described in claim 2/graphene oxide complex microsphere, it is characterized in that: in cellulose/graphene oxide complex microsphere, the content of graphene oxide is 0.5wt%-5.0wt%.
4. according to the preparation method of the modified cellulose described in claim 2/graphene oxide complex microsphere, it is characterized in that: in described modified cellulose/graphene oxide complex microsphere, the content of Weilan gum is 1.0wt%-10.0wt%.
5. according to the preparation method of the modified cellulose described in claim 2/graphene oxide complex microsphere, it is characterized in that: described cellulose origin is in cotton, straw, fiber crops, straw, bagasse or paper.
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Application publication date: 20141224 |