CN109158088A - A kind of preparation method of cellulose aerogels adsorbent - Google Patents

A kind of preparation method of cellulose aerogels adsorbent Download PDF

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CN109158088A
CN109158088A CN201811037035.7A CN201811037035A CN109158088A CN 109158088 A CN109158088 A CN 109158088A CN 201811037035 A CN201811037035 A CN 201811037035A CN 109158088 A CN109158088 A CN 109158088A
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cellulose
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preparation
carbonitride
aerogels
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潘钕
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J13/0091—Preparation of aerogels, e.g. xerogels
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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Abstract

The invention discloses a kind of preparation methods of cellulose aerogels adsorbent, cellulose aerogels are made in cellulose through overactivation, modification, cellulose aerogels are the preparation method comprises the following steps: by cellulose dissolution in deionized water, titanium dioxide-carbonitride of cellulose solution quality 15-35% is added, it stirs evenly, solution is adjusted to neutrality, obtains being mixed with titanium dioxide-carbonitride cellulose gel；Gel is with deionized water soaking and washing 2-3 times rear freeze-drying to get cellulose aerogels adsorbent.Preparation process of the present invention is simple, and raw material sources are abundant, and reaction condition is mild, is convenient for large-scale production, and the adsorbent prepared has stronger adsorption capacity to organic matter in waste water from dyestuff and metal ion, and environmentally protective convenient for recycling, long service life.

Description

A kind of preparation method of cellulose aerogels adsorbent
Technical field
The present invention relates to technical field of sewage, more particularly, to a kind of preparation side of cellulose aerogels adsorbent Method.
Technical background
With society and economic fast development, demand of the mankind to natural resources such as water is sharply increased, however, industry, The waste that agricultural and life generate does not add processing just direct emission, results in water body and is heavily polluted, directly affect the mankind and The water safety of animal.In order to handle water pollution, a large amount of water pollution adsorbent also comes into being, traditional adsorbent such as activity Charcoal, ion-exchange fibre etc. are used and are regenerated very inconvenient since expensive and form is mostly graininess or powdered.For Overcome these disadvantages, people have turned one's attention to native cellulose.Cellulose is the most abundant natural polymer of reserves on the earth One of son, it is abundance, cheap, it is safe and non-toxic and biodegradable, it is a kind of environmentally protective carrier material.Fiber Plain intramolecular contains there are many hydrophilic hydroxyl group, it has the characteristics such as nano-scale, porosity, bigger serface, these Advantage is all used as adsorbent material for it and provides good basis.But native cellulose contain great amount of hydroxy group so that its strand it Between easily form hydrogen bond, limit cellulose and used directly as adsorbent, in order to assign the stronger absorption property of cellulose and more The wide scope of application, people are modified research to its structure by a series of chemical reactions related with hydroxyl, such as pass through ester The reaction such as change, etherificate, nucleophilic displacement of fluorine, graft copolymerization, crosslinking introduces active group in cellulose skeleton and is accordingly adsorbed Agent.
Cellulose is reserves a kind of natural macromolecular material the most abundant in nature.As after inorganic aerogels and conjunction At the third generation aeroge after polymeric aerogels, cellulose aerogels material has had both the reproducible advantage of cellulose green With the porous architectural characteristic of aerogel material, the good biocompatibility and degradability having are in biology, medicine, environment Equal subjects have very big application development prospect, it has also become one of the hot spot of domestic and international researcher concern at present.
High organic content in waste water from dyestuff, complicated component, color are deep, change of water quality is big, are generally acknowledged refractory both at home and abroad One of industrial wastewater is managed, existing pollution risk is printing industry environmental issue urgently to be resolved.Result of study in recent years Show that cellulose base adsorbent material has good effect in terms of handling waste water from dyestuff.
The prior art such as Authorization Notice No. is the Chinese invention patent of 105800757 B of CN, discloses a kind of waste water from dyestuff Inorganic agent is grouped as by the group of following weight percent: polyaluminum ferric chloride 3-12%；Bentonite 10-22%；Sodium Polyacrylate 2-5%；Active carbon 1-5%；Visible light catalyst 0.3-0.8%, and 100% is complemented to distilled water；The dye wastewater treatment The production raw material sources of agent are extensive, can effectively remove the organic dyestuff in water, and processing organic dyestuff is thorough, processing cost is low, nothing It is toxicity, pollution-free.However, the dye wastewater treatment agent of this method preparation does not have adsorption effect to metal ion, and it is unfavorable for Recycling.
Summary of the invention
That the purpose of the present invention is to provide a kind of preparation methods is simple, reaction condition is mild, equipment requirement is low, is convenient for scale The preparation method for the cellulose aerogels adsorbent that metaplasia produces, the adsorbent of this method preparation to organic matter in waste water from dyestuff and Metal ion has stronger adsorption capacity, and environmentally protective convenient for recycling, long service life.
The present invention in background technique aiming at the problem that mentioning, the technical solution taken are as follows:
A kind of preparation method of cellulose aerogels adsorbent, is made fiber for the cellulose through overactivation, modification Plain aeroge, the cellulose aerogels are to be mixed with titanium dioxide-carbonitride cellulose gel.
Preferably, cellulose aerogels preparation step are as follows: by the cellulose dissolution through overactivation, modification in deionized water In, titanium dioxide-carbonitride of cellulose solution quality 15-35% is added, stirs evenly, solution is adjusted to neutrality, obtain It is mixed with titanium dioxide-carbonitride cellulose gel；After gel deionized water soaking and washing 2-3 times freeze-drying to get Cellulose aerogels adsorbent；The cellulose aerogels adsorbent can be used for handling organic matter in dyeing waste water, and in waste water Metal ion have certain suction-operated, have good Environmental compatibility, secondary pollution will not be caused to environment.
Preferably, titanium dioxide-carbonitride preparation step are as follows: take appropriate hydrochloric acid guanidine to be put into crucible, in Muffle furnace 500-650 DEG C of calcining 2-3h, heating rate is 3-5 DEG C/min, and after cooled to room temperature, grinding obtains nitridation carbon dust；By matter Amount is distributed in deionized water than the titanium dioxide and carbonitride for being 1:3-5, stirs 1-2h, and NaOH solution is added to mixed solution PH is 12-14, continues to stir 1-2h, is filtered, washed, dries to obtain titanium dioxide-nitridation carbon composite；Utilize hydrogen bubble template Thermal polymerization prepares carbonitride, have the advantages that it is simple and environmentally-friendly, and by adjust thermal polymerization temperature, different specific surface areas can be prepared Mesoporous carbonitride realizes the adjustability of technique；Mesoporous carbonitride not only shows excellent surface mass transfer diffusion process, moreover it is possible to excellent Change mesoporous band structure, improves light absorpting ability, and then improve the ability of photocatalytic degradation of organic matter；Using titanium dioxide and nitrogen Change the compound building heterojunction structure of carbon, effectively combine broad-band gap and narrow gap semiconductor, realize and expand light abstraction width, improves light Energy utilization rate, and then improve the degradation efficiency to organic pollutant.
Further preferably, the 2- of carbonitride quality 0.02-0.08% is additionally added in titanium dioxide-carbonitride recombination process The Bilobanoate of hydrazinoethanol and 0.01-0.05%, 2- hydrazinoethanol and Bilobanoate have synergistic effect, can be improved dioxy It is uniform in carbonitride Dispersion on surface to change titanium, the building of titanium dioxide-carbonitride heterojunction structure is advantageously implemented, to quickly have Light induced electron on carbonitride semiconductor is transferred in titanium dioxide substrate by effect ground, realize light induced electron and hole separation and Electron-hole recombination probability again is reduced, the utilization rate of photo-generated carrier is improved, final raising photo-generated carrier redox is organic The efficiency of pollutant；Meanwhile being conducive to enhance the anti-light aging ability of composite material, it prolongs its service life, reduces industrialization Cost.
Preferably, cellulose activation step are as follows: with NaOH solution by H2O2The pH of solution is adjusted to 11-12, by drying, powder Natural sawdust that is broken, crossing 20-60 mesh is added to H2O2In solution, it is put into constant temperature oscillation case with 100-200r/min revolving speed in room The lower oscillating reactions 10-15h of temperature, is added the chloro- 2- hydroxypropyl of 3- of the 3- α-furyl base acrylic acid and 0.5-1% of sawdust quality 1-5% Base-trimethyl ammonium chloride, reaction 4-6h obtains sawdust cellulose solution under ultraviolet lighting, filters, after sufficiently being washed with deionized water Dry to obtain activated cellulose；H is mainly utilized using alkaline hydrogen peroxide pre-treatment and activation cellulose2O2Wood is taken off under alkaline medium Quality, and to the mild solubilized function of macromolecular hemicellulose, destroy the package of lignin, change the crystallization knot of cellulose Structure, to increase the contact area of organic pollutant molecule and cellulose；3- α-furyl base acrylic acid and the chloro- 2- hydroxypropyl-three of 3- The special presence of ammonio methacrylate, on the one hand can weaken in sawdust cellulosic molecule and intermolecular hydrogen bonding, reduction cellulose divide Subchain stability is conducive to the infiltration and diffusion of activation or modifying agent in cellulose to reduce the crystallinity of cellulose, Reaction reagent is improved to the accessibility of cellulose, while making the more hydroxyl exposures of cellulose surface, these hydroxyls are to metal Ion has certain chelation；On the other hand, it can be diffused rapidly to up to cellulose amorphous region, occur with cellulose surface Copolyreaction increases cellulose surface acidic-group, so that cellulose can be improved to the adsorption capacity of organic pollutant.
Preferably, sawdust and H2O2The solid-to-liquid ratio of solution is 1:40-60g/mL；H2O2The volumetric concentration of solution is 1- 2.5%.
Preferably, cellulose modified step are as follows: by cyclodextrin in the NaOH solution that mass fraction is 1-50% It is made into the alkaline mixed solution that cyclodextrin mass fraction is 0.001-50%, cellulose is placed in alkaline mixed solution, in 10- 1-24h is reacted under the conditions of 100 DEG C, sufficiently washs and dry to obtain the modified fibre of grafted cyclodextrin after filtering with deionized water Element；The distinctive ring external hydrophilicity of cyclodextrin, the characteristic of ring internal drainage and the cavity microenvironment with certain size, can be with envelope size The organic molecule of suitable size, while its surface is distributed numerous activity hydroxies and also there is certain chelating to make to metal ion With.
Preferably, cyclodextrin is at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and its derivative.
Compared with the prior art, the advantages of the present invention are as follows:
1) present invention prepares adsorbent by carrier of cellulose, and raw material sources are extensive, cheap, environmental-friendly, and Preparation method is simple, reaction condition is mild, and equipment requirement is low, is convenient for large-scale production；
2) present invention uses and is modified the cellulose graft cyclodextrin of activation, the distinctive ring external hydrophilicity of cyclodextrin, ring The characteristic of internal drainage and the cavity microenvironment with certain size, the organic molecule that can be suitable for envelope size, simultaneously Its surface, which is distributed numerous activity hydroxies, also has certain chelation to metal ion；
3) present invention is by cellulose and inorganic material titanium dioxide-carbonitride is compound is prepared into aeroge adsorbent, has Good Environmental compatibility will not cause secondary pollution to environment, and convenient for recycling；Using cellulose to the absorption of organic matter with And titanium dioxide-carbonitride carries out photocatalytic degradation to organic matter, can form the organic matter tupe of complete set, mention significantly High treatment effeciency of the adsorbent to organic matter in waste water from dyestuff.
Specific embodiment
The present invention program is described further below by embodiment:
Embodiment 1:
A kind of preparation method of cellulose aerogels adsorbent, including cellulose activation, cellulose modified and cellulose gas Gel preparation, the specific steps are as follows:
(1) cellulose activation: with NaOH solution by H2O2The pH of solution is adjusted to 11, by drying, crushing, the day for crossing 20 meshes Right sawdust is added to H2O2In solution, sawdust and H2O2The solid-to-liquid ratio of solution is 1:40g/mL, H2O2The volumetric concentration of solution is 1%； It is put into constant temperature oscillation case with 100r/min revolving speed oscillating reactions 10h at room temperature, the 3- α-furyl base of sawdust quality 1% is added Acrylic acid and 0.5% the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3-, reaction 4h obtains sawdust cellulose solution, mistake under ultraviolet lighting Filter, dries to obtain activated cellulose after sufficiently being washed with deionized water；It is mainly using alkaline hydrogen peroxide pre-treatment and activation cellulose Utilize H2O2The delignification under alkaline medium, and to the mild solubilized function of macromolecular hemicellulose, destroy the packet of lignin It wraps up in, changes the crystalline texture of cellulose, to increase the contact area of organic pollutant molecule and cellulose；3- α-furyl base propylene The special presence of acid and the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3-, on the one hand can weaken in sawdust cellulosic molecule and molecule Between hydrogen bond, reduce cellulose molecular chain stability to reduce the crystallinity of cellulose, be conducive to activation or modifying agent in fibre Infiltration and diffusion in dimension element improve reaction reagent to the accessibility of cellulose, while making the more hydroxyls of cellulose surface Exposure, these hydroxyls have certain chelation to metal ion；On the other hand, it can be diffused rapidly to amorphous up to cellulose Area is copolymerized with cellulose surface, increases cellulose surface acidic-group, so that cellulose can be improved to organic contamination The adsorption capacity of object；
(2) cellulose modified: alpha-cyclodextrin being dissolved in the sodium hydroxide solution that mass fraction is 1% and is made into cyclodextrin The alkaline mixed solution that mass fraction is 0.001%, cellulose is placed in alkaline mixed solution, is reacted under the conditions of 10 DEG C 1h sufficiently washs with deionized water and dries to obtain the modified cellulose of grafted cyclodextrin after filtering；Cellulose is mixed with alkalinity The mass ratio of solution is 1:1；The distinctive ring external hydrophilicity of cyclodextrin, the spy of ring internal drainage and the cavity microenvironment with certain size Property, the organic molecule that can be suitable for envelope size, while its surface is distributed numerous activity hydroxies to metal ion With certain chelation；
(3) prepared by cellulose aerogels: modified cellulose being dissolved in deionized water, cellulose solution quality is added 15% titanium dioxide-carbonitride, stirs evenly, and hydrochloric acid conditioning solution is added to neutrality, obtains being mixed with titanium dioxide-nitridation The cellulose gel of carbon；Gel is with freeze-drying after deionized water soaking and washing 2 times to get a kind of absorption of cellulose aerogels Agent；The cellulose aerogels adsorbent can be used for handling organic matter in dyeing waste water, and have centainly to the metal ion in waste water Suction-operated, have good Environmental compatibility, secondary pollution will not be caused to environment；
The preparation step of above-mentioned titanium dioxide-carbonitride are as follows: take appropriate hydrochloric acid guanidine to be put into crucible, 500 DEG C in Muffle furnace 2h is calcined, heating rate is 3 DEG C/min, and after cooled to room temperature, grinding obtains nitridation carbon dust；It is the two of 1:3 by mass ratio Titanium oxide and carbonitride are distributed in 30mL deionized water, stir 1h, and a certain amount of NaOH solution is added to mixed solution pH and is 12, the 2- hydrazinoethanol of carbonitride quality 0.02% and 0.01% Bilobanoate is added, continues to stir 1h, is filtered, washed, does It is dry to obtain titanium dioxide-nitridation carbon composite；Carbonitride is prepared using hydrogen bubble template thermal polymerization, with simple and environmentally-friendly excellent Point, and by adjusting thermal polymerization temperature, the mesoporous carbonitride of different specific surface areas can be prepared, realizes the adjustability of technique；It is mesoporous Carbonitride not only shows excellent surface mass transfer diffusion process, moreover it is possible to and optimize mesoporous band structure, improves light absorpting ability, into And improve the ability of photocatalytic degradation of organic matter；Using titanium dioxide and the compound building heterojunction structure of carbonitride, effectively combine Broad-band gap and narrow gap semiconductor are realized and expand light abstraction width, improve the efficiency of light energy utilization, and then improve to organic pollutant Degradation efficiency；2- hydrazinoethanol and Bilobanoate have synergistic effect, and it is equal in carbonitride Dispersion on surface to can be improved titanium dioxide It is even, it is advantageously implemented the building of titanium dioxide-carbonitride heterojunction structure, thus fast and effeciently will be on carbonitride semiconductor Light induced electron is transferred in titanium dioxide substrate, realizes that the separation of light induced electron and hole and reduction electron-hole are compound several again Rate improves the utilization rate of photo-generated carrier, the final efficiency for improving photo-generated carrier redox organic pollutant；Meanwhile having It conducive to the anti-light aging ability of enhancing composite material, prolongs its service life, reduces industrialization cost.
Embodiment 2:
A kind of preparation method of cellulose aerogels adsorbent, including cellulose activation, cellulose modified and cellulose gas Gel preparation, the specific steps are as follows:
(1) cellulose activation: with NaOH solution by H2O2The pH of solution is adjusted to 11, by drying, crushing, the day for crossing 50 meshes Right sawdust is added to H2O2In solution, sawdust and H2O2The solid-to-liquid ratio of solution is 1:50g/mL, H2O2The volumetric concentration of solution is 2.0%；It is put into constant temperature oscillation case with 200r/min revolving speed oscillating reactions 12h at room temperature, the 3- of sawdust quality 3.2% is added α-furyl base acrylic acid and 0.6% the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3-, reaction 5h obtains sawdust fiber under ultraviolet lighting Plain solution, filtering, dries to obtain activated cellulose after sufficiently being washed with deionized water；
(2) cellulose modified: alpha-cyclodextrin is dissolved in the sodium hydroxide solution that mass fraction is 26% with cyclization paste The alkaline mixed solution that extract Iuality score is 35%, cellulose is placed in alkaline mixed solution, is reacted under the conditions of 65 DEG C 18h sufficiently washs with deionized water and dries to obtain the modified cellulose of grafted cyclodextrin after filtering；Cellulose is mixed with alkalinity The mass ratio 1:60 of solution；
(3) prepared by cellulose aerogels: modified cellulose being dissolved in deionized water, cellulose solution quality is added 30% titanium dioxide-carbonitride, stirs evenly, and hydrochloric acid conditioning solution is added to neutrality, obtains being mixed with titanium dioxide-nitridation The cellulose gel of carbon；Gel is with freeze-drying after deionized water soaking and washing 3 times to get a kind of absorption of cellulose aerogels Agent；
The preparation step of above-mentioned titanium dioxide-carbonitride are as follows: take appropriate hydrochloric acid guanidine to be put into crucible, 600 DEG C in Muffle furnace 3h is calcined, heating rate is 3 DEG C/min, and after cooled to room temperature, grinding obtains nitridation carbon dust；It is the two of 1:4 by mass ratio Titanium oxide and carbonitride are distributed in 40mL deionized water, stir 2h, and a certain amount of NaOH solution is added to mixed solution pH and is 13, the 2- hydrazinoethanol of carbonitride quality 0.05% and 0.03% Bilobanoate is added, continues to stir 2h, is filtered, washed, does It is dry to obtain titanium dioxide-nitridation carbon composite.
Embodiment 3:
A kind of preparation method of cellulose aerogels adsorbent, including cellulose activation, cellulose modified and cellulose gas Gel preparation, the specific steps are as follows:
(1) cellulose activation: with NaOH solution by H2O2The pH of solution is adjusted to 12, by drying, crushing, the day for crossing 60 meshes Right sawdust is added to H2O2In solution, sawdust and H2O2The solid-to-liquid ratio of solution is 1:60g/mL, H2O2The volumetric concentration of solution is 2.5%；It is put into constant temperature oscillation case with 200r/min revolving speed oscillating reactions 15h at room temperature, the 3- α-of sawdust quality 5% is added Furylacrylic acid and 1% the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3-, it is molten to obtain sawdust cellulose by reaction 6h under ultraviolet lighting Liquid, filtering, dries to obtain activated cellulose after sufficiently being washed with deionized water；
(2) cellulose modified: alpha-cyclodextrin is dissolved in the sodium hydroxide solution that mass fraction is 50% with cyclization paste The alkaline mixed solution that extract Iuality score is 50%, cellulose is placed in alkaline mixed solution, is reacted under the conditions of 100 DEG C For 24 hours, sufficiently wash and dry to obtain the modified cellulose of grafted cyclodextrin after filtering with deionized water；Cellulose is mixed with alkalinity The mass ratio 1:100 of solution；
(3) prepared by cellulose aerogels: modified cellulose being dissolved in deionized water, cellulose solution quality is added 35% titanium dioxide-carbonitride, stirs evenly, and hydrochloric acid conditioning solution is added to neutrality, obtains being mixed with titanium dioxide-nitridation The cellulose gel of carbon；Gel is with freeze-drying after deionized water soaking and washing 3 times to get a kind of absorption of cellulose aerogels Agent；
The preparation step of above-mentioned titanium dioxide-carbonitride are as follows: take appropriate hydrochloric acid guanidine to be put into crucible, 650 DEG C in Muffle furnace 3h is calcined, heating rate is 5 DEG C/min, and after cooled to room temperature, grinding obtains nitridation carbon dust；It is the two of 1:5 by mass ratio Titanium oxide and carbonitride are distributed in 50mL deionized water, stir 2h, and a certain amount of NaOH solution is added to mixed solution pH and is 14, the 2- hydrazinoethanol of carbonitride quality 0.08% and 0.05% Bilobanoate is added, continues to stir 2h, is filtered, washed, does It is dry to obtain titanium dioxide-nitridation carbon composite.
Comparative example 1:
It is not added with 3- α-furyl base acrylic acid and the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3- during cellulose activation, Remaining part point and embodiment 2 are completely the same.
Comparative example 2:
2- hydrazinoethanol and Bilobanoate, rest part and embodiment 2 are not added in titanium dioxide-carbonitride recombination process It is completely the same.
The adsorbent prepared to embodiment 2 and comparative example 1 carries out following adsorption test: weighing 0.5g sample of sorbent, sets In certain density Pb2+Their absorption is held with measure and calculation adsorbent after absorption a period of time in the solution of methylene blue Amount；Each adsorption capacity is as shown in table 1 after reacting 60min, and adsorbent prepared by comparative example 1 is either to Pb2+Or methylene blue Adsorption capacity be below embodiment 2, show the spy of 3- α-furyl base acrylic acid and the chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3- It is different to exist, it on the one hand can make the more hydroxyl exposures of cellulose surface, these hydroxyls have certain chelating to make metal ion With；On the other hand, it can be diffused rapidly to up to cellulose amorphous region, be copolymerized with cellulose surface, increase fiber Plain surface acidic groups, so that cellulose can be improved to the adsorption capacity of organic pollutant.
1 adsorbent of table is to Pb2+With the adsorption capacity (reaction 60min) of methylene blue
Project Pb2+Adsorption capacity Methylene blue adsorption number capacity
Embodiment 2 75 200
Comparative example 1 42 147
To the following methylene blue Degrading experiment of adsorbent progress of embodiment 2 and the preparation of comparative example 2: compound concentration is The methylene blue solution of 10mg/L simulates dyeing wastewater；After 150mL dye solution is added into photo catalysis reactor, then The adsorbent of 0.1g preparation is added, entire reaction process is persistently stirred using magnetic agitation；Dark reaction process is by reaction system It is placed in darkroom, photocatalytic process is irradiated using xenon lamp simulated solar irradiation；Every 10min (dark reaction) or 20min (photocatalysis Process) take a solution to be detected, the absorbance of solution is measured after centrifugation, in ultraviolet-visible spectrophotometer for weighing Measure methylene blue palliating degradation degree；The degradation rate of methylene blue is respectively 98.3% and 78.6% after illumination reaction 60min, shows 2- Hydrazinoethanol and Bilobanoate have synergistic effect, can be improved titanium dioxide-nitridation carbon composite photo-generated carrier benefit With rate, the degradation rate of methylene blue is improved.
Routine operation in operation of the present invention step is well known to those skilled in the art, herein without repeating.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention, Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of preparation method of cellulose aerogels adsorbent, is made cellulose for the cellulose through overactivation, modification Aeroge, it is characterised in that: the cellulose aerogels are to be mixed with titanium dioxide-carbonitride cellulose gel.
2. a kind of preparation method of cellulose aerogels adsorbent according to claim 1, it is characterised in that: the fiber Plain aeroge preparation step are as follows: by the cellulose dissolution through overactivation, modification in deionized water, cellulose solution quality is added Titanium dioxide-carbonitride of 15-35%, stirs evenly, and solution is adjusted to neutrality, must be mixed with titanium dioxide-carbonitride fibre Tie up plain gel；Deionized water soaking and washing 2-3 times rear freeze-drying of gel, obtains cellulose aerogels adsorbent.
3. a kind of preparation method of cellulose aerogels adsorbent according to claim 1, it is characterised in that: the dioxy Change titanium-carbonitride preparation step are as follows: by guanidine hydrochloride in 500-650 DEG C of calcining 2-3h, heating rate is 3-5 DEG C/min, naturally cold But to after room temperature, grinding obtains nitridation carbon dust；Titanium dioxide and carbonitride that mass ratio is 1:3-5 are distributed to deionized water In, 1-2h is stirred, it is 12-14 that NaOH solution, which is added, to mixed solution pH, continues to stir 1-2h, is filtered, washed, dries to obtain dioxy Change titanium-nitridation carbon composite.
4. a kind of preparation method of cellulose aerogels adsorbent according to claim 3, it is characterised in that: the dioxy Change in titanium-carbonitride recombination process and is additionally added the 2- hydrazinoethanol of carbonitride quality 0.02-0.08% and the silver of 0.01-0.05% Apricot ketone ester.
5. a kind of preparation method of cellulose aerogels adsorbent according to claim 1, it is characterised in that: the fiber Plain activation step are as follows: with NaOH solution by H2O2The pH of solution is adjusted to 11-12, and the natural sawdust of drying, crushing, sieving is added to H2O2In solution, the 3- α-furyl base acrylic acid and 0.5-1% of sawdust quality 1-5% is added in oscillating reactions 10-15h at room temperature The chloro- 2- hydroxypropyl-trimethyl ammonium chloride of 3-, reaction 4-6h obtains sawdust cellulose solution under ultraviolet lighting, filters, uses deionized water Activated cellulose is dried to obtain after washing.
6. a kind of preparation method of cellulose aerogels adsorbent according to claim 5, it is characterised in that: the sawdust With H2O2The solid-to-liquid ratio of solution is 1:40-60g/mL；H2O2The volumetric concentration of solution is 1-2.5%.
7. a kind of preparation method of cellulose aerogels adsorbent according to claim 1, it is characterised in that: the fiber Plain modification procedure are as follows: cyclodextrin is made into cyclodextrin mass fraction in the NaOH solution that mass fraction is 1-50% is The alkaline mixed solution of 0.001-50%, cellulose is placed in alkaline mixed solution, reacts 1- under the conditions of 10-100 DEG C For 24 hours, the modified cellulose of grafted cyclodextrin is washed with deionized and dried to obtain after filtering.
8. a kind of preparation method of cellulose aerogels adsorbent according to claim 7, it is characterised in that: the ring paste Essence is at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and its derivative.
CN201811037035.7A 2018-09-06 2018-09-06 A kind of preparation method of cellulose aerogels adsorbent Pending CN109158088A (en)

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