CN109225149B - TiO 22Modified chitosan adsorbent and preparation method and application thereof - Google Patents

TiO 22Modified chitosan adsorbent and preparation method and application thereof Download PDF

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CN109225149B
CN109225149B CN201811171208.4A CN201811171208A CN109225149B CN 109225149 B CN109225149 B CN 109225149B CN 201811171208 A CN201811171208 A CN 201811171208A CN 109225149 B CN109225149 B CN 109225149B
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chitosan
adsorbent
toluene
glycidyl methacrylate
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CN109225149A (en
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陈国力
宋坤
黄孝明
王博
殷广明
王文波
刘勇智
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Qiqihar University
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

TiO 22The invention discloses a modified chitosan adsorbent and a preparation method and application thereof, and relates to an adsorption material and a preparation method and application thereof. The invention aims to solve the technical problem that the prior chitosan composite adsorbent has low adsorption capacity on heavy metal ions of mercury and lead in adsorbed water and organic solvent of toluene. The TiO being2The structural formula of the modified chitosan adsorbent is as follows:
Figure DDA0001822462500000011
the preparation method comprises the following steps: firstly preparing colloid TiO2Then reacting with KH-570 to prepare TiO2(KH-570) an intermediate; reacting chitosan, glycidyl methacrylate and benzyltriethylammonium chloride in toluene to prepare chitosan-glycidyl methacrylateAn oleyl ester intermediate; finally adding TiO2(KH-570) reacting the intermediate, chitosan-glycidyl methacrylate intermediate and azobisisobutyronitrile in toluene to obtain TiO2Modified chitosan adsorbent. The adsorbent is used for adsorbing heavy metal and organic substance pollutants in wastewater. It is to Hg2+、Pb2+And the adsorption amounts of the toluene and the water are 25-30.5 mg/g, 589-635 mg/g and 48-57 mg/g in sequence. Can be used in the field of sewage treatment.

Description

TiO 22Modified chitosan adsorbent and preparation method and application thereof
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a TiO (titanium dioxide) adsorbent2A preparation method and application of a modified chitosan adsorbent.
Background
The environmental pollution mainly comprises heavy metal and organic substance pollution, the most serious pollution is water, and the content of heavy metal and organic solvent in the wastewater seriously exceeds the standard, thereby causing serious influence on the water body in the nature and harming the health of human beings. The harm caused by the pollution of mercury and lead ions in heavy gold pollution is particularly serious, and inorganic mercury ions can be combined with enzyme protein of a human body to inhibit the activity of various enzymes so as to cause the normal function of cells to be obstructed; lead has direct toxic action on specific nerve structures in a plurality of central and peripheral nervous systems of a human body, and lead poisoning of children can seriously reduce intelligence; and chronic poisoning of toluene often causes neurasthenia syndrome and damages to liver and kidney, so that removal of water heavy metals and organic substances is very significant.
At present, chitosan polymer adsorbents are the leading and important research points, because the physical and chemical properties of the polymer compounds are various, and different adsorption mechanisms are provided for various pollutants, andand the adsorption effect is better. Existing use of TiO2The modified chitosan is used for preparing more adsorbents because of TiO2The chitosan has good adsorption effect, and the chitosan has good adsorption effect, so that the chitosan and the chitosan are combined together, and the adsorption effect is very good. Article carboxymethyl chitosan-cellulose-nano TiO 22-32 of No. 1 of volume 18 of 2017, fiber and Polymer2Research on effective adsorption and removal of heavy metal pollutants in water by compound (Terry Carboxymethyl Chitosan-hemicellose-nanosized TiO)2Composite as Effective Adsorbent for removing Metal Contaminants from Water) discloses a method for preparing a Composite nano-crystalline cellulose from chitosan, cellulose and nano-TiO2The composite material synthesized is tested for the adsorption removal effect of the composite material on Ni (II), Cd (II), Cu (II), Hg (II), Mn (VII) and Cr (VI), and the result shows that the composite material has better adsorption capacity on the ions, but has better adsorption capacity on Hg2+The adsorption amount of the catalyst is only 4.3mg/g for Hg2+The adsorption of (3) is low. "Taiwan chemical industry institute journal of 2016 58 th 333-2Research on removal of heavy metal ions by functionalized Chitosan nanofibers functionalized by TiO (Chitosan nanofibers)2nanoparticles for the removal of valuable metals) disclosed the preparation of chitosan/titanium dioxide composite nanofiber adsorbents, which showed maximum adsorption capacities for Pb (II), Cu (II) of 526.5, 475.5mg/g, respectively. The research on the adsorbent capable of adsorbing the organic solvent toluene has not been reported yet.
Disclosure of Invention
The invention aims to solve the problem of the existing carboxymethyl chitosan-cellulose-nano TiO2The technical problem of low adsorption amount of heavy metal ions mercury and lead in water and organic solvent toluene when the compound and the chitosan/titanium dioxide compound nanofiber adsorbent are adsorbed is solved, and the TiO compound adsorbent is provided2Modified chitosan adsorbent and its preparation method and application.
TiO of the invention2The structural expression of the modified chitosan adsorbent is as follows:
Figure BDA0001822462480000021
wherein n is 20-30. Is described as TiO2(KH-570)-g-(CS-GMA)。
The above TiO compound2The preparation method of the modified chitosan adsorbent comprises the following steps:
firstly, according to the mass ratio of tetrabutyl titanate to 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) of 1: (0.5-1.5) weighing tetrabutyl titanate and 3- (methacryloyloxy) propyl trimethoxy silane (KH-570);
secondly, according to the mass ratio of tetrabutyl titanate to absolute ethyl alcohol of 1 g: (22-25) mL, wherein the ratio of the mass of tetrabutyl titanate to the volume of hydrochloric acid with the concentration of 0.05mol/L is 1 g: (19-22) mL, adding the tetrabutyl titanate weighed in the step one into absolute ethyl alcohol, uniformly mixing, dropwise adding hydrochloric acid under the stirring condition, and stirring after dropwise adding to obtain colloidal TiO2；
Wherein the stirring speed in the second step is 200-300 r/min, and the stirring time is 25-35 minutes.
Thirdly, adding the 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) weighed in the first step into the colloidal TiO obtained in the second step2Adding absolute ethyl alcohol and deionized water, heating to 40-60 ℃, stirring for reaction for 0.5-2 hours, washing and drying to obtain TiO2(KH-570) an intermediate;
wherein the volume ratio of the absolute ethyl alcohol to the deionized water in the third step is 9:1, and the stirring speed is 200 r/min;
colloidal TiO in the third step2The mass to volume ratio of deionized water of 1 g: 1 mL;
weighing Chitosan (CS), Glycidyl Methacrylate (GMA), benzyl triethyl ammonium chloride and toluene, wherein the mass ratio of the Chitosan (CS) to the Glycidyl Methacrylate (GMA) is 1 (1-1.2), and the mass of the benzyl triethyl ammonium chloride accounts for 7% -8% of the total mass of the Chitosan (CS) and the Glycidyl Methacrylate (GMA); the ratio of the mass of Chitosan (CS) to the volume of toluene was 1 g: (20-25) mL;
uniformly mixing Chitosan (CS), Glycidyl Methacrylate (GMA) and toluene, heating to 70-90 ℃ under the stirring condition, adding benzyltriethylammonium chloride, and stirring to react for 3-3.5 hours at 70-90 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
wherein the viscosity of the Chitosan (CS) is 170-250 mPas,
fifthly, weighing TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA), azobisisobutyronitrile and toluene; TiO 22The mass ratio of the (KH-570) intermediate to the chitosan-glycidyl methacrylate intermediate (CS-GMA) is 1: (1-1.2); the mass of the azodiisobutyronitrile accounts for TiO2(KH-570) 3-3.5% of the total mass of the intermediate and the chitosan-glycidyl methacrylate intermediate (CS-GMA); TiO 22(KH-570) the ratio of the mass of intermediate to the volume of toluene was 1 g: (40-50) mL;
adding TiO into the mixture2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene are uniformly mixed, the temperature is raised to 75-85 ℃ under the stirring condition, azodiisobutyronitrile is added, and the mixture is stirred and reacted for 4-5 hours at the temperature of 75-85 ℃ to obtain TiO2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMA).
TiO of the invention2The application of the modified chitosan adsorbent is used as an adsorbent for adsorbing heavy metals and organic pollutants in wastewater, and the specific method comprises the following steps: adding TiO into the mixture2Adding modified chitosan adsorbent into wastewater containing heavy metal pollutants and organic substances, ultrasonically dispersing uniformly, stirring, filtering, and adding TiO2Filtering the modified chitosan adsorbent to finish the treatment of the wastewater containing heavy metal pollutants.
TiO of the invention2The synthesis reaction process of the modified chitosan adsorbent is as follows:
Figure BDA0001822462480000031
the colloidal TiO modified by 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) of the invention2Ratio of solid TiO to2Easier reaction, KH-570 modified colloidal TiO2To make inorganic TiO2To become organic, colloidal TiO2The hydroxyl on the surface is high, and can react with 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) to introduce a large number of double bonds. Meanwhile, a large number of double bonds are introduced by the reaction of Chitosan (CS) and Glycidyl Methacrylate (GMA). TiO 22The (KH-570) intermediate and the chitosan-glycidyl methacrylate intermediate (CS-GMA) are very easy to react to generate a novel adsorbent TiO2(KH-570) -g- (CS-GMA), the adsorbent has nanometer and high molecular properties, and can be used for adsorbing heavy metal Hg2+、Pb2+Has better adsorption and removal effects on Hg and toluene2+The adsorption amount of the catalyst is 25 to 30.5mg/g, and the catalyst has the effect of adsorbing Pb2+The adsorption amount of the catalyst is 589-635 mg/g, and the adsorption amount of the catalyst on toluene is 48-57 mg/g.
TiO of the invention2The modified chitosan adsorbent can be used in the field of sewage treatment.
Drawings
FIG. 1 is the TiO prepared in example 12(KH-570) intermediate, CS-GMA intermediate and TiO2(KH-570) -g- (CS-GMA) adsorbent.
Detailed Description
The first embodiment is as follows: TiO of the present embodiment2The structural expression of the modified chitosan adsorbent is as follows:
Figure BDA0001822462480000041
wherein n is 20-30. Is described as TiO2(KH-570)-g-(CS-GMA)。
The second embodiment is as follows: detailed description of the invention the TiO2The preparation method of the modified chitosan adsorbent comprises the following steps:
firstly, according to the mass ratio of tetrabutyl titanate to 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) of 1: (0.5-1.5) weighing tetrabutyl titanate and 3- (methacryloyloxy) propyl trimethoxy silane (KH-570);
secondly, according to the mass ratio of tetrabutyl titanate to absolute ethyl alcohol of 1 g: (22-25) mL, wherein the ratio of the mass of tetrabutyl titanate to the volume of hydrochloric acid with the concentration of 0.05mol/L is 1 g: (19-22) mL, adding the tetrabutyl titanate weighed in the step one into absolute ethyl alcohol, uniformly mixing, dropwise adding hydrochloric acid under the stirring condition, and stirring after dropwise adding to obtain colloidal TiO2；
Thirdly, adding the 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) weighed in the first step into the colloidal TiO obtained in the second step2Adding absolute ethyl alcohol and deionized water, heating to 40-60 ℃, stirring for reaction for 0.5-2 hours, washing and drying to obtain TiO2(KH-570) an intermediate;
weighing Chitosan (CS), Glycidyl Methacrylate (GMA), benzyl triethyl ammonium chloride and toluene, wherein the mass ratio of the Chitosan (CS) to the Glycidyl Methacrylate (GMA) is 1 (1-1.2), and the mass of the benzyl triethyl ammonium chloride accounts for 7% -8% of the total mass of the Chitosan (CS) and the Glycidyl Methacrylate (GMA); the ratio of the mass of Chitosan (CS) to the volume of toluene was 1 g: (20-25) mL;
uniformly mixing Chitosan (CS), Glycidyl Methacrylate (GMA) and toluene, heating to 70-90 ℃ under the stirring condition, adding benzyltriethylammonium chloride, and stirring to react for 3-3.5 hours at 70-90 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
fifthly, weighing TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA), azobisisobutyronitrile and toluene; TiO 22The mass ratio of the (KH-570) intermediate to the chitosan-glycidyl methacrylate intermediate (CS-GMA) is 1: (1-1.2); the mass of the azodiisobutyronitrile accounts for TiO2(KH-570) 3-3.5% of the total mass of the intermediate and the chitosan-glycidyl methacrylate intermediate (CS-GMA); TiO 22(KH-570) intermediateThe ratio of mass of (a) to volume of toluene is 1 g: (40-50) mL;
adding TiO into the mixture2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene are uniformly mixed, the temperature is raised to 75-85 ℃ under the stirring condition, azodiisobutyronitrile is added, and the mixture is stirred and reacted for 4-5 hours at the temperature of 75-85 ℃ to obtain TiO2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMA).
The third concrete implementation mode: the second embodiment is different from the second embodiment in that the stirring speed in the second step is 200 to 300r/min, and the stirring time is 25 to 35 minutes. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the second or third embodiment in that the volume ratio of the absolute ethyl alcohol to the deionized water in the third step is 9:1, and the stirring speed is 200 r/min. The rest is the same as the second embodiment.
The fifth concrete implementation mode: the difference between this embodiment and the second to the fourth embodiment is the colloidal TiO in the third step2The mass to volume ratio of deionized water of 1 g: 1 mL. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: this embodiment is different from the second to fifth embodiments in that the viscosity of the Chitosan (CS) in the fourth step is 170 to 250 mPas. The other is the same as one of the second to fifth embodiments.
The seventh embodiment: description of the preferred embodiments2The application of the modified chitosan adsorbent is to use the TiO2The modified chitosan adsorbent is used as an adsorbent for adsorbing heavy metal and organic substance pollutants in wastewater.
The specific implementation mode is eight: seventh embodiment is different from the seventh embodiment in that TiO2The specific application method of the modified chitosan adsorbent comprises the following steps: adding TiO into the mixture2Adding modified chitosan adsorbent into wastewater containing heavy metal pollutants and organic substances, ultrasonically dispersing uniformly, stirring, filtering, and adding TiO2Filtering out the modified chitosan adsorbent to complete the weight contentAnd (3) treating the wastewater containing the metal pollutants.
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: TiO of this example2The preparation method of the modified chitosan adsorbent comprises the following steps:
firstly, weighing 1g of tetrabutyl titanate and 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570);
secondly, adding 1g of tetrabutyl titanate weighed in the step one into 25mL of absolute ethyl alcohol, uniformly mixing, dropwise adding 20mL of hydrochloric acid with the concentration of 0.05mol/L under the stirring condition that the stirring speed is 200r/min, and stirring for 30 minutes at the speed of 200r/min after dropwise adding is finished to obtain the colloidal TiO2；
Thirdly, 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) weighed in the first step is added into the colloidal TiO obtained in the second step2Adding 9mL of absolute ethyl alcohol and 1mL of deionized water, heating to 40 ℃, and stirring at the speed of 200r/min for reaction for 0.5 hour; then ultrasonically washing the product for 30 minutes at 50 ℃ by using an ultrasonic cleaner, adding absolute ethyl alcohol, centrifugally washing for 10 minutes, pouring out the supernatant, repeatedly washing the lower-layer precipitate for three times, finally placing the precipitate into a vacuum drying oven, and drying for 4 hours at the temperature of 60 ℃ to obtain TiO2(KH-570) an intermediate;
weighing 1g of Chitosan (CS) with the viscosity of 190 mPas, 1g of Glycidyl Methacrylate (GMA), 0.14g of benzyltriethylammonium chloride and 20mL of toluene, uniformly mixing the Chitosan (CS), the glycidyl methacrylate and the toluene, heating to 70 ℃ by using a water bath under the stirring condition, adding the benzyltriethylammonium chloride, stirring and refluxing for 3 hours at 70 ℃, standing the reacted product, pouring out the supernatant, adding the precipitate into the toluene, centrifuging and washing for 10 minutes, centrifuging and washing for 3 times, finally placing the precipitate into a vacuum drying oven, and drying for 4 hours at the temperature of 60 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
fifthly, 0.5g of TiO is weighed2(KH-570) intermediate, 0.5g chitosan-glycidyl methacrylateOleyl ester intermediate (CS-GMA), 0.03g azobisisobutyronitrile and 20ml toluene; adding TiO into the mixture2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene are uniformly mixed, the mixture is heated to 80 ℃ by using a water bath under the stirring condition, azodiisobutyronitrile is added, the mixture is stirred and refluxed for 4 hours at 80 ℃, the reacted product is stood, the supernatant is poured out, the sediment is added with toluene and centrifugally washed for 10 minutes and 3 times, then the residual toluene solvent is evaporated by using a rotary evaporator and finally is placed into a vacuum drying oven to be dried for 4 hours at the temperature of 60 ℃, and TiO is obtained2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMA).
FIG. 1 shows TiO prepared in step three of example 12(KH-570) intermediate, CS-GMA intermediate prepared in step four, and TiO prepared in step five2(KH-570) -g- (CS-GMA) adsorbent, as seen in FIG. 1: 1716.36cm-1Respectively, is TiO2Characteristic absorption peak of stretching vibration of KH-570 in KH-570 and GMA ester group (O-C ═ O) in CS-GMA, 1632.07cm-1Respectively, is TiO2(KH-570) shows absorption peaks at KH-570 and GMA carbon-carbon double bond (C ═ C) in CS-GMA, indicating TiO2(KH-570) and CS-GMA intermediates were successfully prepared; 545.4cm-1The absorption peak is TiO2(KH-570) and TiO2(KH-570) -g- (CS-GMA) characteristic absorption peak of stretching vibration of titanium-oxygen single bond (Ti-O); 1164.78cm-1A characteristic absorption peak for absorbing stretching vibration of a carbon-oxygen single bond (C-O) in GMA ester in CS-GMA; 1076.13cm-1And 1028.30cm-1Absorption peaks at are CS-GMA and TiO2(KH-570) -g- (CS-GMA) characteristic absorption peak of carbon-oxygen single bond (C-O) stretching vibration in CS, and TiO2The double bond characteristic absorption peaks of (KH-570) -g- (CS-GMA) adsorbent KH-570 and GMA did not appear, indicating the successful preparation of TiO2(KH-570) -g- (CS-GMA). From the above infrared spectroscopic analysis, TiO2(KH-570) intermediate, CS-GMA intermediate, TiO2Each reaction of (KH-570) -g- (CS-GMA) adsorbent was successful, synthesizing a catalyst having TiO2And a CS functional adsorbent. The true bookExample synthesized TiO2The structural expression of the modified chitosan adsorbent is as follows:
Figure BDA0001822462480000071
wherein n is 25-28.
The TiO prepared in example 12The modified chitosan adsorbent is used for adsorption tests of heavy metals, and the specific operation is as follows:
10mL of HgCL with a concentration of 100mg/L was taken2The solution simulating heavy metal pollution water is put into a weighing bottle with 8 bottles, and 0.005g, 0.010g, 0.015g, 0.020g, 0.025g, 0.030g, 0.035g and 0.040g of TiO are respectively weighed2Adding the modified chitosan adsorbent into each weighing bottle, ultrasonically dispersing for 30 minutes, and stirring for 4 hours by using a four-joint stirrer. Taking out 5mL of the mixture in the weighing bottle, filtering, transferring 1mL of the mixture into a volumetric flask with constant volume of 100mL by using a liquid transfer gun, and detecting Hg2+To finally calculate Hg2+The amount of adsorption of (3). Separately testing and calculating the adsorbent for Pb in the same manner2+And toluene adsorption amount, the results show that TiO prepared in example 12Modified chitosan adsorbent for Hg2+The adsorption quantity of the lead-acid catalyst reaches 26.22mg/g, and the lead-acid catalyst is used for Pb2+The adsorption amount of the catalyst reaches 589.87mg/g, and the adsorption amount of the toluene reaches 53.31 mg/g.
Example 2: TiO of this example2The preparation method of the modified chitosan adsorbent comprises the following steps:
firstly, weighing 1g of tetrabutyl titanate and 1g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570);
secondly, adding 1g of tetrabutyl titanate weighed in the step one into 25mL of absolute ethyl alcohol, uniformly mixing, then dropwise adding 20mL of hydrochloric acid with the concentration of 0.05mol/L under the stirring condition that the stirring speed is 200r/min, and stirring for 30 minutes at the speed of 200r/min after dropwise adding is finished to obtain the colloidal TiO2；
Thirdly, 1g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) weighed in the first step is added into the glue obtained in the second stepBulk TiO2Adding 9mL of absolute ethyl alcohol and 1mL of deionized water, heating to 50 ℃, and stirring at the speed of 200r/min for reaction for 1.5 hours; then ultrasonically washing the product for 30 minutes at 50 ℃ by using an ultrasonic cleaner, adding absolute ethyl alcohol, centrifugally washing for 10 minutes, pouring out the supernatant, repeatedly washing the lower-layer precipitate for three times, finally placing the precipitate into a vacuum drying oven, and drying for 4 hours at the temperature of 60 ℃ to obtain TiO2(KH-570) an intermediate;
weighing 1g of Chitosan (CS) with the viscosity of 190mpa & s, 1g of Glycidyl Methacrylate (GMA), 0.14g of benzyltriethylammonium chloride and 20mL of toluene, uniformly mixing the Chitosan (CS), the Glycidyl Methacrylate (GMA) and the toluene, heating the mixture to 80 ℃ by using a water bath under the stirring condition, adding the benzyltriethylammonium chloride, stirring and refluxing the mixture for 3 hours at 80 ℃, standing the reacted product, pouring out the supernatant, adding the precipitate into the toluene, centrifuging and washing the precipitate for 10 minutes, centrifuging and washing the precipitate for 3 times, finally placing the precipitate into a vacuum drying oven, and drying the precipitate for 4 hours at the temperature of 60 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
fifthly, 0.5g of TiO is weighed2(KH-570) intermediate, 0.5g chitosan-glycidyl methacrylate intermediate (CS-GMA), 0.03g azobisisobutyronitrile and 20mL toluene; adding TiO into the mixture2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene are uniformly mixed, the mixture is heated to 80 ℃ by using a water bath under the stirring condition, azodiisobutyronitrile is added, the mixture is stirred and refluxed for 4 hours at 80 ℃, the reacted product is stood, the supernatant is poured out, the sediment is added with toluene and centrifugally washed for 10 minutes and 3 times, then the residual toluene solvent is evaporated by using a rotary evaporator and finally is placed into a vacuum drying oven to be dried for 4 hours at the temperature of 60 ℃, and TiO is obtained2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMMA).
Hg was measured and calculated, respectively, by the same method as in example 12+、Pb2+And the amount of toluene adsorbed. The results show that TiO prepared in this example 22Modified chitinSugar adsorbent to Hg2+The adsorption quantity of the lead-free acid reaches 30.49mg/g, and the lead-free acid is used for Pb2+The adsorption amount of the catalyst reaches 634.65mg/g, and the maximum adsorption amount of the toluene reaches 56.62 mg/g.
Example 3: TiO of this example2The preparation method of the modified chitosan adsorbent comprises the following steps:
firstly, weighing 1g of tetrabutyl titanate and 1.5g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570);
secondly, adding 1g of tetrabutyl titanate weighed in the step one into 25mL of absolute ethyl alcohol, uniformly mixing, then dropwise adding 20mL of hydrochloric acid with the concentration of 0.05mol/L under the stirring condition that the stirring speed is 200r/min, and stirring for 30 minutes at the speed of 200r/min after dropwise adding is finished to obtain the colloidal TiO2；
Thirdly, 1.5g of 3- (methacryloyloxy) propyl trimethoxy silane (KH-570) weighed in the first step is added into the colloidal TiO obtained in the second step2Adding 9mL of absolute ethyl alcohol and 1mL of deionized water, heating to 60 ℃, and stirring at the speed of 200r/min for reaction for 2 hours; then ultrasonically washing the product for 30 minutes at 50 ℃ by using an ultrasonic cleaner, adding absolute ethyl alcohol, centrifugally washing for 10 minutes, pouring out the supernatant, repeatedly washing the lower-layer precipitate for three times, finally placing the precipitate into a vacuum drying oven, and drying for 4 hours at the temperature of 60 ℃ to obtain TiO2(KH-570) an intermediate;
weighing 1g of Chitosan (CS) with the viscosity of 190mpa & s, 1g of Glycidyl Methacrylate (GMA), 0.14g of benzyltriethylammonium chloride and 20mL of toluene, uniformly mixing the Chitosan (CS), the Glycidyl Methacrylate (GMA) and the toluene, heating the mixture to 90 ℃ by using a water bath under the stirring condition, adding the benzyltriethylammonium chloride, stirring and refluxing the mixture for 3 hours at 90 ℃, standing the reacted product, pouring out the supernatant, adding the precipitate into the toluene, centrifuging and washing the precipitate for 10 minutes, centrifuging and washing the precipitate for 3 times, finally placing the precipitate into a vacuum drying oven, and drying the precipitate for 4 hours at the temperature of 60 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
fifthly, 0.5g of TiO is weighed2(KH-570), intermediate, 0.5gChitosan-glycidyl methacrylate intermediate (CS-GMA), 0.03g azobisisobutyronitrile, and 20mL toluene; adding TiO into the mixture2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene are uniformly mixed, the mixture is heated to 80 ℃ by using a water bath under the stirring condition, azodiisobutyronitrile is added, the mixture is stirred and refluxed for 4 hours at 80 ℃, the reacted product is stood, the supernatant is poured out, the sediment is added with toluene and centrifugally washed for 10 minutes and 3 times, then the residual toluene solvent is evaporated by using a rotary evaporator and finally is placed into a vacuum drying oven to be dried for 4 hours at the temperature of 60 ℃, and TiO is obtained2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMA).
Hg was measured and calculated, respectively, by the same method as in example 12+、Pb2+And the amount of toluene adsorbed. The results show that the TiO prepared in this example2Modified chitosan adsorbent for Hg2+The adsorption capacity of the catalyst reaches 28.37mg/g, and the catalyst is used for Pb2+The adsorption amount of the catalyst reaches 601.03mg/g, and the adsorption amount of the toluene reaches 48.96 mg/g.

Claims (8)

1. TiO 22The modified chitosan adsorbent is characterized in that the structural formula of the adsorbent is as follows:
Figure FDA0001822462470000011
Figure FDA0001822462470000012
wherein n is 20-30 and is marked as TiO2(KH-570)-g-(CS-GMA)。
2. TiO 22The preparation method of the modified chitosan adsorbent is characterized by comprising the following steps:
firstly, according to the mass ratio of tetrabutyl titanate to 3- (methacryloyloxy) propyl trimethoxy silane being 1: (0.5-1.5) weighing tetrabutyl titanate and 3- (methacryloyloxy) propyl trimethoxy silane;
secondly, according to the mass ratio of tetrabutyl titanate to absolute ethyl alcohol of 1 g: (22-25) mL, wherein the ratio of the mass of tetrabutyl titanate to the volume of hydrochloric acid with the concentration of 0.05mol/L is 1 g: (19-22) mL, adding the tetrabutyl titanate weighed in the step one into absolute ethyl alcohol, uniformly mixing, dropwise adding hydrochloric acid under the stirring condition, and stirring after dropwise adding to obtain colloidal TiO2；
Thirdly, adding the 3- (methacryloyloxy) propyl trimethoxy silane weighed in the first step into the colloidal TiO obtained in the second step2Adding absolute ethyl alcohol and deionized water, heating to 40-60 ℃, stirring for reaction for 0.5-2 hours, washing and drying to obtain TiO2(KH-570) an intermediate;
weighing chitosan, glycidyl methacrylate, benzyltriethylammonium chloride and toluene, wherein the mass ratio of the chitosan to the glycidyl methacrylate is 1 (1-1.2), and the mass of the benzyltriethylammonium chloride accounts for 7-8% of the total mass of the chitosan and the glycidyl methacrylate; the ratio of the mass of chitosan to the volume of toluene was 1 g: (20-25) mL; uniformly mixing chitosan, glycidyl methacrylate and toluene, heating to 70-90 ℃ under the stirring condition, adding benzyltriethylammonium chloride, and stirring to react for 3-3.5 hours at 70-90 ℃ to obtain a chitosan-glycidyl methacrylate intermediate; expressed in CS-GMA;
fifthly, weighing TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate, azobisisobutyronitrile and toluene; wherein the TiO is2(KH-570) the mass ratio of the intermediate to the chitosan-glycidyl methacrylate intermediate is 1: (1-1.2); the mass of the azodiisobutyronitrile accounts for TiO2(KH-570) 3-3.5% of the total mass of the intermediate and the chitosan-glycidyl methacrylate intermediate; TiO 22(KH-570) the ratio of the mass of intermediate to the volume of toluene was 1 g: (40-50) mL; adding TiO into the mixture2(KH-570) uniformly mixing the intermediate, the chitosan-glycidyl methacrylate intermediate and toluene, heating to 75-85 ℃ under the stirring condition, and adding azobisisobutyronitrileStirring and reacting for 4-5 hours at the temperature of 75-85 ℃ to obtain TiO2Modified chitosan adsorbent, using TiO2(KH-570) -g- (CS-GMA).
3. A TiO according to claim 22The preparation method of the modified chitosan adsorbent is characterized in that in the second step, the stirring speed is 200-300 r/min, and the stirring time is 25-35 minutes.
4. A TiO according to claim 2 or 32The preparation method of the modified chitosan adsorbent is characterized in that the volume ratio of the absolute ethyl alcohol to the deionized water in the third step is 9:1, and the stirring speed is 200 r/min.
5. A TiO according to claim 2 or 32The preparation method of the modified chitosan adsorbent is characterized in that the colloid TiO adsorbent in the step three is colloidal TiO2The mass to volume ratio of deionized water of 1 g: 1 mL.
6. A TiO according to claim 2 or 32The preparation method of the modified chitosan adsorbent is characterized in that the viscosity range of the chitosan in the step four is 170-250 mPa.
7. A TiO compound according to claim 12The application of modified chitosan adsorbent is characterized in that TiO is used as raw material2The modified chitosan adsorbent is used as an adsorbent for adsorbing heavy metal and organic substance pollutants in wastewater.
8. A TiO according to claim 72The application of the modified chitosan adsorbent is characterized in that the specific application method comprises the following steps: adding TiO into the mixture2Adding modified chitosan adsorbent into wastewater containing heavy metal pollutants and organic substances, ultrasonically dispersing uniformly, stirring, filtering, and adding TiO2Filtering the modified chitosan adsorbent to finish the treatment of the wastewater containing heavy metal pollutants.
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