CN109225149A - A kind of TiO2Modification of chitosan adsorbent and its preparation method and application - Google Patents
A kind of TiO2Modification of chitosan adsorbent and its preparation method and application Download PDFInfo
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- CN109225149A CN109225149A CN201811171208.4A CN201811171208A CN109225149A CN 109225149 A CN109225149 A CN 109225149A CN 201811171208 A CN201811171208 A CN 201811171208A CN 109225149 A CN109225149 A CN 109225149A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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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
- 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
- B01J20/0211—Compounds of Ti, Zr, Hf
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A kind of TiO2Modification of chitosan adsorbent and its preparation method and application, the present invention relates to adsorbent materials and its preparation method and application.The present invention is to solve existing chitosan compound adsorbing agents to heavy metal ion mercury in absorption water, lead and the low technical problem of organic solvent toluene absorption amount.The TiO2The structural formula of modification of chitosan adsorbent are as follows:Preparation method: colloid TiO is first prepared2, preparation TiO is then reacted with KH-5702(KH-570) intermediate；With chitosan, glycidyl methacrylate and benzyltriethylammoinium chloride, reaction prepares chitosan-glycidyl methacrylate intermediate in toluene again；Finally by TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate and azodiisobutyronitrile are reacted in toluene, obtain TiO2Modification of chitosan adsorbent.The heavy metal and organic substance the pollutant adsorbent being used in absorption waste water.It is to Hg2+、Pb2+25~30.5mg/g, 589~635mg/g and 48~57mg/g are followed successively by with the adsorbance of toluene.It can be used for sewage treatment field.
Description
Technical field
The present invention relates to adsorbent material technical field more particularly to a kind of TiO2The preparation method of modification of chitosan adsorbent
With application.
Background technique
Environmental pollution mainly has the pollution of heavy metal and organic substance, pollutes water most serious of all, heavy metal in waste water
And the content of organic solvent severely exceeds, and causes serious influence to the water body of nature, endangers the health of the mankind.In weight
The harm that the pollution of mercury and lead ion generates in gold pollution is especially serious, and inorganic mercury ion can be combined with the zymoprotein of human body,
The activity for inhibiting various enzymes makes the normal function of cell that obstacle occur；Lead is in the multiple maincenters and Peripheral Nervous of human body
Specific neuromechanism have direct toxic action, children's lead poisoning can make intelligence degradation；And toluene slow poisoning often goes out
Existing neurasthenic syndrome, has damage to liver kidney, so removing the heavy metal of water removal and organic substance is significantly thing
Feelings.
Shitosan macromolecule class adsorbent is forward position and the emphasis of research at present, because of the physics of high-molecular compound and change
Property multiplicity is learned, has different adsorption mechanisms to various pollutants, and adsorption effect is relatively good.It is existing to use TiO2It is modified
The adsorbent of chitosan preparation is more, the reason is that TiO2Inherently there is good adsorption effect, and chitosan itself also has
Good adsorption effect, the two is combined together, and adsorption effect is very good." fiber and polymer " the 1st phases of volume 18 in 2017
22-32 pages of article " carboxymethyl chitosan-cellulose-nano TiO2Heavy metal pollution in the effective Adsorption water of compound
The research of object " (Ternary Carboxymethyl Chitosan-hemicellulose-nanosized
TiO2Composite as Effective Adsorbent for Removal of Heavy Metal Contaminants
From Water) it discloses and a kind of utilizes carboxymethyl chitosan, cellulose and nano-TiO2The composite material of synthesis tests multiple
Condensation material is to Ni (II), Cd (II), Cu (II), Hg (II), the absorption removal effect of Mn (VII) and Cr (VI), the results showed that should
Composite material has preferable adsorption capacity to these ions, but to Hg2+Adsorbance only have 4.3mg/g, to Hg2+Absorption compared with
It is low.Article " the nano-TiO of " Taiwan chemical engineering institute journal " 333-343 pages of 58 phase in 20162Functionalization chitosan nano fiber is gone
The research of removing heavy metals ion " (Chitosan nanofibers functionalized by TiO2nanoparticles
For the removal of heavy metal ions) disclose be prepared for chitosan/titanium dioxide composite nano fiber suction
Attached dose, the results showed that the maximum adsorption capacity to Pb (II), Cu (II) is respectively 526.5,475.5mg/g.And it can adsorb organic
The research of the adsorbent of solvent toluene not yet appears in the newspapers.
Summary of the invention
The present invention is to solve existing carboxymethyl chitosan-cellulose-nano TiO2Compound and chitosan/titanium dioxide
Heavy metal ion mercury in titanium composite nano fiber adsorbent absorption water, lead and the low technical problem of organic solvent toluene absorption amount,
And provide a kind of TiO2Modification of chitosan adsorbent and its preparation method and application.
TiO of the invention2The structure expression of modification of chitosan adsorbent are as follows:
,
Wherein n=20~30.It is denoted as TiO2(KH-570)-g-(CS-GMA)。
Above-mentioned TiO2The preparation method of modification of chitosan adsorbent, comprising the following steps:
One, it is 1 by the mass ratio of butyl titanate and 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570):
The ratio of (0.5~1.5) weighs butyl titanate and and 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570)；
Two, it is 1g:(22~25 by the ratio of the quality of butyl titanate and the volume of dehydrated alcohol) mL, butyl titanate
The ratio of the volume for the hydrochloric acid that quality and concentration are 0.05mol/L is 1g:(19~22) ratio of mL, by the weighed metatitanic acid of step 1
Four butyl esters are charged first in dehydrated alcohol and are uniformly mixed, then hydrochloric acid is added dropwise under agitation, after being added dropwise, stirring,
Obtain colloid TiO2；
Wherein mixing speed is 200~300r/min in step 2, and mixing time is 25~35 minutes.
Three, step 1 weighed 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) is added to step 2
Obtained colloid TiO2In, dehydrated alcohol and deionized water are added, is heated to 40~60 DEG C, is stirred to react 0.5~2 hour,
It is washed out, dries, obtain TiO2(KH-570) intermediate；
Wherein the volume ratio of dehydrated alcohol and deionized water is 9:1, mixing speed 200r/min in step 3；
Colloid TiO in step 32Quality and deionized water volume ratio be 1g:1mL；
Four, chitosan (CS), glycidyl methacrylate (GMA), benzyltriethylammoinium chloride and toluene are weighed,
The mass ratio of middle chitosan (CS) and glycidyl methacrylate (GMA) are 1:(1~1.2), benzyltriethylammoinium chloride
Quality account for the 7%~8% of chitosan (CS) and glycidyl methacrylate (GMA) gross mass；The matter of chitosan (CS)
The ratio of amount and the volume of toluene is 1g:(20~25) mL；
First chitosan (CS), glycidyl methacrylate (GMA) and toluene are uniformly mixed, risen under agitation
Temperature adds benzyltriethylammoinium chloride to 70~90 DEG C, is stirred to react 3~3.5 hours, obtains under conditions of 70~90 DEG C
Chitosan-glycidyl methacrylate intermediate；It is indicated with CS-GMA；
Wherein the range of viscosities of chitosan (CS) is 170~250mPas,
Five, TiO is weighed2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA),
Azodiisobutyronitrile and toluene；TiO2(KH-570) intermediate and chitosan-glycidyl methacrylate intermediate (CS-
GMA mass ratio) is 1:(1~1.2)；The quality of azodiisobutyronitrile accounts for TiO2(KH-570) intermediate and chitosan-methyl
The 3%~3.5% of glycidyl acrylate intermediate (CS-GMA) gross mass；TiO2(KH-570) quality and first of intermediate
The ratio of the volume of benzene is 1g:(40~50) mL；
By TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene
It is uniformly mixed, is warming up to 75~85 DEG C under agitation, adds azodiisobutyronitrile, stirred under conditions of 75~85 DEG C
Reaction 4~5 hours, obtains TiO2Modification of chitosan adsorbent, uses TiO2(KH-570)-g- (CS-GMA) is indicated.
TiO of the invention2The application of modification of chitosan adsorbent is that as the heavy metal in absorbent absorption waste water and have
Machine substance pollutant, specific method is: by TiO2Modification of chitosan adsorbent is added to containing heavy metal contaminants and organic substance
Waste water in, ultrasonic disperse is uniform, then stir, filter, by TiO2Modification of chitosan adsorbent filters out, and completes containing a huge sum of money
Belong to the processing of the waste water of pollutant.
TiO of the invention2The synthetic reaction process of modification of chitosan adsorbent is as follows:
Of the invention uses 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) modified colloidal TiO2, than with it is solid
Body TiO2It more easily reacts, KH-570 modified colloidal TiO2, make inorganic TiO2Become Organic, colloid TiO2The hydroxyl on surface is more,
It can react to introduce a large amount of double bond with 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570).Shell is poly- simultaneously
Sugared (CS) is reacted with glycidyl methacrylate (GMA), and double bond has had also been introduced largely.TiO2(KH-570) intermediate with
Chitosan-glycidyl methacrylate intermediate (CS-GMA) easily reacts, and generates novel adsorbent TiO2
(KH-570)-g- (CS-GMA), which has nanometer and high molecular chemical characters, to heavy metal Hg2+、Pb2+With toluene have compared with
Good Adsorption effect, to Hg2+Adsorbance be 25~30.5mg/g, to Pb2+Adsorbance be 589~635mg/g, it is right
The adsorbance of toluene is 48~57mg/g.
TiO of the invention2Modification of chitosan adsorbent can be used for sewage treatment field.
Detailed description of the invention
Fig. 1 is TiO prepared by embodiment 12(KH-570) intermediate, CS-GMA intermediate and TiO2(KH-570)-g-(CS-
GMA) the infrared spectrum of adsorbent.
Specific embodiment
Specific embodiment 1: the TiO of present embodiment2The structure expression of modification of chitosan adsorbent are as follows:
,
Wherein n=20~30.It is denoted as TiO2(KH-570)-g-(CS-GMA)。
Specific embodiment 2: TiO described in specific embodiment one2The preparation method of modification of chitosan adsorbent, including
Following steps:
One, it is 1 by the mass ratio of butyl titanate and 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570):
The ratio of (0.5~1.5) weighs butyl titanate and and 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570)；
Two, it is 1g:(22~25 by the ratio of the quality of butyl titanate and the volume of dehydrated alcohol) mL, butyl titanate
The ratio of the volume for the hydrochloric acid that quality and concentration are 0.05mol/L is 1g:(19~22) ratio of mL, by the weighed metatitanic acid of step 1
Four butyl esters are charged first in dehydrated alcohol and are uniformly mixed, then hydrochloric acid is added dropwise under agitation, after being added dropwise, stirring,
Obtain colloid TiO2；
Three, step 1 weighed 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) is added to step 2
Obtained colloid TiO2In, dehydrated alcohol and deionized water are added, is heated to 40~60 DEG C, is stirred to react 0.5~2 hour,
It is washed out, dries, obtain TiO2(KH-570) intermediate；
Four, chitosan (CS), glycidyl methacrylate (GMA), benzyltriethylammoinium chloride and toluene are weighed,
The mass ratio of middle chitosan (CS) and glycidyl methacrylate (GMA) are 1:(1~1.2), benzyltriethylammoinium chloride
Quality account for the 7%~8% of chitosan (CS) and glycidyl methacrylate (GMA) gross mass；The matter of chitosan (CS)
The ratio of amount and the volume of toluene is 1g:(20~25) mL；
First chitosan (CS), glycidyl methacrylate (GMA) and toluene are uniformly mixed, risen under agitation
Temperature adds benzyltriethylammoinium chloride to 70~90 DEG C, is stirred to react 3~3.5 hours, obtains under conditions of 70~90 DEG C
Chitosan-glycidyl methacrylate intermediate；It is indicated with CS-GMA；
Five, TiO is weighed2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA),
Azodiisobutyronitrile and toluene；TiO2(KH-570) intermediate and chitosan-glycidyl methacrylate intermediate (CS-
GMA mass ratio) is 1:(1~1.2)；The quality of azodiisobutyronitrile accounts for TiO2(KH-570) intermediate and chitosan-methyl
The 3%~3.5% of glycidyl acrylate intermediate (CS-GMA) gross mass；TiO2(KH-570) quality and first of intermediate
The ratio of the volume of benzene is 1g:(40~50) mL；
By TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate (CS-GMA) and toluene
It is uniformly mixed, is warming up to 75~85 DEG C under agitation, adds azodiisobutyronitrile, stirred under conditions of 75~85 DEG C
Reaction 4~5 hours, obtains TiO2Modification of chitosan adsorbent, uses TiO2(KH-570)-g- (CS-GMA) is indicated.
Specific embodiment 3: present embodiment from mixing speed is in step 2 unlike specific embodiment two
200~300r/min, mixing time are 25~35 minutes.It is other to be identical with embodiment two.
Specific embodiment 4: present embodiment dehydrated alcohol in step 3 unlike specific embodiment two or three
Volume ratio with deionized water is 9:1, mixing speed 200r/min.It is other to be identical with embodiment two.
Specific embodiment 5: colloid in step 3 unlike one of present embodiment and specific embodiment two to four
TiO2Quality and deionized water volume ratio be 1g:1mL.It is other identical as one of specific embodiment two to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five described in step 4
Chitosan (CS) range of viscosities be 170~250mPas.It is other identical as one of specific embodiment two to five.
Specific embodiment 7: TiO described in specific embodiment one2The application of modification of chitosan adsorbent, being should
TiO2Modification of chitosan adsorbent is as the heavy metal and organic substance pollutant in absorbent absorption waste water.
Specific embodiment 8: present embodiment is unlike specific embodiment seven, TiO2Modification of chitosan absorption
The concrete application method of agent is: by TiO2Modification of chitosan adsorbent is added to the waste water containing heavy metal contaminants and organic substance
In, ultrasonic disperse is uniform, then stirs, and filters, by TiO2Modification of chitosan adsorbent filters out, and completes to contain heavy metal pollution
The processing of the waste water of object.
Beneficial effects of the present invention are verified with the following examples:
Embodiment 1: the TiO of the present embodiment2The preparation method of modification of chitosan adsorbent, sequentially includes the following steps:
One, 1g butyl titanate and and 0.5g 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) are weighed；
Two, the weighed 1g butyl titanate of step 1 is charged first in 25ml dehydrated alcohol and is uniformly mixed, then stirred
It is 0.05mol/L hydrochloric acid that 20mL concentration is added dropwise under the stirring condition that speed is 200r/min, after being added dropwise, in 200r/
It is stirred 30 minutes under the speed of min, obtains colloid TiO2；
Three, 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) of the weighed 0.5g of step 1 is added to
The colloid TiO that step 2 obtains2In, the dehydrated alcohol of 9mL and the deionized water of 1mL are added, 40 DEG C are heated to, with 200r/
The speed of min is stirred to react 0.5 hour；Then by product ultrasonic cleaner at 50 DEG C supersound washing 30 minutes, then plus
Enter dehydrated alcohol centrifuge washing 10 minutes, supernatant is outwelled, lower sediment washes repeatedly three times, is finally putting into vacuum oven
It is interior, it is 4 hours dry under conditions of temperature is 60 DEG C, obtain TiO2(KH-570) intermediate；
Four, weigh 1g viscosity be the chitosan (CS) of 190mPas, 1g glycidyl methacrylate (GMA),
0.14g benzyltriethylammoinium chloride and 20mL toluene, it is first that chitosan (CS) and glycidyl methacrylate and toluene is mixed
It closes uniformly, adds benzyltriethylammoinium chloride to 70 DEG C with warming-in-water under agitation, stirred back under the conditions of 70 DEG C
Stream 3 hours after standing the product after reaction, outwells supernatant, and precipitating is added toluene centrifuge washing 10 minutes, centrifuge washing 3
It is secondary, it is finally putting into vacuum oven, it is 4 hours dry under conditions of temperature is 60 DEG C, obtain chitosan-methacrylic acid contracting
Water glyceride intermediate；It is indicated with CS-GMA；
Five, 0.5 gram of TiO is weighed2(KH-570) intermediate, 0.5 gram of chitosan-glycidyl methacrylate intermediate
(CS-GMA), 0.03g azodiisobutyronitrile and 20ml toluene；By TiO2(KH-570) intermediate, chitosan-methacrylic acid contracting
Water glyceride intermediate (CS-GMA) and toluene are uniformly mixed, and add azo to 80 DEG C with warming-in-water under agitation
Bis-isobutyronitrile is stirred at reflux 4 hours under the conditions of 80 DEG C, after the product after reaction is stood, outwells supernatant, first is added in precipitating
Benzene centrifuge washing 10 minutes, centrifuge washing 3 times, then remaining toluene solvant is evaporated with Rotary Evaporators, is finally putting into true
It is 4 hours dry under conditions of temperature is 60 DEG C in empty drying box, obtain TiO2Modification of chitosan adsorbent, uses TiO2(KH-
570)-g- (CS-GMA) is indicated.
Fig. 1 is the TiO of 1 preparation step three of the present embodiment preparation2(KH-570) in CS-GMA prepared by intermediate, step 4
Mesosome and the TiO prepared through step 52(KH-570) infrared spectrogram of-g- (CS-GMA) adsorbent, as can be seen from Figure 1:
1716.36cm-1The absorption peak at place is TiO respectively2(KH-570) GMA ester group (O-C=O) carbon oxygen is double in KH-570 and CS-GMA in
The characteristic absorption peak of key stretching vibration, 1632.07cm-1The absorption peak at place is TiO respectively2(KH-570) KH-570 and CS-GMA in
Middle GMA carbon-carbon double bond (C=C) absorption peak, illustrates TiO2(KH-570) it is successfully prepared with CS-GMA intermediate；545.4cm-1Place
Absorption peak is TiO2(KH-570) and TiO2(KH-570) feature of titanyl singly-bound (Ti-O) stretching vibration is inhaled in-g- (CS-GMA)
Receive peak；1164.78cm-1In the absorption CS-GMA at place in GMA ester the stretching vibration of carbon oxygen singly-bound (C-O) characteristic absorption peak；
1076.13cm-1And 1028.30cm-1The absorption peak at place is CS-GMA and TiO2(KH-570) carbon oxygen list in CS in-g- (CS-GMA)
The characteristic absorption peak of key (C-O) stretching vibration, and TiO2(KH-570)-g- (CS-GMA) adsorbent KH-570's and GMA is double
Key characteristic absorption peak does not occur, illustrates to be successfully prepared TiO2(KH-570)-g-(CS-GMA).It can by the above Assignment of Infrared Spectrum
Know, TiO2(KH-570) intermediate, CS-GMA intermediate, TiO2(KH-570) every single step reaction of-g- (CS-GMA) adsorbent is all
It is that successfully, having synthesized has TiO2With the adsorbent of CS function.The TiO of the present embodiment synthesis2The knot of modification of chitosan adsorbent
Structure expression formula are as follows:
,
Wherein n=25~28.
TiO prepared by the present embodiment 12Absorption of the modification of chitosan adsorbent for heavy metal is tested, and concrete operations are such as
Under:
Take the HgCL that the concentration of 10mL is 100mg/L2Solution simulation heavy metal-containing polluted water is put into weighing bottle, and totally 8 bottles, point
Also known as take 0.005g, 0.010g, 0.015g, 0.020g, 0.025g, 0.030g, 0.035g, 0.040g TiO2Modification of chitosan
Adsorbent is added in each weighing bottle, ultrasonic disperse 30 minutes, is stirred 4 hours with tetrad blender.It respectively will be in weighing bottle
Mixture take out 5mL, filtering then pipettes 1mL constant volume into the volumetric flask of 100mL with liquid-transfering gun, detects Hg2+Concentration, most
After calculate Hg2+Adsorbance.Same method tests respectively and calculates adsorbent to Pb2+With the adsorbance of toluene, as a result table
Bright, prepared by the present embodiment 1 TiO2Modification of chitosan adsorbent is to Hg2+Absorption amount reach 26.22mg/g, to Pb2+Absorption
Amount reaches 589.87mg/g, reaches 53.31mg/g to the adsorbance of toluene.
Embodiment 2: the TiO of the present embodiment2The preparation method of modification of chitosan adsorbent, sequentially includes the following steps:
One, 1g butyl titanate and and 1g 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) are weighed；
Two, the weighed 1g butyl titanate of step 1 is charged first in 25mL dehydrated alcohol and is uniformly mixed, then stirred
It is 0.05mol/L hydrochloric acid that 20mL concentration is added dropwise under the stirring condition that speed is 200r/min, after being added dropwise, in 200r/
It is stirred 30 minutes under the speed of min, obtains colloid TiO2；
Three, 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) of the weighed 1g of step 1 is added to step
Rapid two obtained colloid TiO2In, add the dehydrated alcohol of 9mL and the deionized water of 1mL, be heated to 50 DEG C, with 200r/
The speed of min is stirred to react 1.5 hours；Then by product ultrasonic cleaner at 50 DEG C supersound washing 30 minutes, then plus
Enter dehydrated alcohol centrifuge washing 10 minutes, supernatant is outwelled, lower sediment washes repeatedly three times, is finally putting into vacuum oven
It is interior, it is 4 hours dry under conditions of temperature is 60 DEG C, obtain TiO2(KH-570) intermediate；
Four, weigh 1g viscosity be the chitosan (CS) of 190mpas, 1g glycidyl methacrylate (GMA),
0.14g benzyltriethylammoinium chloride and 20mL toluene, first by chitosan (CS) and glycidyl methacrylate (GMA) and first
Benzene is uniformly mixed, and is added benzyltriethylammoinium chloride to 80 DEG C with warming-in-water under agitation, is stirred under the conditions of 80 DEG C
Reflux 3 hours is mixed, after the product after reaction is stood, outwells supernatant, precipitating is added toluene centrifuge washing 10 minutes, and centrifugation is washed
It washs 3 times, is finally putting into vacuum oven, it is 4 hours dry under conditions of temperature is 60 DEG C, obtain chitosan-metering system
Acid glycidyl ester intermediate；It is indicated with CS-GMA；
Five, 0.5 gram of TiO is weighed2(KH-570) intermediate, 0.5 gram of chitosan-glycidyl methacrylate intermediate
(CS-GMA), 0.03g azodiisobutyronitrile and 20mL toluene；By TiO2(KH-570) intermediate, chitosan-methacrylic acid contracting
Water glyceride intermediate (CS-GMA) and toluene are uniformly mixed, and add azo to 80 DEG C with warming-in-water under agitation
Bis-isobutyronitrile is stirred at reflux 4 hours under the conditions of 80 DEG C, after the product after reaction is stood, outwells supernatant, first is added in precipitating
Benzene centrifuge washing 10 minutes, centrifuge washing 3 times, then remaining toluene solvant is evaporated with Rotary Evaporators, is finally putting into true
It is 4 hours dry under conditions of temperature is 60 DEG C in empty drying box, obtain TiO2Modification of chitosan adsorbent, uses TiO2(KH-
570)-g- (CS-GMMA) is indicated.
It is tested respectively using method same as Example 1 and calculates Hg2+、Pb2+With the adsorbance of toluene.As a result table
Bright, prepared by the present embodiment 2 TiO2Modification of chitosan adsorbent is to Hg2+Absorption amount reach 30.49mg/g, to Pb2+Absorption
Amount reaches 634.65mg/g, reaches 56.62mg/g to the maximal absorptive capacity of toluene.
Embodiment 3: the TiO of the present embodiment2The preparation method of modification of chitosan adsorbent, sequentially includes the following steps:
One, 1g butyl titanate and and 1.5g 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) are weighed；
Two, the weighed 1g butyl titanate of step 1 is charged first in 25mL dehydrated alcohol and is uniformly mixed, then stirred
It is 0.05mol/L hydrochloric acid that 20mL concentration is added dropwise under the stirring condition that speed is 200r/min, after being added dropwise, in 200r/
It is stirred 30 minutes under the speed of min, obtains colloid TiO2；
Three, 3- (methacryloxypropyl) propyl trimethoxy silicane (KH-570) of the weighed 1.5g of step 1 is added to
The colloid TiO that step 2 obtains2In, the dehydrated alcohol of 9mL and the deionized water of 1mL are added, is heated to 60 DEG C, with
The speed of 200r/min is stirred to react 2 hours；Then by product ultrasonic cleaner at 50 DEG C supersound washing 30 minutes, then
It is added dehydrated alcohol centrifuge washing 10 minutes, supernatant is outwelled, lower sediment washes repeatedly three times, is finally putting into vacuum drying
It is 4 hours dry under conditions of temperature is 60 DEG C in case, obtain TiO2(KH-570) intermediate；
Four, weigh 1g viscosity be the chitosan (CS) of 190mpas, 1g glycidyl methacrylate (GMA),
0.14g benzyltriethylammoinium chloride and 20mL toluene, first by chitosan (CS) and glycidyl methacrylate (GMA) and first
Benzene is uniformly mixed, and is added benzyltriethylammoinium chloride to 90 DEG C with warming-in-water under agitation, is stirred under the conditions of 90 DEG C
Reflux 3 hours is mixed, after the product after reaction is stood, outwells supernatant, precipitating is added toluene centrifuge washing 10 minutes, and centrifugation is washed
It washs 3 times, is finally putting into vacuum oven, it is 4 hours dry under conditions of temperature is 60 DEG C, obtain chitosan-metering system
Acid glycidyl ester intermediate；It is indicated with CS-GMA；
Five, 0.5 gram of TiO is weighed2(KH-570) intermediate, 0.5 gram of chitosan-glycidyl methacrylate intermediate
(CS-GMA), 0.03g azodiisobutyronitrile and 20mL toluene；By TiO2(KH-570) intermediate, chitosan-methacrylic acid contracting
Water glyceride intermediate (CS-GMA) and toluene are uniformly mixed, and add azo to 80 DEG C with warming-in-water under agitation
Bis-isobutyronitrile is stirred at reflux 4 hours under the conditions of 80 DEG C, after the product after reaction is stood, outwells supernatant, first is added in precipitating
Benzene centrifuge washing 10 minutes, centrifuge washing 3 times, then remaining toluene solvant is evaporated with Rotary Evaporators, is finally putting into true
It is 4 hours dry under conditions of temperature is 60 DEG C in empty drying box, obtain TiO2Modification of chitosan adsorbent, uses TiO2(KH-
570)-g- (CS-GMA) is indicated.
It is tested respectively using method same as Example 1 and calculates Hg2+、Pb2+With the adsorbance of toluene.The result shows that
TiO manufactured in the present embodiment2Modification of chitosan adsorbent is to Hg2+Absorption amount reach 28.37mg/g, to Pb2+Absorption amount reach
To 601.03mg/g, 48.96mg/g is reached to the adsorbance of toluene.
Claims (8)
1. a kind of TiO2Modification of chitosan adsorbent, it is characterised in that the structural formula of the adsorbent are as follows:
Wherein n=20~30 are denoted as TiO2(KH-570)-g-(CS-GMA)。
2. a kind of TiO2The preparation method of modification of chitosan adsorbent, it is characterised in that method includes the following steps:
One, it is 1:(0.5~1.5 by the mass ratio of butyl titanate and 3- (methacryloxypropyl) propyl trimethoxy silicane)
Ratio weighs butyl titanate and and 3- (methacryloxypropyl) propyl trimethoxy silicane；
Two, by the ratio of the quality of butyl titanate and the volume of dehydrated alcohol be 1g:(22~25) mL, butyl titanate quality
The ratio of the volume for the hydrochloric acid for being 0.05mol/L with concentration is 1g:(19~22) ratio of mL, by weighed four fourth of metatitanic acid of step 1
Ester is charged first in dehydrated alcohol and is uniformly mixed, then hydrochloric acid is added dropwise under agitation, and after being added dropwise, stirring is obtained
Colloid TiO2；
Three, step 1 weighed 3- (methacryloxypropyl) propyl trimethoxy silicane is added to the colloid that step 2 obtains
TiO2In, dehydrated alcohol and deionized water are added, is heated to 40~60 DEG C, is stirred to react 0.5~2 hour, is washed out, does
It is dry, obtain TiO2(KH-570) intermediate；
Four, chitosan, glycidyl methacrylate, benzyltriethylammoinium chloride and toluene are weighed, wherein chitosan and first
The mass ratio of base glycidyl acrylate is 1:(1~1.2), the quality of benzyltriethylammoinium chloride accounts for chitosan and methyl-prop
The 7%~8% of olefin(e) acid ethylene oxidic ester gross mass；The ratio of the volume of the quality and toluene of chitosan is 1g:(20~25) mL；First
Chitosan, glycidyl methacrylate and toluene are uniformly mixed, 70~90 DEG C is warming up under agitation, adds
Benzyltriethylammoinium chloride is stirred to react 3~3.5 hours under conditions of 70~90 DEG C, obtains chitosan-methacrylic acid contracting
Water glyceride intermediate；It is indicated with CS-GMA；
Five, TiO is weighed2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate, azodiisobutyronitrile and
Toluene；Wherein TiO2(KH-570) intermediate and chitosan-glycidyl methacrylate intermediate mass ratio are 1:(1
~1.2)；The quality of azodiisobutyronitrile accounts for TiO2(KH-570) in intermediate and chitosan-glycidyl methacrylate
The 3%~3.5% of mesosome gross mass；TiO2(KH-570) ratio of the volume of the quality and toluene of intermediate is 1g:(40~50)
mL；By TiO2(KH-570) intermediate, chitosan-glycidyl methacrylate intermediate and toluene are uniformly mixed, and are being stirred
It is warming up to 75~85 DEG C under the conditions of mixing, adds azodiisobutyronitrile, is stirred to react under conditions of 75~85 DEG C 4~5 hours,
Obtain TiO2Modification of chitosan adsorbent, uses TiO2(KH-570)-g- (CS-GMA) is indicated.
3. a kind of TiO according to claim 22The preparation method of modification of chitosan adsorbent, it is characterised in that in step 2
Mixing speed is 200~300r/min, and mixing time is 25~35 minutes.
4. a kind of TiO according to claim 2 or 32The preparation method of modification of chitosan adsorbent, it is characterised in that step
The volume ratio of dehydrated alcohol and deionized water is 9:1, mixing speed 200r/min in three.
5. a kind of TiO according to claim 2 or 32The preparation method of modification of chitosan adsorbent, it is characterised in that step
Colloid TiO in three2Quality and deionized water volume ratio be 1g:1mL.
6. a kind of TiO according to claim 2 or 32The preparation method of modification of chitosan adsorbent, it is characterised in that step
The range of viscosities of chitosan described in four is 170~250mPas.
7. a kind of TiO described in claim 12The application of modification of chitosan adsorbent, it is characterised in that the application is by TiO2Change
Property chitosan absorbent is as the heavy metal and organic substance pollutant in absorbent absorption waste water.
8. a kind of TiO according to claim 72The application of modification of chitosan adsorbent, it is characterised in that concrete application method
It is: by TiO2Modification of chitosan adsorbent is added in the waste water containing heavy metal contaminants and organic substance, and ultrasonic disperse is uniform,
Then it stirs, filters, by TiO2Modification of chitosan adsorbent filters out, and completes the processing of the waste water containing heavy metal contaminants.
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