CN105854848A - Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof - Google Patents
Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof Download PDFInfo
- Publication number
- CN105854848A CN105854848A CN201610466774.2A CN201610466774A CN105854848A CN 105854848 A CN105854848 A CN 105854848A CN 201610466774 A CN201610466774 A CN 201610466774A CN 105854848 A CN105854848 A CN 105854848A
- Authority
- CN
- China
- Prior art keywords
- tetracycline
- graphene
- titanium nanotube
- composite aquogel
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J20/28—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
-
- 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
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides composite hydrogel on the basis of titanium nano-tubes and graphene. The composite hydrogel comprises the oxidized graphene and the titanium nano-tubes. The titanium nano-tubes are dispersed on the surface of the oxidized graphene. The invention further provides a method for preparing the composite hydrogel. The composite hydrogel and the method have the advantages that the method is easy and convenient to implement, raw materials for preparing the composite hydrogel are low in cost and are easily available, and accordingly the composite hydrogel is easy to industrially produce; organic solvents are omitted in preparation procedures, and participation and generation of pollutants are prevented; the composite hydrogel is high in tetracycline adsorbing capacity and good adsorptive selectivity and can be applied to the technical field of wastewater treatment.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of Self-Assembled adsorbent, can be applicable to tetracycline wastewater adsorption treatment, belong to waste water Treatment and recovery and utilize association area.
Background technology
Tetracycline, is called for short TC.According to statistics, late nineteenth century, the whole world reaches 3000 tons/year for the consumption figure raising pig and poultry.Its molal weight is 444.4g/mol, as veterinary medicine, is mainly used in prevention and the treatment of Acquired Infection, is treatment mycoplasma pneumoniae, Chlamydia pneumoniae and the choice drug of chlamydia pneumonia.In animal husbandry especially pig industry, it is often used as feed additive and anti-disease medicines, is used for promoting growth of animal and disease prevention.
After tetracycline is once taken in by animal, only small part is existed with unchanged parent compound and metabolic intermediate form thereof by human and animal's metabolism and absorption, major part, is excreted in vitro by urine and feces.From agricultural runoff and municipal sewage plant water outlet, the TC of residual generally can be detected.
Being widely used of antibiotic has become as a serious problem, because in use, there is many and plant potential side effect, the normal activities including acute and chronic toxicity, affect aquatic photosynthetic organism, destroy intrinsic microbial population and in microcomputer body propagation antibiotic resistance gene., Science Institute proves, present in water environment, TC can destroy microorganism respiratory in soil, interrupt ferric iron back reaction, upset nitration reaction and phosphatase activity.
According to up-to-date nearly 5 years document reports, use common water technology, be difficult to thoroughly remove the TC in water.In order to thoroughly solve this difficult problem, scientist explores and have studied the different materials absorption property to antibiotic tetracycline, and material includes montmorillonitic clay, montmorillonite, rectorite, Paligorskite, chitosan particle, aluminium oxide, humic acid, activated carbon and SWCN and multi-walled carbon nano-tubes.But, the demand of TC efficient absorption, the development of Treatment process with low cost is increased the most day by day.
According to recent five years foreign study, removing TC method mainly has: (1) MnFe2O4/ activated carbon magnetic material, maximal absorptive capacity 590mmol/kg(262mg/g), the saturated rear desorption rate of adsorbent reaches 25%；(2) using carbon nanotube adsorption, maximal absorptive capacity reaches 1000mmol/kg(444mg/g), adsorb saturated after adsorbent, it is impossible to be desorbed, thus the absorbability that restorer is to TC；(3) with Graphene adsorb, maximal absorptive capacity reaches 704mmol/kg(313mg/g), adsorb saturated after adsorbent, be difficult to the TC being adsorbed onto on adsorbent surface is carried out desorption process, cannot be recovered it the most after a procedure to TC absorbability.
Therefore develop the adsorbent that a kind of adsorbance is big and adsorptive selectivity is high, be used for removing the TC of water middle and high concentration or low concentration, there is significant Research Prospects.
Summary of the invention
The present invention is to solve drawbacks described above and deficiency present in prior art, it is provided that a kind of based on titanium nanotube with the composite aquogel of Graphene, preparation method and application.
For solving above-mentioned technical problem, the present invention provides a kind of based on titanium nanotube with the composite aquogel of Graphene, and including graphene oxide and titanium nanotube, described titanium nanotube is dispersed on the surface of described graphene oxide.
Further, the concentration of described graphene oxide is 2-3.5mg/ml, and the concentration of titanium nanotube is 0.5-1.5mg/ml.
Based on titanium nanotube and the preparation method of the composite aquogel of Graphene, comprise the following steps:
Step one, by graphite oxide, is dissolved in the water, supersound process 36-48 hour, obtains the graphene oxide solution of 2-3.5mg/ml, stand-by；
Step 2, adds titanium nanotube in the graphene oxide solution that step one obtains, and the concentration of titanium nanotube is 0.5-1.5mg/ml, then supersound process 36-48 hour, obtains titanium nanotube-graphene oxide mixed solution；
Step 3, the titanium nanotube that removing step two obtains-graphene oxide mixed solution 10ml, add the vitamin c solution 0.5ml that concentration is 40mg/ml, stir 3-4 minute；
Step 4, by the mixed solution of step 3 insulation reaction 6-8 hour in the water bath with thermostatic control of 85-90 DEG C, obtains titanium nanotube-graphene oxide hydrogel.
Composite aquogel based on titanium nanotube and Graphene is the application of tetracycline in removing waste water, comprises the following steps:
Step one, makes the standard curve of tetracycline；
Step 2, sets adsorption conditions, is equipped with by composite aquogel in the sample bottle of tetracycline wastewater solution, by sample bottle bottle sealing, is then placed in temperature and is 25 DEG C, in the constant-temperature table of selection of speed 160rpm, after 12 hours, measures absorbance at 357nm；
Step 3, calculates according to standard curve, absorbance is scaled concentration, thus draws the composite aquogel adsorbance to tetracycline, and then determine the hydrogel optimal adsorption condition to tetracycline.
Further, in step 2, adsorption conditions includes the initial concentration of tetracycline, pH value and salinity in waste water solution.
Further, when hydrogel used is 20mg, in waste water solution, the initial concentration of tetracycline is 500
During mg/L, hydrogel is maximum to the adsorbance of the tetracycline in waste water.
Further, pH value is 2-12.
Further, salinity is 20-100 mmol/L.
The Advantageous Effects that the present invention is reached: the present invention provide based on titanium nanotube and Graphene composite aquogel, its preparation method is easy and simple to handle, preparation low raw-material cost be easy to get, it is easy to industrialization go into operation；And preparation process does not use organic solvent, contamination-free is participated in and is produced；The composite aquogel that the present invention provides, big to tetracycline adsorbance and that adsorptive selectivity is good feature, can be applicable to technical field of waste water processing, the absorption principle of tetracycline is by it: surface of graphene oxide has abundant carboxyl and hydroxyl, can react with the amino on TC surface.Additionally, TC molecular structure has four hexatomic rings, one of them is phenyl ring, phenyl ring and and between Graphene, by the effect of pi-pi bond, TC firmly can be adsorbed at graphenic surface.In addition, hydroxyl on TC phenyl ring, belong to electron donating group, phenyl ring cloud density is increased, and titanium nanotube TN is positively charged nanotube, mixed in graphene oxide, the positive charge in TN structure can with TC/in electron cloud send out electrostatic attraction effect upper, can largely improve the composite absorbability to TC.
Accompanying drawing explanation
The titanium nanotube of Fig. 1 present invention and Graphene composite aquogel transmission electron microscope figure；
The titanium nanotube of Fig. 2 present invention and Graphene composite aquogel Raman spectrum collection of illustrative plates；
The titanium nanotube of Fig. 3 present invention and Graphene composite aquogel X-X-ray photoelectron spectroscopy X spectrogram；
The titanium nanotube of Fig. 4 present invention and the Graphene composite aquogel adsorption isotherm to tetracycline；
The salinity of Fig. 5 present invention is to titanium nanotube and the influence curve figure of Graphene composite aquogel tetracycline adsorption；
The pH value of Fig. 6 present invention is to titanium nanotube and the influence curve figure of Graphene composite aquogel tetracycline adsorption；
The titanium nanotube of Fig. 7 present invention and Graphene composite aquogel reach tetracycline to adsorb saturated after desorption curve figure；
The grain size distribution of the graphene oxide of the variable concentrations of Fig. 8 present invention；
Composite aquogel prepared by the titanium nanotube of the variable concentrations of Fig. 9 present invention adsorption isothermal curve to tetracycline.
Detailed description of the invention
The invention will be further described below in conjunction with the accompanying drawings.Following example are only used for clearly illustrating technical scheme, and can not limit the scope of the invention with this.
The present invention provides a kind of based on titanium nanotube with the composite aquogel of Graphene, and including graphene oxide and titanium nanotube, described titanium nanotube is dispersed on the surface of described graphene oxide.Wherein, the concentration of described graphene oxide is 2-3.5mg/ml, and the concentration of titanium nanotube is 0.5-1.5mg/ml.
nullDue to，In composite aquogel，Titanium nanotube is dispersed on the surface of graphene oxide，Therefore，The particle diameter of composite aquogel depends on the particle diameter of graphene oxide，Therefore，Before preparing titanium nanotube and Graphene composite aquogel，First the particle diameter of graphene oxide is screened，Concrete operations are as follows: accurately weigh in graphene oxide and the beaker of different quality，It is subsequently adding deionized water，Room temperature ultrasonic agitation 36-48 hour，Obtain concentration and be respectively 2、2.5、The graphene oxide solution of 3mg/ml and 3.5mg/ml，The particle diameter distribution of the graphene oxide solution of variable concentrations tested respectively by employing potentiometric analysis instrument，As shown in Figure 8，As can be seen from Figure，Graphene oxide concentration is 3.5mg/ml、Ultrasonic agitation 36 is little constantly，The graphene oxide particle diameter obtained is distributed in about 10nm，The particle diameter of the graphene oxide solution of remaining concentration is about 20nm.Owing to the particle diameter of graphene oxide is the least, its surface area is the biggest, can be the best to the adsorption effect of tetracycline, therefore, as preferred technical scheme, the graphene oxide selecting ultrasonic agitation 36 hours, concentration to be 3.5mg/ml is best to the adsorption effect of tetracycline to prepare titanium nanotube and Graphene composite aquogel.
Embodiment
1
Accurately weigh graphene oxide, in 500ml beaker, add 400ml deionized water, room temperature ultrasonic agitation 36-48 hour, it is thus achieved that concentration is the graphene oxide solution of 2-3.5mg/ml；Titanium nanotube is added so that the concentration of titanium nanotube is 0.5mg/ml, the most ultrasonic 36-48 hour, it is thus achieved that titanium nanotube-graphene oxide mixed solution in graphene oxide solution；Liquid-transfering gun is used accurately to pipette in titanium nanotube-graphene oxide mixed solution 10ml and beaker, it is subsequently adding the vitamin c solution 0.5ml that concentration is 40mg/ml, ultrasonic agitation 3-4 minute, beaker puts into insulation reaction 6-8 hour in 85-90 DEG C of water bath with thermostatic control after sealing, obtain titanium nanotube and Graphene composite aquogel, write a Chinese character in simplified form H-TN-GO.
Embodiment
2
Process is same as in Example 1, and simply the concentration of titanium nanotube is different, by the concentration of titanium nanotube by 0.5
Mg/ml becomes 1 mg/ml.
Embodiment
3
Process is same as in Example 1, and simply the concentration of titanium nanotube is different, by the concentration of titanium nanotube by 0.5
Mg/ml becomes 1.5 mg/ml.
Composite aquogel embodiment 3 prepared is freezing 8 hours in freeze drying equipment, are dried 24 hours, it is thus achieved that titanium nanotube and the pressed powder of Graphene composite aquogel under vacuum the most again, are called for short aeroge A-TN-GO.Then characterizing aeroge A-TN-GO, as Figure 1-3, wherein, Fig. 1 is transmission electron microscope (TEM) photo, and Fig. 2 is Raman spectrum (Ramman) collection of illustrative plates, and Fig. 3 is X-X-ray photoelectron spectroscopy X (XPS) spectrogram.From figure 1 it appears that graphene dispersion is effective, and titanium nanotube is dispersed in graphene platelet；From figure 2 it can be seen that its D peak at 1349 cm-1 and 1578 cm-1The Jun Chu peak, G peak at place, composes peak position with the Graphene Ramman light of report in existing document consistent, illustrates that, after Doped with Titanium nanotube, the structure of Graphene does not change；In Fig. 3, a is that the XPS of composite aquogel always schemes, and b is C1SCracking peak, c is Ti2p
Cracking peak, it can be seen that the combination of carbon can be 284.5 eV, 285.5 eV and 287.8 eV, the combination of titanium elements can be 458.5 eV and 464.5 eV, matches with document report, illustrates that titanium nanotube has been supported as in graphene-structured.
Embodiment
4
The composite aquogel 20mg above-mentioned 3 embodiments prepared is in sample bottle, be subsequently adding tetracycline concentration be respectively 50,100,200,300,400, in the waste water solution of 500mg/L, after sample bottle sealing, sample bottle is put into temperature be 25 DEG C, cyclotron frequency be 160rpm constant-temperature table in 12 hours, measure absorbance at 357nm；Standard curve c=35.468A-0.0493 according to tetracycline, wherein, a is tetracycline concentration, and unit is mg/L；A is absorbance, calculate after absorption the concentration of tetracycline in waste water solution, thus draw the composite aquogel adsorbance to tetracycline, and the adsorption isothermal curve that the composite aquogel prepared of the titanium nanotube making variable concentrations is to tetracycline, as shown in Figure 9, it can be seen that when the concentration of titanium nanotube is 1.5mg/ml, hydrogel reaches maximum to the adsorbance of tetracycline.
Embodiment
5
Hydrogel 20mg embodiment 3 prepared is in sample bottle, be subsequently adding tetracycline concentration be respectively 50,100,200,300,400, in the waste water solution of 500mg/L, after sample bottle sealing, sample bottle is put into temperature be 25 DEG C, cyclotron frequency be 160rpm constant-temperature table in 12 hours, measure absorbance at 357nm；Standard curve c=35.468A-0.0493 according to tetracycline, wherein, a is tetracycline concentration, and unit is mg/L；A is absorbance, calculate after absorption the concentration of tetracycline in waste water solution, thus draw the composite aquogel adsorbance to tetracycline, and produce the adsorption isotherm of composite aquogel tetracycline adsorption, as shown in Figure 4, it can be seen that when the initial concentration of tetracycline is less than 4.06 less than 50 mg/L, last equilibrium concentration
Mg/L, and TC removal efficiency is higher than 91.87
%, along with the raising of initial concentration, equilibrium adsorption capacity is stepping up, and when initial concentration reaches 500 mg/L, hydrogel reaches maximum, for 680mg/g to the adsorbance of TC.
Embodiment
6
Accurately weigh the sodium chloride of different quality to be dissolved separately in and be respectively 100 mg/L equipped with concentration, 200 mg/L, 400mg/L, volume is in the sample bottle of the tetracycline of 40ml, ultrasonic mixing 5-10 minute, make the abundant solution of sodium chloride, wherein the concentration of sodium chloride is respectively 20mmol/L, 40mmol/L, 60mmol/L, 80mmol/L, 100 mol/L, hydrogel 20mg embodiment 3 prepared adds in above-mentioned solution, after sample bottle sealing, it is 25 DEG C that sample bottle is put into temperature, cyclotron frequency be 160rpm constant-temperature table in 12 hours, measure absorbance at 357nm；Standard curve c=35.468A-0.0493 according to tetracycline, wherein, a is tetracycline concentration, and unit is mg/L；A is absorbance, calculate after absorption the concentration of tetracycline in waste water solution, thus draw the composite aquogel adsorbance to tetracycline, and make salinity to titanium nanotube and the influence curve figure of Graphene composite aquogel tetracycline adsorption, as it is shown in figure 5, it can be seen that when TC concentration less than 200mg/L time, when salinity is not more than 100mmol/L, the Adsorption Effect of TC can be ignored by salinity；When salinity is more than 60mmol/L, salinity is adsorbed with a certain degree of impact to the TC of 400mg/L.
When the initial concentration of tetracycline is less than 200mg/L when, the Na of 20～100mmol/L+Concentration is difficult to affect the absorbability of hydrogel tetracycline adsorption.When the initial concentration of tetracycline reaches 400 mg/L when, due to, join the NaCl in tetracycline, the absorbability of hydrogel tetracycline adsorption is affected by electrostatic repulsion, increase ionic strength, inhibit the mutual electrostatic interaction between the charged amino group on tetracycline and the deprotonation carboxylic group on graphene oxide, electrical charge rejection effect is there occurs between surface charge, the effect making cation-π key is weakened, and therefore the absorbability of hydrogel can drop to 472 mmol/Kg from 1193 mmol/Kg.
Embodiment
7
Hydrogel 20mg prepared by embodiment 3, it is equipped with in the sample bottle of tetracycline wastewater solution of different PH, wherein pH value is 2-12, the concentration of tetracycline is respectively 100mg/L, 400mg/L, volume is 40ml, after sample bottle sealing, sample bottle is put into temperature be 25 DEG C, cyclotron frequency be 160rpm constant-temperature table in 12 hours, measure absorbance at 357nm；Standard curve c=35.468A-0.0493 according to tetracycline, wherein, a is tetracycline concentration, and unit is mg/L；A is absorbance, calculate after absorption the concentration of tetracycline in waste water solution, thus draw the composite aquogel adsorbance to tetracycline, and make pH value to titanium nanotube and the influence curve figure of Graphene composite aquogel tetracycline adsorption, as shown in Figure 6, as can be seen from the figure, pH value is had the strongest according to lazyness in the range of pH is 3～12 by the ability of composite aquogel tetracycline adsorption: as pH=6～7, initial concentration is 100 mg/L and the tetracycline of 400 mg/L, its absorbability can reach maximum, and respectively 535.2
Mmol/kg and 975.7 mmol/kg；When pH value of solution is 12, its absorbability is minimum, and corresponding adsorbance is respectively 377.2 mmol/kg and 407.9 mmol/kg.
PH is the most relevant with the existence of the molecular structure of tetracycline and composite aquogel surface functional group on the impact of composite aquogel tetracycline adsorption, includes pi-pi bond and interacts and cation-π key effect.There is abundant oxygen-containing functional group on composite aquogel surface so that it is surface is electronegative.Fourth Ring have several polarization or ionizable gene, including amino, carboxyl and carbonyl.Tetracycline has three ionization constant (pKa=3.3,7.7 and 9.7), under the conditions of acid, appropriateness acidity arrive neutrality, alkalescence, it exists as cation, amphion and anionic species state.Particularly C in amido functional group, tetracycline4Ring has amino group (pKa=9.7), it is easier to be protonated.Containing amino and enol group in tetracycline molecule,
Carboxylic group on H-TN-GO, along with the raising of pH, above-mentioned group is easier to by deprotonation.Increasing pH value, these groups are by deprotonation so that connect nucleophobic ability and drastically decline, finally inhibit the cation-π key of graphene oxide and pi-pi bond interphase interaction.
nullTitanium nanotube that the present invention provides and Graphene composite aquogel is used to remove in waste water in the application of tetracycline，The feature that its adsorbance is big and adsorptive selectivity is good，Can be applicable in technical field of waste water processing，And，Composite aquogel can reuse，Hydrogel absorbability after desorption the most substantially reduces，Now by embodiment 5，Tetracycline initial concentration is the waste water solution of 500mg/L，Dehydrated alcohol is used to be desorbed after reaching adsorption equilibrium，And make the tetracycline that hydrogel adsorption concentration is 500mg/L after desorption，So 6 times repeatedly，Result is as shown in Figure 7，As can be seen from the figure composite aquogel infiltrates 3 h in 10 mL ethanol solution，Can be with circular regeneration 20 mg composite aquogel，Show that composite aquogel has and has good reproducing characteristic，After this regenerative process can repeat to regenerate 6 times，And the absorbability of composite aquogel will not be weakened.Result shows that the saturated extent of adsorption of composite aquogel tetracycline adsorption is about 690 mg/g, the hydrogel after 6 circular regenerations, and the loss of its absorbability is less than 10 %.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, on the premise of without departing from the technology of the present invention principle; can also make some improvement and deformation, these improve and deformation also should be regarded as protection scope of the present invention.
Claims (8)
1. based on titanium nanotube and the composite aquogel of Graphene, it is characterised in that: including graphene oxide and titanium nanotube, described titanium nanotube is dispersed on the surface of described graphene oxide.
2. according to described in right 1 based on titanium nanotube and the composite aquogel of Graphene, it is characterised in that: the concentration of described graphene oxide is 2-3.5mg/ml, and the concentration of titanium nanotube is 0.5-1.5mg/ml.
3. according to described in any one of right 1-2 based on titanium nanotube and the preparation method of the composite aquogel of Graphene, it is characterised in that comprise the following steps:
Step one, by graphite oxide, is dissolved in the water, supersound process 36-48 hour, obtains the graphene oxide solution of 2-3.5mg/ml, stand-by；
Step 2, adds titanium nanotube in the graphene oxide solution that step one obtains, and the concentration of titanium nanotube is 0.5-1.5mg/ml, then supersound process 36-48 hour, obtains titanium nanotube-graphene oxide mixed solution；
Step 3, the titanium nanotube that removing step two obtains-graphene oxide mixed solution 10ml, add the vitamin c solution 0.5ml that concentration is 40mg/ml, stir 3-4 minute；
Step 4, by the mixed solution of step 3 insulation reaction 6-8 hour in the water bath with thermostatic control of 85-90 DEG C, obtains titanium nanotube-graphene oxide hydrogel.
4. according to the application of tetracycline in removing waste water of the composite aquogel based on titanium nanotube and Graphene described in any one of right 1-2, it is characterised in that comprise the following steps:
Step one, makes the standard curve of tetracycline；
Step 2, sets adsorption conditions, is equipped with by composite aquogel in the sample bottle of tetracycline wastewater solution, by sample bottle bottle sealing, be then placed in temperature be 25 DEG C, rotating speed choose in the constant-temperature table of 160rpm, after 12 hours, measure absorbance at 357nm；
Step 3, calculates according to standard curve, absorbance is scaled concentration, thus draws the composite aquogel adsorbance to tetracycline, and then determine the hydrogel optimal adsorption condition to tetracycline.
5. according to the application of tetracycline in removing waste water of the composite aquogel based on titanium nanotube and Graphene described in right 4, it is characterised in that: in step 2, adsorption conditions includes the initial concentration of tetracycline, pH value and salinity in waste water solution.
6. according to the application of tetracycline in removing waste water of the composite aquogel based on titanium nanotube and Graphene described in right 5, it is characterized in that: when hydrogel used is 20mg, when in waste water solution, the initial concentration of tetracycline is 500 mg/L, hydrogel is maximum to the adsorbance of the tetracycline in waste water.
7. according to the application of tetracycline in removing waste water of the composite aquogel based on titanium nanotube and Graphene described in right 5, it is characterised in that: pH value is 2-12.
8. according to the application of tetracycline in removing waste water of the composite aquogel based on titanium nanotube and Graphene described in right 5, it is characterised in that: salinity is 20-100
mmol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610466774.2A CN105854848A (en) | 2016-06-23 | 2016-06-23 | Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610466774.2A CN105854848A (en) | 2016-06-23 | 2016-06-23 | Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105854848A true CN105854848A (en) | 2016-08-17 |
Family
ID=56655431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610466774.2A Pending CN105854848A (en) | 2016-06-23 | 2016-06-23 | Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854848A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11517023B2 (en) | 2019-09-09 | 2022-12-06 | Imam Abdulrahman Bin Faisal University | Device and method for antibiotic removal from dairy products |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002331237A (en) * | 2001-05-09 | 2002-11-19 | Toray Ind Inc | Adsorbing material |
| CN104107681A (en) * | 2014-06-18 | 2014-10-22 | 同济大学 | Preparation method of three-dimensional graphene-protein composite aerogel |
| CN105170085A (en) * | 2015-09-18 | 2015-12-23 | 同济大学 | Method for preparing three-dimensional graphene hydrogel of loaded anatase type titanium dioxide nanotube |
| CN105582891A (en) * | 2016-02-03 | 2016-05-18 | 上海应用技术学院 | Preparation method of three-dimensional modified carbon nano tube graphene composite adsorption material for removing tetracycline from water solution |
| CN105642236A (en) * | 2016-02-03 | 2016-06-08 | 上海应用技术学院 | Method for preparing graphene and carbon nano tube compounded adsorbing material for removing tetracycline in water solution |
-
2016
- 2016-06-23 CN CN201610466774.2A patent/CN105854848A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002331237A (en) * | 2001-05-09 | 2002-11-19 | Toray Ind Inc | Adsorbing material |
| CN104107681A (en) * | 2014-06-18 | 2014-10-22 | 同济大学 | Preparation method of three-dimensional graphene-protein composite aerogel |
| CN105170085A (en) * | 2015-09-18 | 2015-12-23 | 同济大学 | Method for preparing three-dimensional graphene hydrogel of loaded anatase type titanium dioxide nanotube |
| CN105582891A (en) * | 2016-02-03 | 2016-05-18 | 上海应用技术学院 | Preparation method of three-dimensional modified carbon nano tube graphene composite adsorption material for removing tetracycline from water solution |
| CN105642236A (en) * | 2016-02-03 | 2016-06-08 | 上海应用技术学院 | Method for preparing graphene and carbon nano tube compounded adsorbing material for removing tetracycline in water solution |
Non-Patent Citations (3)
| Title |
|---|
| 常阳等: "钛纳米管的制备和对铀离子的吸附", 《材料研究学报》 * |
| 肖蓝灯: "石墨烯及其复合材料在水处理中的应用", 《化学进展》 * |
| 谢昆: "《纳米技术在水污染控制中的应用》", 30 June 2014, 武汉大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11517023B2 (en) | 2019-09-09 | 2022-12-06 | Imam Abdulrahman Bin Faisal University | Device and method for antibiotic removal from dairy products |
| US11659846B2 (en) | 2019-09-09 | 2023-05-30 | Imam Abdulrahman Bin Faisal University | Separation column containing titanium oxide nanotubes |
| US11659847B2 (en) | 2019-09-09 | 2023-05-30 | Imam Abdulrahman Bin Faisal University | Dairy purification mixture |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Amino-functionalized biomass-derived porous carbons with enhanced aqueous adsorption affinity and sensitivity of sulfonamide antibiotics | |
| Wang et al. | Adsorption of antibiotics from water by using Chinese herbal medicine residues derived biochar: Preparation and properties studies | |
| Gong et al. | A review of pristine and modified biochar immobilizing typical heavy metals in soil: applications and challenges | |
| Zhou et al. | Single and simultaneous adsorption of pefloxacin and Cu (II) ions from aqueous solutions by oxidized multiwalled carbon nanotube | |
| Sun et al. | Graphene oxide-facilitated transport of levofloxacin and ciprofloxacin in saturated and unsaturated porous media | |
| CN101818140B (en) | Immobilization pseudomonas aeruginosa as well as preparation method and application thereof | |
| Li et al. | Competitive adsorption of tylosin, sulfamethoxazole and Cu (II) on nano-hydroxyapatitemodified biochar in water | |
| CN101805037B (en) | Method for removing humic acid pollutants in water by magnetic chitosan particle | |
| Sayin et al. | From green biowaste to water treatment applications: Utilization of modified new biochar for the efficient removal of ciprofloxacin | |
| CN103523849B (en) | The methods and applications of sulfamethoxazole in a kind of straw charcoal Adsorption water body | |
| Zhang et al. | Removal of Cd (II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems | |
| CN105754984B (en) | Compound immobilized microbial inoculum of sodium alginate and preparation method thereof and purposes | |
| WO2023065752A1 (en) | Preparation method for and use of clay/tannic acid/metal ion composite material for efficiently adsorbing antibiotics | |
| CN103691411A (en) | Formaldehyde adsorbent containing chitosan and beta-cyclodextrin and preparation method for formaldehyde adsorbent | |
| CN102774847A (en) | Preparation and application methods for novel magnetic molecular sieve adsorbent material | |
| CN104128161A (en) | Amino-modified active coke heavy metal adsorbent and preparation method thereof | |
| Chen et al. | Mechanisms underlying enhanced bioremediation of sulfamethoxazole and zinc (II) by Bacillus sp. SDB4 immobilized on biochar | |
| Mirizadeh et al. | Efficient removal of tetracycline, ciprofloxacin, and amoxicillin by novel magnetic chitosan/microalgae biocomposites | |
| CN105944684A (en) | Preparation method and application of oxidized graphene and magnetic chitosan compound | |
| CN106512933B (en) | A kind of while the adsorbent of adsorbing and removing carbamazepine and sulfamethoxazole preparation method | |
| CN107376857A (en) | It is a kind of to be used to adsorb compound hydrogel material of heavy metal and preparation method thereof | |
| Zhang et al. | Adsorption-reduction coupling mechanism and reductive species during efficient florfenicol removal by modified biochar supported sulfidized nanoscale zerovalent iron | |
| CN105854848A (en) | Composite hydrogel on basis of titanium nano-tubes and graphene, method for preparing composite hydrogel and application thereof | |
| Cela-Dablanca et al. | Simultaneous adsorption of amoxicillin and ciprofloxacin on agricultural soils and by-products used as bio-adsorbents: unraveling the interactions in complex systems | |
| CN102826607A (en) | Mesoporous zinc ferrite, preparation method thereof, and magnetic carbon nanotube prepared from same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160817 |